JP2001521996A - Fabric dipping method with liquid aqueous persulfate-containing composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a step of diluting a liquid aqueous composition in the form of a stock solution having a pH of less than 7 and containing a persulfate in an aqueous bath, wherein the fabric is added to the aqueous bath comprising the liquid composition. Contacting and then rinsing said fabric with water. The bleaching method is particularly safe for fabrics and fabric colors, while exhibiting effective bleaching performance and effective overall stain removal performance.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to bleaching fabrics with a liquid aqueous persulfate-containing bleaching composition having a pH of less than 7.

BACKGROUND OF THE INVENTION [0002] Liquid aqueous bleaching compositions suitable for laundry applications are known in the art. Bleaching compositions based on hypochlorite as a bleaching agent, especially for performance at low temperatures,
It is also known to be preferred over oxygen bleaches such as hydrogen peroxide.

[0003] However, the convenience of hypochlorite bleaches is limited. In particular, bleaching with hypochlorite can cause yellowing and / or damage to the bleached fabric,
Known from consumers. This is especially true for synthetic fabrics, and there is an old prejudice against the use of hypochlorite bleach in synthetic fabrics, as evidenced by the warnings on the label of commercially available hypochlorite bleach. . In addition, various fabrics made of or containing synthetic fibers are indicated by the manufacturer as not bleachable. Another drawback with hypochlorite-based compositions is that the undesired typical chlorine odor may occur during or after use, for example, in the hands of users or in fabrics bleached with such compositions. It is felt.

[0004] Color and fabric damage can be minimized by using milder oxygen bleaches such as persulfates. However, the bleaching properties of such peroxide bleaches are much less desirable than harsh halogen bleaches. Accordingly, liquid aqueous peroxide bleach-containing compositions have been developed that include an activator, a compound that improves peroxide bleaching properties. Such an activated hydrogen peroxide-containing composition is, for example, EP
-598 170. However, consumers are still not completely satisfied with bleaching fabrics with such compositions, and have improved overall stain removal performance against a variety of stains, including greasy and enzymatic stains, as well as bleaching. There is a need for improved bleaching performance.

Accordingly, it is an object of the present invention to address the above-mentioned problems, that is, providing improved overall stain removal performance for a wide range of stains and improved bleaching performance when bleaching fabrics. More specifically, it is an object of the present invention to provide effective overall stain removal and effective bleaching performance while being safe for the fabric and color being bleached.

The inventors have found that these problems are efficiently addressed when a soiled (colored) fabric is bleached with an acidic liquid aqueous composition containing persulfate (pH less than 7). Was. In fact, the fabric bleaching method according to the present invention comprises the steps of: diluting an acidic liquid aqueous composition containing persulfate in an aqueous bath, contacting said fabric with said aqueous bath comprising said composition, A composition comprising the same acidic liquid aqueous composition, but comprising hydrogen peroxide activated (eg, acetyltriethyl citrate) instead of persulfate, for example, when the fabric includes a water rinsing step. It has been found that the material exhibits improved overall stain removal performance as well as improved bleaching performance as compared to the same bleaching method used at the same overall bleach level.

Conveniently, the bleaching methods herein starting from the liquid aqueous persulfate-containing compositions described herein typically have less than 30 minutes, more preferably less than 10 minutes, and most preferably It provides effective bleaching performance and effective stain removal performance even under short immersion time conditions of less than 5 minutes. Further, the bleaching methods herein starting from the liquid persulfate-containing compositions described herein may be used in aqueous baths where the aqueous bath is cold, typically up to 4 ° C (preferably less than 40 ° C, most preferably 10 ° C To 30 ° C.) provides effective bleaching performance and effective stain removal performance. Accordingly, the present invention provides a fabric bleaching method that most needs today's consumer needs, i.e., a fabric bleaching method that provides effective bleaching and stain removal performance through reduced time and / or use of cold water. . In fact, an advantage of the fabric bleaching method herein is that the acidic liquid aqueous persulfate-containing composition herein is effective from the first moment of its dilution in an aqueous bath. This is because the composition dissolves rapidly in the aqueous bath.

[0008] Advantageously, these improved bleaching performance and improved overall stain removal performance are achieved with acidic liquid aqueous persulfate compositions that have been stored for a long period of time until used by the methods herein. Nevertheless, it is provided with the method according to the invention.

[0009] In a preferred embodiment of the fabric bleaching method according to the present invention, the acidic liquid aqueous composition used is further characterized by improved bleaching performance and improved stain removal performance.
Preferably, it comprises a bleach activator which is an aldehyde and / or ketone and / or halide activator compound in addition to the persulfate.

[0010] Advantageously, the laundry bleaching operation according to the invention is safe for the fabric itself and / or the color of the fabric. In fact, when the persulfate and optionally the activator compound are formulated into a liquid aqueous composition having a pH of less than 7, as described below, the safety exhibited by the bleached fabric by the method of the present invention ( It has been surprisingly found that fabric safety and color safety) are improved compared to formulating the same ingredients into a particulate composition.

Finally, the fabric bleaching method according to the invention has the advantage that there is no smell on the hands when the bleaching operation is performed manually and / or on the fabric to be bleached.

SUMMARY OF THE INVENTION The present invention is a method for bleaching a fabric, comprising diluting a liquid aqueous composition in the form of a stock solution comprising a persulfate having a pH of less than 7 in an aqueous bath, wherein the liquid Contacting the fabric with the aqueous bath comprising: then rinsing the fabric with water.

In the broadest aspect, the present invention relates to a method for bleaching a fabric, wherein the persulfate and optionally an aldehyde, ketone and / or halide having a pH of less than 7 to reduce the decrease in tensile strength of said fabric. Includes the use of a liquid aqueous bleach composition comprising a bleach activator, which is an activator. In addition, the present invention relates to a persulfate and optionally an aldehyde, ketone and / or halide activator having a pH of less than 7, for bleaching of colored fabrics, to reduce color damage to said fabrics. The use of a liquid aqueous bleaching composition comprising a bleach activator.

DETAILED DESCRIPTION Fabric Bleaching Method The present invention encompasses the fabric bleaching method described below.

“Fabric” is understood to mean any type of fabric, including, for example, clothes, curtains, hangers, linens for bedding, linens for bathrooms, tablecloths, sleeping bags, tents, stuffed furniture and the like.

The fabric bleaching method herein is suitable for both natural and synthetic fabrics. By "natural" fabric is meant a fabric made of cotton, viscose, linen, silk and / or wool. By "synthetic" fabrics is meant those made of synthetic fibers, such as polymeric fibers (polyamide, polyester, lycra® and elastane®), and those made of both natural and synthetic fibers. .

The method for bleaching a fabric according to the present invention comprises the steps of: diluting a liquid aqueous composition in the form of a stock solution having a pH of less than 7 and containing a persulfate in an aqueous bath; Contacting the aqueous bath with water, and then rinsing the fabric with water.

“Diluting a liquid composition in undiluted form in an aqueous bath” means herein that the liquid composition itself described herein is typically diluted with water and bleached. The fabric to form an aqueous bath that is contacted prior to rinsing.

In the fabric bleaching method of the present invention, the fabric is kept in contact with an aqueous bath for a time sufficient to bleach the fabric (a so-called “dipping step”). This time typically ranges from 1 minute to 24 hours, preferably 3 minutes to 12 hours, more preferably 4 minutes to 6 hours. Advantageously, the bleaching method according to the invention has a shorter soaking time, typically less than 1 hour, preferably less than 20 minutes, more preferably from 4 minutes to 1 minute.
An immersion time of 5 minutes still provides effective bleaching performance and effective stain removal performance.

The dilution level experienced by the liquid aqueous compositions described herein in the fabric bleaching method herein may be up to 500 times the weight of the composition, preferably 5 to 200 times, more preferably A dilution of the composition in water by a factor of 10 to 80. Such dilution occurs for example by hand washing applications as well as by other means such as a washing machine.

[0021] The temperature of the bleaching method affects the stain removal performance and / or bleaching performance of the liquid aqueous persulfate-containing composition composition used herein, but the effective stain removal performance and / or bleaching performance. Alternatively, bleaching performance is provided even at low temperatures, typically up to 4 ° C. More specifically, these benefits are seen not only at low temperatures, but also at shorter soak times, typically less than 20 minutes. It is also understood that by increasing the temperature, the bleaching process is accelerated, ie, the time required to bleach certain soiled fabrics is reduced. Typically, the aqueous bath produced in the bleaching process according to the invention, in which the persulfate bleaching compositions described herein are diluted, is from 4 ° C to 60 ° C, preferably from 10 ° C to 50 ° C, more preferably Has a temperature of 15 ° C to 30 ° C.

Surprisingly, the fabric bleaching method according to the present invention is characterized in that the bleaching composition used is the same bleaching agent as compared to the same method in which the activated aqueous hydrogen peroxide based liquid aqueous composition is used. At an overall level, it provides improved bleaching performance and improved overall stain removal performance. Also, these advantages are obtained with the fabric bleaching method according to the present invention in a cold or warm aqueous bath with short immersion times.

In fact, effective bleaching performance is provided for a variety of hydrophobic to hydrophilic bleachable stains on both hydrophilic and hydrophobic fabrics. Effective bleaching performance herein also includes effective whitening.

Advantageously, the present invention provides not only effective bleaching performance, but also greasy stains (eg, lipstick, tomato, cosmetics) and / or enzymatic stains (eg, blood, chocolate pudding).
It also provides effective stain removal performance for various types of stains, including.

When the fabric is washed, that is, when washed with a conventional laundry detergent composition comprising at least one surfactant, the washing may involve washing the fabric with a liquid aqueous solution as described herein. The bleaching of the fabric may be performed by simultaneously contacting the bleaching composition and the laundry detergent composition, or the washing may be performed before or after bleaching the fabric. Thus, the method according to the invention allows the bleaching of the fabric, while at the same time prior to the step of contacting said fabric with said aqueous bath comprising said liquid aqueous composition and / or contacting said fabric with said aqueous bath. A detergent composition, optionally comprising at least one surfactant during and / or after the step of contacting the fabric with the aqueous bath, prior to the rinsing step and / or after the rinsing step. To wash the fabric.

In a preferred embodiment herein, the fabric is washed, preferably in a separate step from the bleaching step, for optimal bleaching and stain removal performance. In fact, if the bleaching and washing with the detergent composition are performed in the same step, the persulfate coming from the liquid aqueous composition and the conventional detergent components typically present in the conventional detergent composition, i.e. enzymes, surfactants, etc. Can cause chemical interactions, which can reduce bleaching performance and / or overall stain removal performance.

In a highly preferred embodiment of the present invention, it is preferred that the fabric is first washed with a conventional laundry detergent composition before performing the bleaching method herein. Indeed, when the fabric is washed with a detergent composition and then bleached with the composition according to the present invention, the superior bleaching and stain removal performance is less than when the fabric is first bleached and then washed, with less energy and Supplied in detergent.

In fact, when the fabric is washed with a conventional detergent composition, residual alkalinity remains on the fabric even if the fabric is subsequently rinsed with water. Such alkaline residues on the fabric further increase the bleaching and stain removal performance of the acidic liquid aqueous persulfate composition described herein when the composition contacts the fabric in a dilute form of the composition. It is thought to cause.

When bleaching a fabric according to the present invention using a liquid aqueous composition comprising a persulfate and optionally a bleach activator composition, reduced color damage (ie, discoloration and / or discoloration)
Or bleaching) and reduced loss of tensile strength was further observed.

[0030] The composition may be combined with the acidic liquid aqueous composition described below with reduced tensile strength loss and reduction, even if the fabric is left soaked for an extended period of time, eg, 24 hours, prior to rinsing. Damaged color is observed. In fact, formulating the persulfate and optionally the bleaching activator in a liquid aqueous composition having a pH of less than 7 will require a bleach sensitive dye and / or a bleach sensitive dye if the fabric is bleached by the methods described herein. Prevents the decomposition (oxidation) of dyes commonly present on the surface of colored fabrics, such as metallized dyes, including copper-formazan dyes and / or metal-azo dyes.

For example, typical problems associated with particulate persulfate-containing compositions known in the art (
For example, see US 3822114) is a fabric and color damage associated with residual persulfate that slowly dissolves in an aqueous bath obtained by diluting such a composition with water. When preparing an aqueous bath (immersion bath) with a slowly dissolving particulate persulfate-containing composition, the prolonged mixing of the particulate form of the persulfate with the fabric without the agitation that typically occurs with hand-wash immersion. May cause contact. Accordingly, an advantage of the present invention is that the rapid dissolution of the liquid aqueous composition used herein reduces fabric and color damage typically associated with the use of particulate persulfate-containing compositions. It is.

The tensile strength of the fabric can be measured by pulling the fabric until it breaks. The force required to break the fabric is the "extreme tensile stress", which can be measured by a stress-strain INSTRON (trade name) machine commercially available from INSTRON. Loss in tensile strength is the difference between the tensile strength of the fabric to be referenced, eg, unbleached fabric, and the same fabric after bleached with the composition of the present invention. Zero loss in tensile strength means that no damage to the fabric is observed.

[0033] Color safety can be assessed visually by comparing side by side fabrics soaked in the composition of the present invention and the reference composition. Color differences and grading are assessed visually and classified by a panel score unit (PSU) using a suitable scale. P
SUs can be treated statistically using conventional techniques. Alternatively, various types of optics and procedures can be used to evaluate the improved color safety provided by the present invention. For example, when evaluating the color safety of a fabric, Hunterlab
Measurements using a color Quest 45/0 instrument are available.

An advantage of the persulfate-containing composition suitable for use in the fabric bleaching method according to the present invention is that it is physically and chemically stable during long-term storage.

The chemical stability of these compositions can be evaluated by measuring the concentration of available oxygen at a particular storage time after the composition is made. “Chemically stable”
As used herein, a composition herein comprising a persulfate or a mixture thereof and optionally an activator compound is subject to more than 15%, preferably more than 10% AvO loss per month at 25 ° C. Means not.

[0036] The loss of available oxygen (AvO) of the persulfate-containing composition can be measured by titration with potassium permanganate after reduction with an ammonium iron sulfate solution. Said stability test methods are known in the art and are, for example, Cur available from Interox.
ox (product name) is reported in the technical information sheet. Alternatively, a chromatographic method described in the literature on peracids (F. Di Furia et. Al.
, Gas-liquid Chromatography Method fo
r Determination of Peracids, Analyst,
Vol. 113, May, 1988, p. 793-795) can be used to measure the persulfate concentration.

“Physically stable” as used herein means that no phase separation occurs in the acidic liquid aqueous persulfate-containing composition used herein for a period of 7 days at 50 ° C. means.

Liquid Aqueous Composition Used in the Fabric Bleaching Method The liquid persulfate-containing composition used in the fabric bleaching method according to the present invention is not a solid or gas, but a liquid composition. "Liquid" as used herein includes "pasty" compositions. These liquid compositions herein are aqueous compositions. These liquid compositions according to the invention have a content of less than 7, preferably 0.1 to 6
, More preferably from 0.5 to 4, even more preferably from 1 to 3, most preferably from 1 to 2. Formulating these compositions in the acidic pH range is critical to the chemical stability of these compositions when stored for extended periods before use in the fabric bleaching method according to the present invention.

The pH of these compositions may be adjusted with any acidifying or alkalizing agent known to those skilled in the art. Examples of acidifying agents are organic acids such as citric acid and inorganic acids such as sulfuric acid, sulfonic acid and / or methanesulfonic acid. Examples of alkalinizing agents are sodium hydroxide, potassium hydroxide and / or sodium carbonate.

Persulfate The liquid aqueous composition used in the fabric bleaching method according to the present invention comprises, as an essential element, a persulfate or a mixture thereof.

Suitable persulfates include alkali metal persulfates, including sodium and / or potassium persulfate. Preferred persulfates to be used herein are
Monopersulfate. Examples of commercially available monopersulfates include Interox under the trade name Curox (trade name) and D under the trade name Caroat (trade name).
Some are sold by DuPont under the trademark Oxone (trade name) from Egussa. When commercially available Curox (trade name), Caroat (trade name) and / or Oxone (trade name) are used, the weight percentage of persulfate referred to herein is the aforementioned Curox (trade name), Caroat. (Product name)
And / or with respect to the overall weight of Oxone®. The activity concentration is about 1/2 of the total weight. Especially Peroxide
Other persulfates such as dispersulfate commercially available from Chemie GMBH include:
It can be used in the composition according to the invention. Another suitable persulfate is ammonium persulfate.

Typically, the liquid composition used in the fabric bleaching method according to the present invention comprises from 0.01% to 50%, preferably from 0.5% to 20%, based on the total weight of the composition. Preferably it comprises 1% to 15%, most preferably 2% to 10% of said persulfate or a mixture thereof.

Optional Ingredients The liquid aqueous persulfate-containing composition used in the fabric bleaching method according to the present invention further comprises a bleach activator compound, a surfactant, a chelating agent, a radical scavenger, an antioxidant, other stabilizers, Various optional ingredients such as builders, soil suspending agents, polymeric soil release agents, catalysts, dye transfer agents, solvents, foam inhibitors, brighteners, fragrances, pigments, dyes, etc., may be included.

Bleach activators Suitable bleach activators for use in these liquid persulfate-containing compositions include aldehyde activator compounds, ketone activator compounds, halide activator compounds or mixtures thereof.

As used herein, the term “aldehyde” refers to any compound containing at least one carbonyl group and containing two hydrogen atoms or a carbon atom and a hydrogen atom directly bonded to at least one of the carbonyl carbon atoms. I do.

As used herein, “ketone” includes at least one carbonyl group,
Any compound containing at least two carbon atoms directly attached to one of the carbonyl carbon atoms is meant.

These compounds may be aliphatic or aromatic, substituted or unsubstituted, saturated or unsaturated, acyclic, carbocyclic or heterocyclic.

“Halide” means chlorinated, brominated and / or iodided.

As used herein, “activator” refers to an activated bleaching species that reacts with persulfate, ie, dioxirane (if the activator compound is a ketone or aldehyde) or hypohalogenite (if the activator compound is Ketones, aldehydes and halide compounds and mixtures thereof, if they are halides. These activation mechanisms are known in the art and are described, for example, in US Pat. No. 3,822,114.

Advantageously, the bleaching performance and overall stain removal performance are further improved when the liquid aqueous composition used in the fabric bleaching method herein further comprises such a bleach activator. It is the activated species, i.e., dioxirane and hypo, which are believed to significantly improve bleaching in the present invention over persulfate alone or other activated bleaching systems, such as hydrogen peroxide and acetyltriethyl citrate. It is a halogenite. These activation mechanisms predominantly coincide with the dilution of the compositions herein with water, and are accentuated by the pH jump associated with this dilution from the neutral to alkaline pH range (ie, above about 6). It is at such a pH that more dioxirane and / or hypohalogenite is generated, and thus the bleaching performance of the composition of the invention is significantly improved.

Aldehyde activator compounds suitable for use herein include chloral hydrate, acetaldehyde, butyraldehyde, benzaldehyde and / or 4-
There is trimethylammoniobenzaldehyde methyl sulfate. Particularly suitable aldehyde activator compounds for use herein are acetaldehyde, butyraldehyde and / or benzaldehyde, with acetaldehyde being most preferred. Aldehyde activator compounds are generally less preferred than ketone activator compounds because they can be oxidized during prolonged storage.

For example, acetaldehyde is commercially available from Aldrich.

Aliphatic ketone activator compounds suitable for use herein include acetoacetone, 2,3-hexanedione, trimethylammonioacetone nitrate, 5-
Diethylbenzylammonio 2-pentanone nitrate, 5-diethylmethylammonio 2-pentanone nitrate, methylpyruvate, diethylketomalonate, 3-hydroxy-2-butanone, acetol, hexachloroacetone, 2,
5-hexanedione, phenylacetone, ethyl levulinate, 3-hydroxy-2-pentanone, acetone, 3-penten-2-one, methyl ethyl ketone,
4-hydroxy-3-methyl-2-butanone, 3-pentanone and / or 2
-Heptanone is present.

For example, acetoacetone is commercially available from Aldrich under its chemical name.

Aromatic ketone activator compounds suitable for use herein include hydroxyquinoline, 4-acetyl-1-methylpyridinium nitrate, di-2-pyridyl ketone N-oxide, 2-acetylquinoxaline, -Acetyl-3-methylquinoxaline oxaline, di-2-pyridyl ketone, 6-acetyl-1,2,4-
Trimethylquinolinium nitrate, 8-hydroxyquinoline N-oxide, methylphenylglyoxalate, N-methyl-p-morpholinoacetophenone methyl sulfate, 3-acetylpyridine N-oxide, p-nitroacetophenone, m-nitroacetophenone, Sodium p-acetylbenzenesulfonate, p-acetylbenzonitrile, 3,5-dinitroacetophenone, 4-trimethylammonioacetophenone nitrate, 4-methoxy-3-nitroacetophenone, p-chloroacetophenone, p-diacetylbenzene, N- Methyl-
p-morpholinoacetophenone nitrate, phenacyltriphenylphosphonium nitrate, 2-acetylpyridine, 2-acetylpyridine N-oxide, 3
-Acetylpyridine, 4-acetylpyridine, 4-acetylpyridine N-oxide, 2,6-diacetylpyridine, 3-acetylpyridine N-oxide and / or
Or there is triacetylbenzene.

Suitable cyclic ketone activator compounds for use herein include cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 3-methylcyclohexanone, 4-ethylcyclohexanone, 4-t-butylcyclohexanone, 4,4-dimethylcyclohexanone, methyl 4-oxo-cyclohexanone carboxylate, sodium 4-oxo-cyclohexanone carboxylate, 2-trimethylammoniocyclohexanone nitrate, 4-trimethylammoniocyclohexanone nitrate, 3-oxo-cyclohexylacetic acid, cyclo Heptanone, 1,4-cyclohexadione, dehydrochloric acid, tropinone methonitrile, N-methyl-3-oxoquinuclidinium nitrate, cyclooctanone And / or cyclopentanone.

For example, cyclohexanone is commercially available from Aldrich under its chemical name.

Heterocyclic ketone activator compounds suitable for use in the present invention include 2,2,6
6-tetramethyl-4-piperidone hydrate, 1-methyl-4-piperidone N-oxide, N-carbethoxy-4-piperidone, tetrahydrothiopyran-4-one methnitrate, tetrahydrothiopyran-4-one S, There are S-dioxide, tetrahydrothiopyran-3-one S, S-dioxide and or 4-oxacyclohexanone.

All of the above examples of aldehydes and ketones are either commercially available or can be obviously synthesized by those skilled in the art having the teachings of the prior art. Gardini
Other J. Chem. Soc. (C), (1970) page 929 and Lyl
e. Org. Chem. , Vol. 24 (March, 1959), pa
Ge 342 is an example of such a technique, which is incorporated herein by reference.
Further, a method for synthesizing an oxopiperidinium compound is described in "SE Denmark,
D. C. Forbes, D .; S. Hays, J.M. S. De Pue and R
. G. FIG. Wilde, J .; Org. Chem. 1995, 60, 1391-140
7 ".

[0060] Particularly preferred bleach activators for use herein are ketone activator compounds, with positively charged ketone activator compounds being highly preferred.

Particularly preferred positively charged ketone activator compounds are, for example, oxopiperidinium salts having the formula:

[0062]

Embedded image

In the above formula, the carbonyl group> C ＝ O is 2,3 or 4 of oxopiperidinium
R1 and R2 each independently represent a substituted or unsubstituted hydrocarbon chain having 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. a substituted or unsubstituted alkyl or alkenyl or alkynyl group containing, be a C1-C20 alkylaryl group including substituted or unsubstituted aryl group or a carbon atom of an aryl group of 6 to 12, including 6 to 12 atoms; X ^- May be any anion, such as triflate, tosylate, mesylate, nitrate, more preferably triflate, mesylate, tosylate, most preferably triflate, and the oxopiperidinium ring has 2,2
At the 3,5 or 6 position, of the substituents defined for R1 or R2 above
It may be mono- or polysubstituted by one or more or halogen atoms.

Examples of oxopiperidinium salts particularly suitable for use herein include 1
, 1-dimethyl-3-oxopiperidinium nitrate, 1,1-dimethyl-4
-Oxopiperidinium triflate, 1,1-dimethyl-3-oxopiperidinium triflate, 1,1-dimethyl-4-oxopiperidinium nitrate, 1-benzyl-4-piperidone methnitrate, 1-t -Butyl-1-methyl-4-oxopiperidinium nitrate, 1- (4-dodecylbenzyl) 1-methyl-4-oxopiperidinium chloride, 3- (N-methyl-4-oxopiperidinium) -Propanesulfonate, 1-allyl-1-methyl-4-oxopiperidinium chloride, 1-methyl-1- (1-naphthyl-methyl) -4-
Oxopiperidinium chloride, 1-methyl-1-pentamethylbenzyl-4
-Oxopiperidinium chloride, N, N'-dimethyl-N, N'-phenylenedimethylene-bis (4-oxopiperidinium nitrate), 1-benzyl-1-methyl-4-oxopiperidinium triflate , 1-benzyl-1-methyl-3-oxopiperidinium triflate, 1-benzyl-1-methyl-4
-Oxopiperidinium nitrate, 1-dodecyl-1-methyl-4-oxopiperidinium nitrate, 1-octyl-1-methyl-4-oxopiperidinium nitrate, 1-nonyl-1-methyl- There is 4-oxopiperidinium nitrate or a mixture thereof.

Other positively charged ketone activator compounds suitable for use herein are:
For example, an ammonium acetophenone salt according to the following formula:

[0066]

Embedded image

In the above formula, the ammonium group is at the 2-, 3- or 4-position; R1, R2,
And R3 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted hydrocarbon group containing 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. An alkyl or alkenyl or alkynyl group, or a substituted or unsubstituted aryl group containing 6 to 10 atoms or a C1-C20 alkylaryl group containing 6 to 10 carbon atoms;
4 is a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably methyl or trifluoromethyl or trichloromethyl or tribromomethyl; ^- it may be a Yes become anions, for example triflate, tosylate, mesylate, a nitrate, in the benzene ring 2, 3 and / or 4-position, the above R1, R
It may be substituted by one or more of the substituents defined for 2 or R3 or a halogen atom.

As used herein, such ammonium acetophenone salts include 4-trimethylammonium acetophenone nitrate, 2-trimethylammonium acetophenone nitrate, 4-triethylammonium acetophenone mesylate, 3-trimethylammonium acetophenone mesylate And trihalogenated methyl phenyl ketones such as trifluoromethyl phenyl ketone, trichloromethyl phenyl ketone, tribromomethyl phenyl ketone or mixtures thereof.

[0069] As used herein, suitable halide activator compounds include chloride, bromide, iodide and mixtures thereof. Alkali metal chlorides are particularly preferred halide activator compounds for use herein. For example,
Sodium chloride is commercially available from Aldrich under its chemical name.

Typically, the compositions herein comprise up to 10%, preferably 0.05% to 5%, more preferably 0.1% to 2%, most preferably 10% by weight of the total composition. Preferably it comprises from 0.2% to 1.5% of said ketone, aldehyde and / or halide activator compound.

Surfactants Liquid persulfate-containing compositions suitable for use in the fabric bleaching methods herein include nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants And / or surfactants including amphoteric surfactants or mixtures thereof. Typically, these surfactants contain no functional groups that are oxidizable by persulfate or substantially hydrolysable at low pH.

Typically, the composition according to the invention comprises 0.01% by weight of the total composition
To 50%, preferably 0.1% to 30%, more preferably 0.2% to 10% of a surfactant or a mixture thereof.

Anionic surfactants suitable for use in the compositions herein include those of the formula ROS
O ₃ is water-soluble salts or acids of M, but in the above formulas, R is preferably C ₁₀ -C _{2 4} hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component, More preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium) or ammonium or substituted ammonium (eg, methyl-, dimethyl- and trimethylammonium) Cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine and triethylamine and the like Mixture, or the like). Typically, low wash temperatures (eg, about 5
_C.sub.12-16 alkyl chains are preferred (less than 0.degree. C.) and _C.sub.16-18 alkyl chains are preferred for high wash temperatures (eg, above about _50.degree . C.).

Other anionic surfactants suitable for use herein are RO (A)_mSO_Three A water-soluble salt or acid of M wherein R is C_Ten-C_{twenty four}Alkyl component
Unsubstituted C having_Ten-C_{twenty four}An alkyl or hydroxyalkyl group, preferably
Kuha C₁₂-C₂₀Alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈ Alkyl or hydroxyalkyl, A is ethoxy or propoxy
M is greater than zero, typically between about 0.5 and about 6, more preferably
Or between about 0.5 and about 3, wherein M is H or a cation, such as a metal cation
(Eg, sodium, potassium, lithium, calcium, magnesium, etc.)
, Ammonium or substituted ammonium cations. Alkyl ethoxylated sulfur
Acid salts as well as alkylpropoxylated sulfates are contemplated herein. Replace
Specific examples of the ammonium cation include methyl, dimethyl, and trimethyl.
Quaternary ammonium cations such as ammonium and tetramethylammonium
, Dimethylpiperidinium and ethylamine, diethylamine, triethyl alcohol
Cations derived from alkanolamines such as mine and mixtures thereof
There is. A typical surfactant is C₁₂-C₁₈Alkyl polyethoxylate (1.0
) Sulfate, C₁₂-C₁₈E (1.0) M), C₁₂-C₁₈Alkyl polyethoxy
Silate (2.25) sulfate, C₁₂-C₁₈E (2.25) M), C₁₂-C ₁₈ Alkyl polyethoxylate (3.0) sulfate, C₁₂-C₁₈E (3.0
) And C₁₂-C₁₈Alkyl polyethoxylate (4.0) sulfate, C₁₂ -C₁₈E (4.0) M), where M is conveniently selected from sodium and potassium.
Selected.

Other anionic surfactants particularly suitable for use herein are those of the formula RSO_ThreeM is a water-soluble salt or an alkyl sulfonate containing an acid, wherein R is C ₆ ―C_{twenty two}A linear or branched, saturated or unsaturated alkyl group, preferably₁₂ -C₁₈An alkyl group, more preferably C₁₄-C₁₆An alkyl group, M is H or
Cations, such as alkali metal cations (eg, sodium, potassium, lithium
) Or ammonium or substituted ammonium (eg, methyl, dimethyl
Ru- and trimethylammonium cations and tetramethylammonium
Quaternary ammonium cation and dimethylpiperidinium cation
Alkylamines such as ethylamine, diethylamine and triethylamine
Quaternary ammonium cations derived therefrom, as well as mixtures thereof).

Alkylaryl sulfonates suitable for use herein include those of the formula RSO _Three There is a water-soluble salt or acid of M wherein R is C₆-C_{twenty two}Linear or branched
A saturated or unsaturated alkyl group, preferably C₁₂-C₁₈Alkyl group, more preferably
Is C₁₄-C₁₆Aryl substituted with an alkyl group, preferably benzyl,
Is H or a cation, such as an alkali metal cation (eg, sodium, potassium
, Lithium, calcium, magnesium, etc.) or ammonium or
Exchanged ammonium (eg, methyl-, dimethyl- and trimethylammonium
Cations and quaternary ammonium cations such as tetramethylammonium
Piperidinium cation and ethylamine, diethylamine, triet
For quaternary ammonium cations derived from alkylamines such as tylamine
And mixtures thereof).

As used herein, alkylsulfonates and alkylarylsulfonates are primary and secondary alkylsulfonates and primary and secondary alkylarylsulfonates. “Secondary C ₆ -C ₂₂ alkylsulfonate or C ₆ -C ₂₂ alkylarylsulfonate” refers herein to a compound as defined herein above in which the SO3M or aryl-SO3M group is an alkyl chain. Is bonded to the carbon atom (secondary carbon atom) of the alkyl chain between the two carbon atoms.

For example, C ₁₄ -C ₁₆ alkyl sulfonate salts are available from Hoechst to Host
apur (trade name) SAS is commercially available, and C8-alkyl sulfonate sodium salt is commercially available from Witco SA under the name Witconate NAS 8 (trade name). Examples of commercially available alkylaryl sulfonates include S
u. Ma. Is a commercially available lauryl aryl sulfonate. Particularly preferred alkylaryl sulfonates are available from Albright & Wilson as N
An alkyl benzene sulfonate commercially available under the trademark ansa (trade name).

[0079] Other anionic surfactants useful for cleaning purposes can also be used herein. They can include salts (e.g., sodium, potassium, ammonium and mono-, - di - and substituted ammonium salts such as triethanolamine salt), C ₈ - C ₂₄ olefin sulfonates, British Patent Specification No. 1,082 , sulfonated polycarboxylic acids prepared by sulfonation of an alkaline earth metal citrates pyrolysis products, such as described in No. 179, the ethylene oxide to C ₈ -C ₂₄ alkyl polyglycol ether sulfates (10 moles including); C _14-16 alkyl ester sulfonates such as methylmercury ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates Isethionates such as the acyl isethionates, N- acyl taurates, alkyl succinamates and sulfosuccinates, sulfosulfuron monoesters of succinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinates (Especially saturated and unsaturated C ₆ -C ₁₄ diesters), sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycoside (nonionic non-sulfated compounds are described below), branched primary alkyls There are alkyl polyethoxy carboxylates such as sulfates, of the formula RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ⁺ , where R is C ₈ -C ₂₂ alkyl and k is 0 to 10 And M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, for example, rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from tall oil. A further example is “Surface Active Agents and Deter.
gents "(Vol. I and II, Schwartz, Perry a
nd Berch). A variety of such surfactants are disclosed in US Pat. No. 3,929,678 issued to Laughlin et al. On Dec. 30, 1975.
No. 23, line 58 to column 29, line 23 (incorporated herein by reference).

Other anionic surfactants particularly suitable for use herein are alkyl carboxylates having 4 to 24, preferably 8 to 18, more preferably 8 to 16 carbon atoms in the alkyl chain. And alkylalkoxycarboxylates, wherein alkoxy is propoxy and / or ethoxy, preferably ethoxy with a degree of alkoxylation of 0.5 to 20, preferably 5 to 15.
Preferred alkylalkoxycarboxylates for use herein are Ka
o Chemical Gbmh to Akyposoft (brand name) 100 NV
Sodium laureth 11 carboxylate commercially available under the name
R is a _{C12-C14 RO (C 2 H} 4 O) 10 -CH 2 COONa).

Suitable amphoteric surfactants for use herein include amine oxides having the formula R ₁ R ₂ R ₃ NO wherein R _1, R _{2 and} R ₃ are each independently carbon It is a saturated or substituted, straight-chain or branched hydrocarbon chain of the formulas 1 to 30. Preferred amine oxide surfactants to be used according to the invention are amine oxides having the formula R ₁ R ₂ R ₃ NO, wherein R 1 is 1 to 30, preferably 6 to 20, more preferably 8 to 16 , Most preferably 8 to 12
Wherein R 2 and R 3 are independently 1 to 4
A substituted or unsubstituted, straight-chain or branched hydrocarbon chain comprising, preferably 1 to 3 carbon atoms, more preferably a methyl group. R1 can be a saturated, substituted or unsubstituted linear or branched hydrocarbon chain. Amine oxides suitable for use herein are, for example, natural blend C8-C10 amine oxides as well as C12-C16 amine oxides available from Hoechst.

[0082] Zwitterionic surfactants suitable for use herein contain both cationic hydrophilic groups, ie, quaternary ammonium groups and anionic hydrophilic groups, on the same molecule over a relatively wide pH range. I do. Typical anionic hydrophilic groups are carboxylate and sulfonate, but other groups such as sulfate, phosphonate can be used. The general formula of the zwitterionic surfactant used herein is R ₁ -N ⁺ (R ₂ ) (R ₃ ) R ₄ X ^- where R ₁ is a hydrophobic group R ₂ is hydrogen, C ₁ -C ₆ alkyl,
A hydroxyalkyl or other substituted C ₁ -C ₆ alkyl group; R ₃ is also a C ₁ -C ₆ alkyl, hydroxyalkyl or other substituted C ₁ -C which can also bond to R ₂ to form a ring structure with N. A C ₆ alkyl group or a C ₁ -C ₆ carboxylic acid group or a C ₁ -C ₆ sulfonate group; R ₄ is a moiety that links a cationic nitrogen atom to a hydrophilic group, typically 1 to 10 X is a hydrophilic group which is a carboxylate or sulfonate group.

A preferred hydrophobic group R ₁ is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain which can contain a binding group such as an amide group or an ester group.
More preferred R ₁ is an alkyl group containing 1 to 24, preferably 8 to 18, more preferably 10 to 16 carbon atoms. These simple alkyl groups are preferred for cost and stability reasons. However, the hydrophobic group R ₁ has the formula _Ra- C
(O) —NH— (C (R _b ) ₂ ) _m may be an amide residue, wherein _Ra is
An aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain;
Preferably, it is an alkyl group containing from 8 to 20, preferably up to 18, more preferably up to 16 carbon atoms, R _b is selected from the group consisting of hydrogen and hydroxy groups and m is from 1 to 4, preferably 2 to 3, more preferably 3, having no more than 1 hydroxy group in the (C (R _b ) ₂ ) moiety.

Preferred R ₂ is hydrogen or C ₁ -C ₃ alkyl, more preferably methyl. Preferred R ₃ is C ₁ -C ₄ carboxylic acid group or C ₁ -C ₄ sulfonate group, or C ₁ -C ₃ alkyl, more preferably methyl. Preferred R ₄ is (CH ₂ ) _n , where n is an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3.

Some common examples of betaines / sulfobetaines are described in US Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, which are incorporated herein by reference. Has been described.

Examples of particularly suitable alkyl dimethyl betaines include coconut dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N
, N-dimethyl ammonia) acetate, 2- (N-coco N, N-dimethyl ammonium) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, and stearyl dimethyl betaine. For example,
Coconut dimethyl betaine is a trademark of Amonyl 265 (trade name)
Commercially available from ppic. Lauryl betaine is available from Empigen BB / L
Commercially available from Albright & Wilson under the trade name (trade name).

Examples of amidobetaines are cocoamidoethylbetaine, cocoamidopropylbetaine or C10-C14 aliphatic acylamidopropylene (hydropropylene) sulfobetaine. For example, C10-C14 aliphatic acylamide propylene (hydropropylene) sulfobetaine is referred to as “Varion CAS (trade name)
It is commercially available from Sherex Company under the trademark "sulfobetaine".

A further example of betaine is lauryl-imino-dipropionate, which is commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®.

[0089] Suitable cationic surfactants for use herein include quaternary ammonium,
There are derivatives of the phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants for use herein are quaternary ammonium compounds in which one or two of the hydrocarbon groups attached to the nitrogen have 6 to 30 carbon atoms.
, Preferably a saturated linear or branched alkyl group having 10 to 25 carbon atoms, more preferably 12 to 20 carbon atoms, and other hydrocarbon group bonded to nitrogen (
That is, when one hydrocarbon group is the above-mentioned long-chain hydrocarbon group, 3) when two hydrocarbon groups are the above-mentioned long-chain hydrocarbon group, 2) is independently 1 to 4 carbon atoms. A quaternary ammonium compound, preferably a substituted or unsubstituted, linear or branched alkyl chain having 1 to 3 carbon atoms, more preferably a methyl group. Preferred quaternary ammonium compounds suitable for use herein are non-chlorinated / non-halogen quaternary ammonium compounds. The counter ion used in the quaternary ammonium compound is compatible with any persulfate and is selected from a group such as methyl sulfate or methyl sulfonate.

[0090] Myristyl trimethyl sulfate, cetyl trimethyl sulfate and / or
Alternatively, trimethyl quaternary ammonium compounds such as tallow trimethyl sulfate are particularly preferred for use in the compositions of the present invention. Such trimethyl quaternary ammonium compounds are commercially available from Hoechst or from Albright & Wilson under the trademark EMPGEN CM®.

Among the nonionic surfactants, alkoxylated nonionic surfactants and especially ethoxylated nonionic surfactants are suitable for use herein. Particularly preferred nonionic surfactants for use herein are capped alkoxylated nonionic surfactants because of their improved persulfate stability.

A capped alkoxylated nonionic surfactant suitable for use herein is represented by the following formula: R ₁ (O—CH ₂ —CH ₂ ) _n — (OR ₂ ) _m —O— R _{3 In the} above formula, R ₁ is a C ₈ -C ₂₄ linear or branched alkyl or alkenyl group, an aryl group, or an alkaryl group, preferably, R ₁ is a C ₈ -C ₁₈ alkyl or alkenyl group. R ₂ is a C ₁ -C ₁₀ linear or branched alkyl group, preferably a C ₁₀ -C ₁₅ alkyl or alkenyl group, more preferably a C ₁₀ -C ₁₅ alkyl group. A C ₂ -C ₁₀ straight or branched alkyl group; R ₃ is a C ₁ -C ₁₀ alkyl or alkenyl group, preferably a C ₁ -C ₅ alkyl group, more preferably methyl; n and m Is independently 1 Luo 20, preferably from 1 to 10, more preferably lies an integer ranging from 1 to 5; or a mixture thereof.

[0093] These surfactants are available from BASF under the trademark Plurafac ™.
Symperonic from HOECHST under the trademark Genapol (trade name)
Commercially available from ICI under the trade name (trade name). A preferred capped nonionic alkoxylated surfactant represented by the above formula is Genapol®.
It is commercially available from Hoechst under the trademark L2.5 NR and from BASF under the trademark Plurafac®.

Chelating Agents Liquid aqueous persulfate-containing compositions suitable for use in the fabric bleaching methods herein may include a chelating agent as a preferred optional ingredient. Suitable chelators can be any of those known to those skilled in the art, such as phosphonate chelators, aminocarboxylate chelators, other carboxylate chelators, polyfunctionally-substituted aromatic chelators, ethylenediamine N, N′-disuccinic acid or And those selected from the group comprising mixtures thereof.

[0095] The presence of a chelating agent contributes to further improving the chemical stability of the composition. Chelating agents are desirably included in the compositions herein as they increase the ionic strength of the compositions herein and thus improve stain removal and bleaching performance on various surfaces.

Suitable phosphonate chelators for use herein include alkyl metal ethane 1-hydroxydiphosphonate (HEDP), alkylene poly (alkylene phosphonate) and aminoaminotri (methylene phosphate) (ATMP), nitrilotrimethylene Phosphonate (NTP), ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate (DTP
There are aminophosphonate compounds containing MP). The phosphonate compounds may be present either in their acid form or as salts of different cations, based on some or all of their acid functionality. Preferred phosphonate chelators to be used herein are diethylenetriaminepentamethylenephosphonate (DTPMP) and ethane 1-hydroxydiphosphonate (HEDP). These phosphonate chelators are commercially available from Monsanto under the trademark DEQUEST®.

[0097] Polyfunctionally substituted aromatic chelators are also useful in the compositions herein. 197
See U.S. Pat. No. 3,812,044, issued May 21, 4 to Connor et al. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine N
, N'-disuccinic acid, or an alkali metal, alkaline earth, ammonium or substituted ammonium salt thereof, or a mixture thereof. Ethylenediamine N, N
The '-disuccinic acid, especially the (S, S) isomer, was obtained on November 3, 1987 by Hartm.
US Pat. No. 4,704,233 issued to An and Perkins has been described extensively. Ethylenediamine N, N'-disuccinic acid is, for example, ED
Palmer Research Laboratories under the trademark DS (trade name)
Commercially available from ies.

Suitable aminocarboxylates to be used herein include ethylenediaminetetraacetate, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Triethylene tetraamine hexaacetate, ethanol diglycine,
Propylenediaminetetraacetic acid (PDTA) and methylglycinediacetate (MGDA
), Each of which is in the form of its acid or its alkali metal, ammonium and substituted ammonium salts. Particularly suitable aminocarboxylates for use herein are diethylenetriaminepentaacetic acids such as Trilon F
Propylenediaminetetraacetic acid commercially available from BASF under the trademark S (trade name) (
PDTA) and methylglycine diacetate (MGDA).

[0100] Additional carboxylate chelators as used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid and mixtures thereof.

Other chelators used herein have the formula:

[0102]

Embedded image

R ₁ , R ₂ , R ₃ and R ₄ are independently —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO ₂ , —C (O) R ′ and —SO ₂ R "is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy Selected; R ₅ , R ₆ , R ₇ and R ₈ are independently selected from the group consisting of —H and alkyl.

Particularly preferred chelating agents to be used herein are aminoaminotri (methylene phosphate), diethylenetriaminopentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine N, N′-diamine. Succinic acid and mixtures thereof.

Typically, liquid aqueous persulfate-containing compositions suitable for use in the fabric bleaching methods herein comprise up to 5%, preferably from 0.01% to 1%, of the total weight of the composition.
. Comprising 5% by weight, more preferably 0.01% to 0.5%, of a chelating agent or a mixture thereof.

Radical Scavenger Liquid aqueous persulfate-containing compositions suitable for use in the fabric bleaching methods herein may include a radical scavenger or a mixture thereof. Suitable radical scavengers for use herein include known substituted mono- and dihydroxybenzenes and analogs thereof, alkyl and aryl carboxylates and mixtures thereof. Such radical scavengers preferred for use herein include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid , Toluic acid, catechol, t-butylcatechol, benzylamine, 1,1,3-tris (2-methyl-
4-Hydroxy-5-tert-butylphenyl) butane, n-propyl gallate or mixtures thereof, very preferred is di-tert-butylhydroxytoluene. Radical scavengers such as n-propyl gallate are Ni
It is commercially available from Nipa Laboratories under the trademark panox S1. When used, the radical scavenger is typically present herein in an amount of up to 10% by weight, preferably 0.001% to 0.5% by weight, based on the total composition.

[0107] The presence of radical scavengers may contribute to the chemical stability of the bleaching compositions herein as well as the safety profile of these compositions.

Test Methods The bleaching performance of various types of bleachable stains can be evaluated by the following test methods.

A suitable test method for evaluating the bleaching performance of a stained cloth under immersion conditions is as follows. The composition according to the invention is diluted with water, typically at a dilution level of 1 to 100 ml / L, preferably 20 ml / L (composition: water), and the soiled cloth is immersed therein for 20 minutes to 6 hours. And then rinse. Alternatively, the bleaching composition may be used in a washing machine, typically at a dilution level of 1 to 100 ml / L (composition: water). In the washing machine, the soiled cloth is washed at a temperature of 30 ° C. to 70 ° C. for 10 to 100 minutes and then rinsed. The reference composition in this comparative test also undergoes the same treatment. For example, stained cloth / cloth with tea, coffee, etc. M. C. Co. Inc
. It is commercially available from.

The stained fabric treated with the composition used in the present invention is then referred to, for example, the same composition but other bleaching systems, such as hydrogen peroxide and acetyltriethyl citrate at equal bleach levels. Bleaching performance is assessed by side-by-side comparison with those treated with the composition comprising. Visual grading can be used to assign differences in panel units (psu) ranging from 0 to 4.

For stain removal performance on various stains, the same test method is performed for enzymatic and greasy stains.

EXAMPLES The following liquid aqueous persulfate compositions were made by mixing the listed ingredients in the listed proportions (% by weight unless otherwise noted).

[0113]

Table 1 Composition (% by weight) I II III IV V Akysoft 100 NV (trade name) 0.5 0.5-0.3 0.4 Curox (trade name) 3 2 4 4.3 5 Trifluoromethylphenyl ketone 0.5--0.3-acetoacetone- 0.4--0.4 HEDP 0.1 0.05 0.16 0.1-BHT 0.05---0.1 Propyl gallate-0.1-0.05-NaCl--0.1 0.5-NaBr-----1.0 Water and trace components up to 100% Alkalinizing agent up to the right pH 2 2.5 4 4 1.5

[0114]

Table 2 Composition (% by weight) VI VII VIII IX X XI Akysoft 100 NV (trade name) 0.5 0.5 0.5 0.2 0.2-Curox (trade name) 5 7 10 10 6 9.5 Acetylacetone 0.5 0.5 0.5---N, N -Dimethyl-4 -oxopiperidinium nitrate---0.5 0.5 -Propyl gallate 0.05 0.05 0.1 0.1 0.05-Water and trace components up to 100% pH 2 1.8 1.5 1.5 2 2

[0115]

Table 3 Composition (% by weight) XII XIII XIV XV XVI XVII Akysoft 100 NV (trade name) 0.5 0.5 0.5 0.2 0.2 0.2 Curox (trade name) 5 7 10 10 6 9.5 Cyclohexanone 0.5-0.5 0.5--N, N -Dimethyl-3-0.5--0.5--Oxopiperidinium nitrate Propyl gallate 0.05 0.05 0.1 0.1 0.05 0.1 Water and trace components up to 100% pH 2 1.8 1.5 1.5 2 2

[0116]

Table 4 Composition XVIII XIX XX XXI XXII XXIII (% by weight) Witoconate 55 5 55-NAS 8 (40% active) (trade name) Curox (trade name) 9.5 9.5 9.5 9.5 9.5 9.5 9.5 N, N-dimethyl -4 0.5 1 0.1 0.5 0.5--Oxopiperidinium triflate HEDP 0.1 0.2 0.1--0.1 BHT 0.05 0.05 0.1 0.1 0.05 0.05 Water and trace components up to 100% pH 1.5 1.5 1.5 1.5 1.5 1.5

[0117]

Table 5 Composition XVIV XXV (% by weight) Witconate 55 NAS 8 (40% active) (trade name) Curox (trade name) 9.5 9.5 Cycloheptanone 0.5 0.5 HEDP-0.1 BHT-0.05 Water and trace components 100% Up to pH 1.5 1.5

Akyposoft 100 NV (trade name) is a product of Kao Chemicalla.
C12-C14 alkyl ethoxy carboxylate (EO10) commercially available from Gmbh. BHT is di-tertbutylhydroxytoluene. HEDP is ethane 1-hydroxydiphosphonate, commercially available from Monsanto under the name serieDequest. Cyclohexanone is commercially available from Aldrich. Witconate NAS 8 (trade name) is commercially available from Witco SA.
8 alkyl sulfonate. Curox® is a triple salt of potassium monopersulfate, potassium sulfate and potassium bisulfate, commercially available from Interox.

The following method of fabric bleaching illustrates the invention.

Example 1 100 ml of the liquid persulfate composition exemplified above (compositions I to XXV) was
Diluted with L water. The soiled cloth was then contacted with the aqueous bath so obtained for 20 minutes, after which it was rinsed with water.

Example 2 200 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was
Diluted with L water. The soiled cloth was then contacted with the aqueous bath so obtained for 20 minutes and then rinsed with water for 20 minutes.

Example 3 300 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was
Diluted with L water. The soiled cloth was then contacted with the aqueous bath so obtained for 20 minutes and then rinsed with water for 20 minutes.

Example 4 100 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was treated with 5
Diluted with L water. The soiled cloth was then brought into contact with the aqueous bath so obtained for 1 hour and then rinsed with water for 20 minutes.

Example 5 100 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was
Diluted with L water. The soiled cloth was then brought into contact with the aqueous bath so obtained for 6 hours and then rinsed with water for 20 minutes.

Example 6 100 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was
Diluted with L water. The soiled cloth was then brought into contact with the aqueous bath so obtained for 24 hours and then rinsed with water for 20 minutes.

Example 7 100 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was
Diluted with L water. The soiled cloth was then brought into contact with the aqueous bath so obtained for 1 hour and then rinsed with water for 20 minutes. Finally, the so bleached fabric was contacted with 40 g of Dash Futur (trade name) diluted in 5 L of water for 1 hour, and then rinsed with water.

Example 8 140 ml of Ariel a mano (trade name) was diluted with 5 L of water. The soiled cloth was contacted with the soaking solution so obtained for 1 hour and then rinsed with water.
100 ml of the liquid persulfate composition exemplified above (compositions I to XXV) is added to 5 L
Diluted with water. The fabric is then contacted with the aqueous bath so obtained for 1 hour,
Then rinsed with water for 20 minutes.

Example 9 100 ml of the liquid persulfate composition exemplified above (Compositions I to XXV) was
An aqueous bath was obtained by diluting with L of water, and the soiled cloth was contacted for 20 minutes. Then, the fabric is
Rinse with water for 20 minutes and wash in a washing machine with 225 g Dash Futur (trade name) (eg, San Giorgio 352ZX (trade name), main cycle).

All of the above methods are fabric and color safe, while providing excellent bleaching performance and effective stain removal performance when bleaching fabrics.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG , KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBL E PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Spadoni, Luca, Italy 0149, Rome, Via, San Torre, Santa Rosa 30 (72) Inventor, Massotti, Valentina Italy 40033, Casalettio, Di, Reno, Via, Pertini 5F Term (reference) 4H003 AB05 BA12 DA01 EA19 EA20 EB03 EB04 EB09 EB12 EB19 EB20 EB24 ED02 EE05 FA08 FA28 FA43

Claims (14)

[Claims] 1. A method for bleaching a fabric, comprising: diluting a liquid aqueous composition in the form of a stock solution having a pH of less than 7 and comprising a persulfate in an aqueous bath. Contacting said fabric with said aqueous bath comprising the step of rinsing said fabric with water. 2. An aqueous bath comprising the liquid aqueous composition, wherein the aqueous bath comprises
The fabric is left soaked for a period of 4 hours, preferably 3 minutes to 12 hours, more preferably 4 minutes to 6 hours, most preferably 4 minutes to 15 minutes.
The method described in. 3. The composition according to claim 1, wherein the composition is diluted with water at a dilution level of up to 500 times its weight, preferably 5 to 200 times, more preferably 10 to 80 times. The described method. 4. The process of contacting the fabric with the aqueous bath comprising the liquid aqueous composition before and / or during the process of contacting the fabric with the aqueous bath and / or removing the fabric from the aqueous bath. The fabric is washed with a laundry detergent composition comprising at least one surfactant after the step of contacting the bath, before the rinsing step and / or after the rinsing step. The method according to any one of claims 1 to 4. 5. The composition according to claim 1, wherein said liquid aqueous composition is 0.01% by weight based on the total weight of the composition.
To 50%, preferably 0.5% to 20%, more preferably 1% to 15%.
5. A process according to any one of the preceding claims, comprising%, most preferably 2% to 10% of the persulfate or a mixture thereof. 6. The liquid composition according to claim 1, wherein the persulfate is a monopersulfate, preferably sodium monopersulfate and / or potassium monopersulfate. Method. 7. The method of claim 1, wherein the liquid composition comprises up to 10% by weight of the total composition.
Preferably, it further comprises 0.05% to 5%, more preferably 0.1% to 2%, most preferably 0.2% to 1.5% of a ketone, aldehyde and / or halide activator compound. The method according to any one of claims 1 to 6. 8. The method according to claim 1, wherein the activator is oxopiperidinium salt, ammonium acetophenone salt, acetoacetone, 2,3-hexanedione, trimethylammonioacetone nitrate, 5-diethylbenzylammonio-2-pentanone nitrate, 5-diethylmethylammonio 2-pentanone nitrate, methylpyruvate, diethylketomalonate, 3-hydroxy-2-butanone, acetol,
Hexachloroacetone, 2,5-hexanedione, phenylacetone, ethyl levulinate, 3-hydroxy-2-pentanone, acetone, 3-pentene-2-
On, methyl ethyl ketone, 4-hydroxy-3-methyl-2-butanone, 3-
Pentanone, 2-heptanone, hydroxyquinoline, 4-acetyl-1-methylpyridinium nitrate, di-2-pyridyl ketone N-oxide, 2-acetylquinoxaline, 2-acetyl-3-methylquinoxaline oxaline, di-2- Pyridyl ketone, 6-acetyl-1,2,4-trimethylquinolinium nitrate, 8-hydroxyquinoline N-oxide, methylphenylglyoxalate, N
-Methyl-p-morpholinoacetophenone methyl sulfate, 3-acetylpyridine N-oxide, p-nitroacetophenone, m-nitroacetophenone,
Sodium p-acetylbenzenesulfonate, p-acetylbenzonitrile,
3,5-dinitroacetophenone, 4-trimethylammonioacetophenone nitrate, 4-methoxy-3-nitroacetophenone, p-chloroacetophenone, p-diacetylbenzene, N-methyl-p-morpholinoacetophenone nitrate, phenacyltriphenyl Phosphonium nitrate, 2-acetylpyridine, 2-acetylpyridine N-oxide, 3-acetylpyridine, 4-acetylpyridine, 4-acetylpyridine N-oxide, 2,6-diacetylpyridine,
3-acetylpyridine N-oxide, triacetylbenzene, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 3-methylcyclohexanone, 4-ethylcyclohexanone, 4-t-butylcyclohexanone, 4,4-dimethylcyclohexanone, Methyl 4-oxo-cyclohexanone carboxylate, sodium 4-oxo-cyclohexanone carboxylate, 2-trimethylammoniocyclohexanone nitrate, 4-trimethylammoniocyclohexanone nitrate, 3-oxo-cyclohexylacetic acid, cycloheptanone, 1,4- Cyclohexadione, dehydrochloric acid, tropinone methionitrate, N-methyl-3-oxoquinuclidinium nitrate, cyclooctanone, cyclopen Non, 2,2,6,6-tetramethyl-4-piperidone hydrate, 1-methyl-4-piperidone N-oxide, N-carbethoxy-4-piperidone, tetrahydrothiopyran-4-one methnitrate, tetrahydro Thiopyran-4-one S, S-dioxide, tetrahydrothiopyran-3-one S,
The method according to claim 7, which is S-dioxide, 4-oxacyclohexanone or a mixture thereof. 9. In the liquid aqueous composition, the bleach activator is an oxopiperidinium salt having the following formula: In the above formula, the carbonyl group> C ＝ O is 2,3 or 4 of oxopiperidinium.
R1 and R2 each independently represent a substituted or unsubstituted hydrocarbon chain having 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. A substituted or unsubstituted alkyl or alkenyl or alkynyl group comprising, or a substituted or unsubstituted aryl group comprising from 6 to 12 atoms, or a C1-C20 alkylaryl group wherein the aryl group comprises from 6 to 12 carbon atoms; X ^- may be any anion, for example a triflate, preparative Shirato, mesylate, nitrate, triflate, mesylate, tosylate, more preferably, and most preferably triflate, oxo piperidinium ring, at 2, 3, 5 or 6 One or more of the substituents defined for R1 or R2 above Or an oxopiperazinium salt which may be mono- or polysubstituted by a halogen atom and / or an ammonium acetophenone salt represented by the following formula: In the above formula, the ammonium group is at the 2-, 3- or 4-position; R1, R2,
And R3 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 12 carbon atoms. An alkenyl or alkynyl group, or a substituted or unsubstituted aryl or aryl group containing 6 to 10 atoms
A C1-C20 alkylaryl group containing from 1 to 10 carbon atoms; R4 is a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably Methyl or trifluoromethyl or trichloromethyl or tribromomethyl; X ^- can be any anion, such as triflate, tosylate, mesylate, nitrate, and the benzene ring is as defined above at the 2,3 and / or 4 position. R1, R2 or R
9. The process according to claim 7 or 8, wherein the salt is an ammonium acetophenone salt optionally substituted by one or more of the substituents defined for 3 or a halogen atom. 10. The liquid aqueous composition, wherein the bleaching activator comprises 1,1
-Dimethyl-3-oxopiperidinium nitrate, 1,1-dimethyl-4-oxopiperidinium triflate, 1,1-dimethyl-3-oxopiperidinium triflate, 1,1-dimethyl-4-oxopi Peridinium nitrate, 1
-Benzyl-4-piperidone methnitrate, 1-t-butyl-1-methyl-4
-Oxopiperidinium nitrate, 1- (4-dodecylbenzyl) 1-methyl-4-oxopiperidinium chloride, 3- (N-methyl-4-oxopiperidinium) -propanesulfonate, 1-allyl- 1-methyl-4-oxopiperidinium chloride, 1-methyl-1- (1-naphthyl-methyl) -4-oxopiperidinium chloride, 1-methyl-1-pentamethylbenzyl-4-oxopiperidinium Chloride, N, N′-dimethyl-N, N′-phenylene dimethylene-bis (4-oxopiperidinium nitrate), 1-benzyl-1
-Methyl-4-oxopiperidinium triflate, 1-benzyl-1-methyl-3-oxopiperidinium triflate, 1-benzyl-1-methyl-4-oxopiperidinium nitrate, 1-dodecyl-1- Methyl-4-oxopiperidinium nitrate, 1-octyl-1-methyl-4-oxopiperidinium nitrate, 1-nonyl-1-methyl-4-oxopiperidinium nitrate, 4
10. Trimethyl ammonium acetophenone nitrate, 2-trimethyl ammonium acetophenone nitrate, 4-triethyl ammonium acetophenone mesylate, 3-trimethyl ammonium acetophenone mesylate, trihalogenated methyl phenyl ketone or a mixture thereof. A method according to any one of the preceding claims. 11. The liquid composition according to claim 1, wherein said liquid composition is 0.1 to 6, more preferably 0.5.
Method according to any of the preceding claims, having a pH in the range from 1 to 4, more preferably from 1 to 3, most preferably from 1 to 2. 12. The liquid composition may comprise a chelating agent, a radical scavenger, a builder, a surfactant, an antioxidant, a stabilizer, a soil suspending agent, a polymeric soil releasing agent, a catalyst, a dye transfer agent, a solvent, an inhibitor. The method according to any one of claims 1 to 11, further comprising at least one optional component selected from the group consisting of foaming agents, whitening agents, fragrances, dyes, pigments and mixtures thereof. 13. A persulfate having a pH of less than 7 and optionally an aldehyde, ketone and / or halide activator compound for bleaching the fabric, for reducing the loss of tensile strength of said fabric. Use of a liquid aqueous bleaching composition comprising a bleach activator compound that is: 14. A persulfate having a pH of less than 7 and optionally an aldehyde, ketone and / or halide activator for bleaching a colored fabric, for reducing color damage of said fabric. Use of a liquid aqueous bleaching composition comprising a bleach activator compound that is a compound.