JP2001521981A - Multipurpose liquid aqueous bleaching composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a liquid having a pH of less than 7 and comprising a persulfate and a bleach activator selected from the group consisting of aldehyde activator compounds, ketone activator compounds, halide activator compounds and mixtures thereof. It relates to an aqueous composition. These compositions are suitable for exhibiting improved bleaching performance while being chemically and physically stable for long-term storage.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention bleaches hard surfaces such as, but not limited to, walls, tiles, floors, glass, bathroom surfaces, kitchen surfaces, toilet bowls, dishes, and various surfaces including fabrics, clothes, carpets, and the like. To a stable liquid aqueous bleach-containing composition that can be used for:

BACKGROUND OF THE INVENTION Various liquid aqueous bleach-containing cleaning compositions have been described extensively in the art. Typically, such compositions can be divided into hard surface bleach containing compositions and laundry bleach containing compositions. Conventionally, these two types of liquid compositions have greatly different formulations, and are sold as different products based on different marketing concepts. Due to such differences, consumers must purchase and use at least two types of products. Furthermore, the above two compositions, especially cleaning compositions containing hard surface bleach, can be classified into subtypes. In fact, many different hard surface cleaners are commercially available, such as, for example, bathroom cleaners, kitchen cleaners and floor cleaners.

[0003] The variety of such formulations may be attributed to the essential difference between soil found on laundry and soil found on various hard surfaces. For example,
Kitchen soils mainly contain cooking oil, while bathroom soils mainly contain sebum and soap scum. Floor stains are mainly granular stains, and laundry has a variety of different stains / stains, including oil stains (eg, olive oil, mayonnaise, vegetable oils, cosmetics), enzymatic stains (eg, blood), etc. Sometimes.

[0004] However, liquid aqueous bleach-containing compositions with some better performance, such as multipurpose liquid aqueous bleach compositions that can be used satisfactorily in laundry applications simultaneously with various hard surfaces and exhibit effective bleaching performance They tend to develop things.

Accordingly, it is an object of the present invention to provide a multipurpose liquid aqueous bleaching composition that exhibits effective bleaching performance on various surfaces.

[0006] Commonly experienced liquid aqueous bleaching compositions suitable for bleaching stains on fabrics and hard surfaces are based on halogen bleaches, especially hypochlorous acid bleaches. However, the disadvantages associated with these halogen bleaches, such as chlorine bleaches, are that undesired typical chlorine odors are present to consumers during and after use (e.g., in the hands of consumers and / or surfaces treated with bleach). It is a point that can be felt. Moreover, such liquid aqueous halogen bleach-containing compositions (typically hypochlorite) can cause relatively severe damage to fabrics at relatively high concentrations and / or repeated use. Although the use of milder oxygen bleaches, such as hydrogen peroxide, can minimize color and fabric damage, the bleaching properties of such peroxide bleaches are much greater than the more aggressive halogen bleaches. Less desirability. Accordingly, liquid aqueous activated 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-
A-598 170. In fact, this patent application discloses a liquid aqueous laundry composition comprising hydrogen peroxide and acetyl triethyl citrate emulsified in a bleach activator, such as a nonionic surfactant system. However, these compositions have not been found to be completely satisfactory from a consumer standpoint in terms of their bleaching performance. Rather, there is a continuing need for liquid aqueous bleaching compositions other than those already used in the art so that improved bleaching performance can be exerted on the various surfaces being treated.

It is therefore an object of the present invention to use in laundry applications and any household applications (eg bleaching / sterilizing hard surfaces) while being safe for the surface to be treated, for example the fabric itself and / or color. Even so, it is an object of the present invention to provide a multipurpose liquid aqueous bleaching composition exhibiting effective bleaching performance.

[0008] Another problem encountered when formulating such liquid aqueous bleaching compositions, especially liquid aqueous activated peroxide bleach-containing compositions, is that when stored for extended periods of time, the chemical and
May have a tendency to be physically unstable.

[0009] It is therefore a further object of the present invention to provide a multipurpose liquid aqueous bleaching composition that is chemically and physically stable when stored for a long period of time and exhibits effective bleaching performance.

By formulating a liquid aqueous composition having a pH of less than 7 and comprising as a bleaching system a persulfate and a bleach activator which is an aldehyde and / or ketone and / or halide activator compound. It has been found that the object of the invention is efficiently satisfied. More specifically, in various applications, for example, 100 ml / L
Conventional dilution levels of from 1 to 1 ml / L (composition: water), for example in washing operations, contain the same level of total bleach and bleach activator, such as hydrogen peroxide and acetyltriethyl citrate as bleach activator. Improved bleaching performance compared to the bleaching performance exhibited by other activated bleaching compositions consisting of, or as compared to said composition without said aldehyde and / or ketone and / or halide activator compound Has been found to be present in the composition according to the invention.

[0011] The combination of these components provides a liquid aqueous multipurpose bleaching composition that has great applicability to bleaching surfaces and soils. In fact, the composition according to the invention comprises
It is particularly suitable for any laundry application, for example as a laundry detergent or laundry additive, especially when used as a laundry pre-treatment agent or in other household applications such as hard surface cleaning applications.

[0012] An advantage of the compositions according to the invention is that these bleaching compositions can be used on natural fabrics (eg,
Suitable for bleaching different types of fabrics, including those made from polymeric fibers of synthetic origin, such as those made from cotton and linen), synthetic fibers (eg, polyamide-elastane), and those made from both natural and synthetic fibers. That is. For example, the bleaching compositions of the present invention based on the persulfate and activator compounds described herein may be labeled with warnings on commercial bleaching compositions, such as clothing and hypochlorite-containing compositions. Obviously, it can be used on synthetic fabrics despite the old prejudice against the use of bleach on synthetic fabrics.

Another advantage of the bleaching composition according to the invention is that it can perform under various conditions, for example in hard and soft water as well as in neat or diluted form. More particularly, it has been found that the liquid aqueous composition of the present invention finds a preferred use when used in its diluted form in any application, and especially in any conventional laundry application. In fact, when diluted (typically 20 ml /
L (composition: water) or higher), the composition of the invention has reduced acidity,
For example, a pH of about 1.5 to a pH of about 6.5 or more. The composition according to the invention comprises
Effective bleaching performance is exhibited even in the form of a stock solution, but surprisingly, the diluted form exhibits further improved bleaching performance. In fact, due to this "pH jump" effect, acidic liquid aqueous compositions (ie, less than 7, preferably less than 7, preferably Less than 3,
More preferably, a pH of less than 2) can be formulated.

Yet another advantage of the composition according to the invention is that it also exhibits effective stain removal performance against various stains, including enzymatic stains and / or greasy stains. Further, when used in any hard surface application, these compositions exhibit excellent descaling performance, such as stripes / coatings remaining on the treated surface as compared to, for example, hypochlorite-based compositions. Is found to be low. Thus, an advantage of the composition herein is that it is not necessary to flush its surface with water after treatment with the composition of the present invention, especially when used in diluted form.

US Pat. No. 3,822,114 discloses (a) from 1% to 75% by weight of a peroxide bleaching agent, for example a monophosphate or monopersulfate, (b) 0.01% by weight. To 75% by weight of a ketone or aldehyde activator compound and (c) an aqueous solution comprising said peroxide bleach and said activator can maintain the pH in the range of 7 to 12.
A concentrated peroxide bleach-containing composition comprising between about 85% and about 85% buffer is disclosed.
US-3 822 114 is for a granular composition. The liquid composition according to the invention is not disclosed in said specification.

[0016] Liquid aqueous compositions comprising persulfates are known and are described, for example, in EP-A-59.
8 694, EP-A-672 748 or WO 96/17044. However, none of these documents disclose ketone, aldehyde and / or halide activator compositions.

SUMMARY OF THE INVENTION The present invention provides a persulfate and aldehyde activator compound having a pH of less than 7.
Includes a liquid aqueous composition comprising a bleach activator selected from the group consisting of a ketone activator compound, a halide activator compound and mixtures thereof.

The present invention further encompasses a method of treating a surface, such as a fabric or a hard surface, starting with a liquid composition as defined herein. For example, the treatment method, in particular, the method for bleaching a fabric, comprises the step of contacting the fabric with a stock solution or a diluted liquid composition according to the present invention, the fabric being added to the bleaching composition for a period sufficient to bleach the fabric. Leaving in contact and then rinsing the fabric with water. The method of treating a hard surface herein comprises applying the composition herein in neat or diluted form to the hard surface and optionally rinsing the hard surface.

DETAILED DESCRIPTION OF THE INVENTION Liquid Bleach Composition The composition according to the present invention is not a solid or gas, but a liquid composition. "Liquid" as used herein includes "pasty" compositions. The liquid composition herein is an aqueous composition. The liquid composition according to the invention has a pH of less than 7. Preferably, the pH of the composition according to the invention is from 0.1 to 6, more preferably from 0.5 to 4, even more preferably from 1 to 3, and most preferably from 1 to 2. Formulating the composition according to the invention in the acidic pH range is critical for the chemical stability of the composition according to the invention. Typically, acidic pH limits / limits the formation of labile highly reactive species upon storage in acidic media such as dioxirane, and thus contributes to the stability of the composition during long term storage. . In fact, the reaction between the persulfate and the bleach activator compound (aldehyde and / or ketone activator compound) can result in dioxirane.

The pH of the composition 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.

As a first essential element, the composition according to the invention comprises a persulfate or a mixture thereof.

Suitable persulfates include alkali metal persulfates, including sodium and / or potassium persulfates. 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 compositions herein comprise from 0.01% to the total weight of the composition
To 50%, preferably 0.5% to 20%, more preferably 1% to 15%.
%, Most preferably 2% to 10% of said persulfate or a mixture thereof.

As a second essential component, the composition according to the invention comprises, as bleach activator, an aldehyde activator compound, a ketone activator compound, a halide activator compound or a mixture thereof.

As used herein, the term “aldehyde” means 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 chloride, bromide and / or iodide.

As used herein, “activator” refers to an activated bleaching species that reacts with persulfate, ie, dioxirane (when the activator compound is a ketone or aldehyde) or hypohalogenite (when the activator compound is a ketone or aldehyde). 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.

It is the activated species that is believed to significantly improve bleaching in the present invention over persulfate alone or other activated bleaching systems, such as hydrogen peroxide and acetyltriethyl citrate, ie, Dioxirane and hypohalogenite. 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.

[0036] 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 clearly 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 ".

[0040] 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:

[0042]

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:

[0046]

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.

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 0.01% by weight of the total composition.
To 10%, preferably 0.05% to 5%, more preferably 0.1% to 2%
, Most preferably from 0.2% to 1.5% of said ketone, aldehyde and / or halide activator compound.

In fact, this activated bleaching system has an effective bleaching performance on a variety of stains from hydrophobic to hydrophilic stains in all household applications and especially in laundry applications for both hydrophilic and hydrophobic fabrics. I will provide a.

The present invention not only has effective bleaching performance, but also has a greasy stain (eg, lipstick, tomato, cosmetics) and a reduced oiliness compared to the same formulation without the active compound described herein. Conveniently, it also provides good stain removal performance to remove various types of stains, including / or enzymatic stains (eg, blood, chocolate pudding).

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

A preferred test method for evaluating the bleaching performance of a stained cloth under dilution conditions is as follows. The composition according to the invention is typically diluted with water to a dilution level of 1 to 100 ml / L, preferably 20 ml / L (composition: water), and the soiled cloth is then immersed therein for 20 minutes to 6 hours. 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 to 70 ° C. for 10 to 100 minutes,
Then rinse. The reference composition in this comparative test also undergoes the same treatment. For example, a cloth / cloth stained with tea, coffee, or the like can be obtained from E.I. M. C. Co. Inc. It is commercially available from.

The stained fabric treated according to the invention is then referred to as a reference, for example the same composition comprising only persulphate or other bleaching systems, such as hydrogen peroxide and acetyl at equal bleach and bleach activator levels. Bleaching performance is assessed by comparing side by side with those treated with a composition comprising triethyl citrate. Visual grading can be used to assign differences in panel units (psu) ranging from 0 to 4.

An advantage of the composition of the present invention is that it is physically and chemically stable even for long-term storage.

[0057] The chemical stability of the compositions herein 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 means that a composition of the invention comprising a persulfate or a mixture thereof and an activator compound has more than 15%, preferably 10%, per month at 25 ° C. Means that no AvO loss is exceeded.

The loss of available oxygen (AvO) of the persulfate-containing composition can be measured by reduction with a solution of ammonium iron sulfate followed by titration with potassium permanganate. 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 composition according to the invention at 50 ° C. for a period of 7 days.

Optional Ingredients The compositions herein further comprise surfactants, chelating agents, radical scavengers, antioxidants, other stabilizers, builders, soil suspending agents, polymeric soil release agents, catalysts, inversions. Various optional components such as dyes, solvents, foam inhibitors, brighteners, fragrances, pigments, dyes and the like may be included.

Surfactant The composition of the present invention comprises a surfactant comprising a nonionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and / or an amphoteric surfactant or a surfactant thereof. It may contain a mixture. 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).

[0069] 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.

[0072] Zwitterionic surfactants suitable for use herein contain both cationic hydrophilic groups, ie, quaternary ammonium groups and anionic hydrophilic groups, over a relatively wide pH range on the same molecule. 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 that 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®.

[0079] 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.

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®.

[0081] 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.

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 The compositions of the present invention 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.

[0085] The presence of a chelating agent contributes to further improving the chemical stability of the composition. Chelating agents are desirably included in the compositions of the present invention because 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®.

[0087] 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).

Further carboxylate chelators used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid and mixtures thereof.

Other chelators used herein have the formula:

[0092]

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, the composition according to the invention comprises up to 5% of the total weight of the composition, preferably 0.01% to 1.5%, more preferably 0.01% to 0%. .5%
Or a mixture thereof.

Radical Scavenger The compositions of the present invention 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 preferred radical scavengers for use herein include di-tert-butylhydroxytoluene (B
HT), 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-t-butylphenyl) butane, N-Propyl gallate or a mixture thereof, very preferred is di-tert.
-Butylhydroxytoluene. Radical scavengers such as n-propyl gallate are sold under the trademark Nipanox S1 under the trademark Nipa Labor
commercially available from Atories.

When used, radical scavengers are typically used herein,
It is present in an amount up to 10% by weight, preferably from 0.001% to 0.5% by weight, based on the total composition.

The presence of a radical scavenger may contribute to the chemical stability of the bleaching composition of the present invention as well as the safety profile of the composition of the present invention.

Foam Inhibitors The compositions according to the present invention may further comprise a foam inhibitor as a preferred optional ingredient, such as a 2-alkylalkanol or a mixture thereof. An alkyl chain comprising from 6 to 16, preferably from 8 to 12, carbon atoms and a terminal hydroxy group, said alkyl chain being from 1 to 10, preferably from 2 to 8, more preferably from 3 in the alpha position. 2-Alkyl alkanols, such as those substituted with an alkyl chain comprising from 6 to 6 carbon atoms, are particularly preferred for use in the present invention. Such suitable compounds include, for example, Isofo (trade name) 12 (2-butyl octanol) or Isofo (trade name) such as Isofo 16 (2-hexyldecanol).
It is commercially available in the l (trade name) series.

Other suds suppressors are alkali metal salts of fatty acids containing about 8 to about 24, preferably about 10 to about 20 carbon atoms (eg, sodium or potassium) or soaps thereof.

Fatty acids, including those used in making soaps, include glycerides derived from, for example, plants or animals (eg, palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow) , Grease, lard and mixtures thereof). The fatty acids can also be prepared synthetically (for example, by the oxidation of petroleum stocks or the Fischer-Tropsch process).

[0103] Alkali metal soaps can be made by direct saponification of fats or oils or neutralization of free fatty acids prepared in another manufacturing process. Particularly useful are the sodium and potassium salts of a mixture of fatty acids derived from coconut oil and tallow, ie, sodium and potassium tallow and coconut soap.

The term “tallow” is used herein to refer typically to 2.5% C14,
In connection with a fatty acid mixture having an approximate carbon chain length distribution of 29% C16, 23% C18, 2% palmitolein, 41.5% olein and 3% linole (the first three fatty acids listed are saturated) I have. Other mixtures having similar distributions, such as various animal tallows and fatty acids derived from lard, are also included in the term tallow. The tallow can be cured (ie, hydrogenated) to convert some or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.

When the term “coconut” is used herein, it is typically 8% C8, 7% C10, 48% C12, 17% C14, 9% C
16, 2% C18, 7% olein and 2% linole (first 6
(Two fatty acids are saturated)). Other sources having a similar carbon chain length distribution, such as palm kernel oil and babassu oil, are also included in the term coconut oil.

Other suitable foam control agents are exemplified by silicone and silica silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials, while silica is used in finely divided form, exemplified by silica airgels and xerogels and various types of hydrophobic silica. These materials can be mixed as particles, and the foam inhibitor is conveniently releasably incorporated into a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. Alternatively, the foam inhibitor may be dissolved or dispersed in a liquid carrier and applied by spraying onto one or more other ingredients.

[0107] Preferred silicone suds suppressors are disclosed in US Pat. No. 3,933, Bartollota et al.
No. 3,672. Other particularly preferred defoamers are 2 April 1977
Self-emulsifying silicone foam inhibitors described in German patent application DTOS 2 646 126, published on the 8th. Examples of such compounds are siloxanes
A glycol copolymer, DC-544, commercially available from Dow Corning.
It is.

Particularly preferred silicone suds suppressors are the co-pending European Patent Application N ° 922164
9.8. It is described in. The composition comprises a non-porous full Yumushirika combined with silicone / silica mixture such as Aerosil ^R.

A particularly preferred foam inhibitor is a foam inhibitor system comprising a mixture of silicone oil and a 2-alkyl-alkanol.

Typically, the compositions herein comprise up to 4%, preferably from 0.1% to 1.5%, most preferably from 0.1% to 0.1% by weight of the total composition. It may contain 8% of a foam inhibitor or a mixture thereof.

Method for Treating a Surface In the present invention, the liquid aqueous composition of the present invention needs to be brought into contact with the surface to be treated.

"Surface" means herein any inanimate surface. These inanimate surfaces include hard surfaces typically found in homes such as kitchens and bathrooms, or, for example, tiles, walls, floors, chrome, glass, smooth vinyl, plastic, plasticized wood, table tops Hard surfaces found in car interiors, such as sinks, sinks, cookware tops, dishes, sinks, showers, shower curtains, handwashers, toilets, and other sanitaryware, as well as clothes, curtains, hangers, linens for bedding, and linens for bathrooms. ,
Fabrics and carpets include, but are not limited to, tablecloths, sleeping bags, tents, stuffed furniture, and the like. Inanimate surfaces include refrigerators, freezers, washing machines,
Household appliances including, but not limited to, automatic dryers, ovens, microwave ovens, dishwashers and the like are also included.

“Treating a surface” means that the composition according to the invention comprises a bleaching system based on persulphate and a ketone, aldehyde or halide activator compound or mixtures thereof, so that said surface is bleached. Is used herein to mean bleaching and / or disinfecting, and optionally washing as the composition may comprise surfactants or other conventional detergents.

The invention therefore encompasses a method of treating, in particular bleaching, a fabric as an inanimate surface. In such a method, the composition according to the invention is contacted with the fabric to be treated.

This is because in a so-called “pre-treatment mode”, the liquid bleaching composition as defined herein is applied undiluted on the fabric before the fabric is rinsed or washed and rinsed. Or a "soak mode" in which the liquid bleaching composition as defined herein is first diluted in an aqueous bath and soaked before the fabric is rinsed into said bath, or as defined herein. The liquid bleaching composition to be applied can be performed either "in the wash mode", which is added to the wash liquor formed by dissolution or dispersion of a typical laundry detergent. In each case, it is imperative that the fabric be rinsed after the fabric comes into contact with the composition and then the composition be completely dried.

The method for bleaching a surface, especially a fabric, according to the present invention exhibits effective white performance as well as effective stain removal performance.

The compositions according to the invention are preferably brought into contact with the fabric in liquid form. In fact, "
By "in liquid form" herein is meant the liquid composition itself according to the invention in neat or diluted form.

The compositions according to the invention are typically used in a washing operation in diluted form.
By "in diluted form" is meant herein that the fabric bleaching composition according to the invention is diluted by the user, preferably with water. Such a dilution
Occurs in hand washing applications as well as other means such as washing machines. The composition comprises 50
It can be diluted up to 0 times, preferably from 5 to 200 times, more preferably from 10 to 80 times.

More specifically, the method for bleaching a fabric according to the present invention comprises the steps of first contacting said fabric with a bleaching composition according to the invention in diluted form, and then for a time sufficient to bleach said fabric, typically Maintaining the fabric in contact with the composition for 1 to 60 minutes, preferably 5 to 30 minutes, and then rinsing the fabric with water.
If the fabric is to be washed, i.e. if it is to be washed with a conventional composition comprising at least one surfactant, by contacting the fabric simultaneously with the bleaching composition according to the invention and the detergent composition The washing may be performed simultaneously with the bleaching of the fabric, or the washing may be performed before or after the fabric is bleached. Accordingly, the method according to the present invention allows for bleaching of the fabric while at the same time prior to the step of contacting the fabric with the bleaching composition and / or during the step of contacting the fabric with the bleaching composition and / or Washing the fabric with a detergent composition comprising at least one surfactant, optionally after the step of contacting the fabric with the bleaching composition, before the rinsing step and / or after the rinsing step Enable

In another embodiment of the present invention, a method for bleaching a fabric comprises contacting the fabric with a liquid bleaching composition in the neat form according to the present invention, for a time sufficient to bleach said fabric, typically Maintaining the fabric in contact with the bleaching composition for 5 seconds to 30 minutes, preferably 1 minute to 10 minutes, and then rinsing the fabric with water. If the fabric is to be washed, that is, if it is to be washed with a conventional composition comprising at least one surfactant, the washing may be performed before or after the fabric is bleached. Advantageously, the present invention provides a liquid that is safe for color and the fabric itself, and that can be bleached on the fabric in its neat form, despite the old prejudice against using the bleach-containing composition in the neat form for the fabric. A bleaching composition is provided.

Alternatively, after the above-described stock bleaching method (pretreatment agent application), instead of performing a water rinsing step and / or a conventional washing step using a liquid or powder conventional detergent, a bleaching pretreatment operation may be performed. Later, the dilution bleaching method as described above may be performed in a bucket (hand washing operation) or in a washing machine.

It is preferred that the bleaching method herein be performed after the fabric has been washed with a conventional laundry detergent composition. In fact, after the fabric has been washed with a detergent composition, bleaching the fabric with a composition according to the present invention (typically a dilute bleaching method) results in better whiteness than when the fabric is first bleached and then washed. Debris and stain removal is provided with less energy and detergent.

In another embodiment, the present invention also includes a method of treating a hard surface as an inanimate surface. In such a method, the composition as defined herein contacts the surface to be treated. Accordingly, the present invention also includes a method of treating a hard surface with a composition as defined herein, said method comprising applying the composition only to the hard surface, preferably only the soiled portion thereof; Optionally rinsing said hard surface.

In the method of treating a hard surface according to the invention, the composition as defined herein, even in neat form, typically has up to 200 times its weight of water, preferably from 80 to its weight. In a form diluted with 2 times water, more preferably 60 to 2 times water,
It may be applied to the surface to be treated.

When used as a hard surface bleaching / sterilizing composition, the compositions of the present invention are easy to rinse and give good gloss properties to the treated surface.

By “hard surface” is understood hard surfaces as well as tableware as described above.

Packaging Forms of Liquid Compositions Depending on the end use envisioned, the compositions herein can be packaged in a variety of containers, including conventional bottles, roll-ons, sponges, brushes or bottles with atomizers. .

The present invention is further described by the following examples.

[0129]

【Example】

The following compositions were made by mixing the listed components in the listed proportions (% by weight unless otherwise noted).

[0130]

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) 6 4 4 4.3 10 Trifluoromethyl phenyl 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

[0131]

Table 2 Composition (% by weight) VI VII VIII IX X Akysoft 100 NV (trade name) 0.5 0.5 0.5 0.2 0.2 Curox (trade name) 5 7 10 10 6 Acetylacetone 0.5 0.5 0.5--N, N-dimethyl-4 -Oxopiperidinium nitrate---0.5 0.5 Propigallate 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

[0132]

Table 3 Composition (% by weight) XI XII XIII XIV XV Akysoft 100 NV (trade name) 0.5 0.5 0.5 0.2 0.2 Curox (trade name) 5 7 10 10 6 Cyclohexanone 0.5-0.5 0.5-N, N-dimethyl-3 -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

[0133]

Table 4 Composition XVI XVII XVIII XIX XX XXI XXII (% by weight) Witoconate 55 5 55 55 5 NAS 8 (40% active) (trade name) Curox (trade name) 9.5 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 cycloheptanone-----0.5 0.5 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 100 % 1.5 pH 1.5 1.5 1.5 1.5 1.5 1.5 1.5

Akyposoft 100 NV (trade name) is a product of Kao Chemicalla.
C12-C14 alkyl (ethoxy) 10 carboxylate commercially available from Gmbh. Wikconate NAS 8 (trade name) is an alkyl sulfonate commercially available from Witco AS. BHT is di-tertbutylhydroxytoluene. HEDP is ethane 1-hydroxydiphosphonate, commercially available from Monsanto under the name serieDequest. Cycloheptanone is commercially available from Aldrich. Curox® is a triple salt of potassium monopersulfate, potassium sulfate and potassium bisulfate, commercially available from Interox.

All of the above compositions, when used to bleach fabrics or to treat hard bleaching, show excellent bleaching performance as well as stock solutions and especially diluted conditions, as well as good stain removal performance.

The compositions are physically and chemically stable, ie they do not lose more than 15% of AvO after a storage period of 1 month at 25 ° C.

──────────────────────────────────────────────────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 DA05 EA19 EA20 EB03 EB04 EB09 EB12 EB19 EB20 EB24 ED02 EE05 FA16 FA28 FA43

Claims (16)

[Claims] 1. A composition comprising a persulfate and a bleach activator selected from the group consisting of aldehyde activator compounds, ketone activator compounds, halide activator compounds and mixtures thereof, having a pH of less than 7. Liquid aqueous composition. 2. The composition according to claim 1, wherein the composition comprises from 0.01% to 50% of the total weight of the composition.
%, Preferably 0.5% to 20%, more preferably 1% to 15%, most preferably 2% to 10% of said persulfate or a mixture thereof.
A composition according to claim 1. 3. The composition according to claim 1, wherein the persulfate is a monopersulfate, preferably sodium monopersulfate and / or potassium monopersulfate. 4. The composition according to claim 1, wherein the composition comprises from 0.01% to 10% of the total weight of the composition.
%, Preferably 0.05% to 5%, more preferably 0.1% to 2%, most preferably 0.2% to 1.5% of said ketone, aldehyde and / or halide activator compound. The composition according to any one of claims 1 to 3, comprising: 5. The bleach 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, ethyllevulinate , 3-hydroxy-2-pentanone, acetone, 3-pentene-
2-one, 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-nitro Acetophenone, p-chloroacetophenone, p-diacetylbenzene, N-methyl-p-morpholinoacetophenone nitrate, phenacyltriphenylphosphonium nitrate, 2-acetylpyridine, 2-acetyl Pyridine N-oxide, 3-acetylpyridine, 4-acetylpyridine, 4-acetylpyridine N-oxide, 2,6-diacetylpyridine, 3-acetylpyridine N-oxide, triacetylbenzene, cyclohexanone, 2-methylcyclohexanone, , 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, 3oxo-cyclohexylacetic acid,
Cycloheptanone, 1,4-cyclohexadione, dehydrochloric acid, tropinone methonitrile, N-methyl-3-oxoquinuclidinium nitrate, cyclooctanone, cyclopentanone, 2,2,6,6 -Tetramethyl-4-piperidone hydrate, 1-methyl-4-piperidone N-oxide, N-carbethoxy-4-
Claims: piperidone, tetrahydrothiopyran-4-one methnitrate, tetrahydrothiopyran-4-one S, S-dioxide, tetrahydrothiopyran-3-one S, S-dioxide, 4-oxacyclohexanone or a mixture thereof. Item 6. The composition according to any one of Items 1 to 5. 6. The bleach activator is an oxopiperidinium salt having the formula: ## STR1 ## 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
The composition according to any one of claims 1 to 5, which is an ammonium acetophenone salt optionally substituted by one or more of the substituents defined for 3 or a halogen atom. 7. The bleach activator according to claim 1, wherein the 1,1-dimethyl-3-oxopiperidinium nitrate, 1,1-dimethyl-4-oxopiperidinium triflate, 1,1-dimethyl-3-oxopiperidine. Peridinium 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-4-oxopiperidinium nitrate 4-trimethylammonium acetophenone nitrate, 2-trimethylammonium acetophenone nitrate,
The composition according to any one of claims 1 to 6, which is 4-triethylammonium acetophenone mesylate, 3-trimethylammonium acetophenone mesylate, trihalogenated methylphenyl ketone, or a mixture thereof. 8. The composition according to claim 1, wherein said composition is from 0.1 to 6, more preferably from 0.5 to 4.
More preferably having a pH in the range from 1 to 3, most preferably from 1 to 2,
A composition according to any one of claims 1 to 7. 9. The composition according to claim 1, wherein the composition typically comprises up to 5% by weight of the total composition.
9. The composition according to any of the preceding claims, further comprising preferably 0.01% to 1.5% of a chelating agent or a mixture thereof. 10. The chelating agent is a phosphonate chelating agent, an aminocarboxylate chelating agent, another carboxylate chelating agent, a polyfunctionally substituted aromatic chelating agent, ethylenediamine N, N′-disuccinic acid or a mixture thereof. Preferably, it is aminoaminotri (methylene phosphate), diethylenetriaminopentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine N, N'-succinic acid and a mixture thereof. Composition. 11. The composition further comprises up to 10%, preferably 0.001% to 0.5% by weight, of a radical scavenger or a mixture thereof, wherein the radical scavenger comprises: Preferably, di-ter
t-butylhydroxytoluene, hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1,1,3- 2. Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and / or n-propyl gallate.
0. The composition according to any one of 0. 12. The composition according to claim 1, wherein said composition is 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, a foam inhibitor, a whitening agent, The composition according to any one of claims 1 to 11, further comprising at least one optional component selected from the group consisting of a fragrance, a pigment, a dye, and a mixture thereof. 13. A method of bleaching a fabric, comprising: contacting the fabric with a bleaching composition according to any of the preceding claims in diluted or undiluted form, for a time sufficient to bleach the fabric. Maintaining the fabric in contact with the bleaching composition, and then rinsing the fabric with water. 14. The method according to claim 13, 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. 15. Before the step of contacting said fabric with said bleaching composition and / or
Alternatively, during the step of contacting the fabric with the bleaching composition in a diluted form and / or after the step of contacting the fabric with the bleaching composition, prior to the rinsing step and / or after the rinsing step, the fabric may have at least one 15. The method according to claim 13 or 14, wherein the method is washed with a detergent composition comprising two surfactants. 16. The method according to any one of claims 1 to 12, wherein the method comprises the steps of applying the composition in a neat or diluted form to a hard surface and optionally rinsing the hard surface. A method of treating said hard surface with a composition as described.