JP2001522932A - Laundry bleaching composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a garment having a pH of up to 7 and comprising a peroxide bleach, 0.1% to 10% of a pH buffer by weight of the total composition, and 0.0001% to 5% of a fragrance by weight. Liquid compositions suitable for pre-treating The composition is suitable for bleaching soiled textile fabrics, especially for pretreatments which do not impair the color of the fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD This invention relates to bleaching of soiled garments, and to compositions suitable for use as laundry detergents and especially as laundry pre-treatment agents.

BACKGROUND Peroxide bleach-containing compositions have been described extensively in laundry applications as laundry detergents, laundry additives or even pre-washing agents. In fact, in the application of laundry treatment, acidic to neutral pH (typically up to 7,
Liquid peroxide bleach-containing compositions, preferably having 1 to 6, and more preferably about 5), are greases, coffees, teas, which are particularly difficult to remove otherwise.
It is known to be used to enhance the removal of stickiness / soil such as grass, mud / clay containing soils and the like. However, we note that the disadvantages associated with such peroxide bleach-containing compositions are that when these compositions are used for pretreatment applications, i.e., they are applied directly on the garment (neat) and the garments are rinsed. It has been found that the color of the garment may be impaired when left to work on the garment for an extended period of time before washing or rinsing the clothing and subsequently rinsing them.

[0003] Thus, especially in pretreatment applications where the composition is left in the neat solution before being rinsed or washed and subsequently contacted with clothing for a long time before rinsing them, It is an object of the present invention to provide improved color safety for garments. In fact, when pre-treating clothing with a composition consisting of a peroxide bleach such as hydrogen peroxide formulated at a pH of up to 7, it is applied to the clothing in a stock solution and acts before it is rinsed off. The composition left untreated tends to evaporate on clothing. It has been observed that when such peroxide bleach-containing compositions evaporate, the water contained in such compositions evaporates faster than the peroxide bleach. In other words, water evaporation contributes to increasing the concentration of peroxide bleach in the liquid composition poured onto the surface of the garment. This higher concentration hasten the production of free radicals and consequently damage to the garment and its color. It is also assumed that when the liquid composition is left to dry on clothing, evaporation of water causes an autoxidation reaction. This autoxidation reaction contributes to the decomposition of cellulose and certain dyes present in the garment, thereby resulting in bleaching and / or chemical damage of the dye molecules, which is seen as a change in hue. Thus, instructions for the use of such commercially available peroxide bleach-containing compositions may require that the liquid bleach composition not be left dry on the garment in the pre-treatment step of the soiled garment. Highly recommended. More surprisingly, this process of evaporation is also accompanied by an increase in bleach concentration plus pH
Is known to result in a decrease in Strong acidity, typically lowering the pH to below pH 2, accelerates color damage in the pretreatment of colored garments. Improved color safety has a pH of up to 7, and a peroxide bleach, 0.1% to 10% pH buffer by weight of the total composition and 0.0001% to 5% fragrance by weight It has now been found that this can be achieved by formulating a liquid bleach composition consisting of More particularly, the use of a pH buffer for the pretreatment of soiled, colored clothing in a peroxide bleach-containing composition having a pH of up to 7 is pretreated by such a composition. It has been found to significantly reduce the color damage of worn clothing.

[0004] Advantageously, the compositions according to the invention also provide effective garment safety in addition to effective color safety. Another advantage of the present invention is that it also provides excellent bleaching ability against a wide range of stains and stains, such as bleachable stains and / or oily stains. Another advantage of the present invention is not only when the composition according to the invention is used for application in laundry pre-treatment, but also for application in laundry, for example when used as a laundry detergent or laundry additive. It also provides superior performance when used in other applications, such as hard surface cleaning applications. Yet another advantage is that the compositions herein are physically and chemically stable upon long-term storage. In a preferred embodiment, the composition according to the invention further comprises a surfactant such as, for example, a zwitterionic betaine surfactant or a mixture thereof together with an alkoxylated nonionic surfactant. In fact, such surfactant systems of the compositions herein further increase bleaching capacity and are effective against various types of soils, including oily stains such as mayonnaise, vegetable oils, sebum, make-up and the like. It has been found to contribute to the ability to remove stains. In a highly preferred embodiment herein, the composition of the present invention comprises a salt-free zwitterionic betaine surfactant. In fact, the use of such salt-free zwitterionic betaine surfactants in place of conventional zwitterionic betaine surfactants further enhances the benefits of the present composition, i.e., improved color and clothing safety. Contribute.

SUMMARY OF THE INVENTION The present invention has a pH of up to 7 and a peroxide bleach, a pH buffer from 0.1% to 10% by weight of the total composition, and a pH bleach from 0.0001% by weight. Includes a suitable liquid composition for pretreating garments consisting of up to 5% perfume. The invention further includes the step of bleaching the garment starting from the liquid composition as defined herein. The process involves contacting the garment with a stock or dilute liquid bleach composition, and subsequently rinsing the garment. In a preferred embodiment, when the garment is "pre-treated", the composition is applied to the garment in a neat solution, and the garment is rinsed or washed in a normal wash cycle and subsequently rinsed with water. .

Detailed Description of the Invention Liquid Composition The composition according to the present invention is a liquid composition relative to a solid or a gas. "Liquid" as used herein includes "pasty" compositions. The liquid composition here is desirably an aqueous composition. The liquid composition according to the invention preferably has a pH of up to 7, more preferably 1 to 6, and even more preferably 1.5 to 5.5.
Formulation of the composition according to the invention in the acidic pH range contributes to the chemical stability of the composition and the ability of the composition to remove stains.

[0007] Peroxide bleaches: As an essential element, the compositions according to the invention consist of peroxide bleaches or mixtures thereof. In fact, the presence of peroxide bleach provides excellent bleaching and cleaning benefits. Suitable peroxide bleaches for use herein are hydrogen peroxide, their water-soluble ingredients, or mixtures thereof. As used herein, the source of hydrogen peroxide refers to any compound that produces perhydroxy ions when the compound contacts water. Suitable sources of water-soluble hydrogen peroxide for use herein are percarbonate,
Persilicate, perborate, diperoxide decanedioic acid (DPDA),
Includes peroxy acids, such as magnesium perphthalate, perlauric acid, perbenzoic acid and alkyl perbenzoic acid, hydroperoxides, aliphatic and aromatic diacyl peroxides and mixtures thereof. Preferred peroxide bleaches here are hydrogen peroxide, hydroperoxides and / or diacyl peroxides. Hydrogen peroxide is the most desirable peroxide bleach here. Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-
Hydroperoxide, di-isopropylbenzene-monohydroperoxide, t
ert-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-
Dihydroperoxide. Such hydroperoxides have the advantage of being particularly safe for clothing and color while providing excellent bleaching power. Aliphatic diacyl peroxides suitable for use herein are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof. Aromatic diacyl peroxide suitable for use herein is, for example, benzoyl peroxide. Such diacyl peroxides have the advantage of being particularly safe for clothing and colour, while providing excellent bleaching power. Typically, the compositions herein comprise from 0.1% to 20%, preferably from 1% to 15% and most preferably from 2% to 10% of the above-mentioned peroxide bleaches or their weight, based on the total composition. Consisting of a mixture of

[0008] pH buffer: As an essential component, the composition according to the invention consists of a pH buffer or a mixture thereof at a level of from 0.1% to 10% by weight of the total composition. Desirably, the compositions herein are 0.2% to 8%, preferably 0.3% to 5%, more preferably 0.3% to 3%, and most preferably 0.3% by weight of the total composition. % To 2% of a pH buffer or a mixture thereof. By "pH buffer" is meant a compound that, when added to a solution, forms a solution that resists changes in hydrogen ion concentration due to the addition of acids or alkalis. A preferred pH buffer for use herein is a pKa in the range of from 1.5 to 6.5, preferably from 2 to 6, and more preferably from 4 to 6, or at least one of the pKas. Consists of a weak acid with one and its conjugate base. pKa is defined by the following equation: pKa = −logKa where Ka is the dissociation constant of the weak acid in water and corresponds to the following equation: [A ⁻ ] [H ⁺ ] / [HA] = Ka where Where HA is an acid and A ^- is a conjugate base.

By “conjugate base” is meant here the corresponding base (A ⁻ ) of a weak acid (HA). This conjugate base is obtained by adding an alkali source to a composition according to the invention consisting of a weak acid as defined herein. Suitable alkali sources suitable for use herein are caustic such as sodium hydroxide, potassium hydroxide and / or lithium hydroxide and / or alkali metal oxides such as sodium and / or potassium oxide. A preferred source of alkali is caustic, more preferably sodium hydroxide and / or potassium hydroxide. Alternatively, the conjugate base is itself available for purchase and may be added directly to the weak acid herein. Typically, according to the present invention the weak acid (HA) and its conjugate base (A ^-) is in equilibrium according to the following equation in the compositions of the present ^{invention: HA ← → A - + H} + ( hydrogen ions) preferably The pH buffer herein is preferably a weight ratio of weak acid to its conjugate base of from 0.1: 1 to 10: 1, more preferably from 0.2: 1 to 5: 1, and a weak acid as defined herein. And its conjugate base. A very desirable ratio of weak acid to its conjugate base is 1, as this is the best combination to achieve optimal buffering capacity. Desirably, the pH buffer given here is pH = P each of its pKa
It will be used to buffer compositions having a pH between Ka-1 and pH = pKa + 1. For example, citric acid / citrate is between 3.74 and 5.74 (pKa
2 = 4.74) and a pH comprised between 2.06 and 4.06 (pKa1 = 3.06)
It is particularly suitable for buffering compositions having Suitable weak acids having at least one pKa from 1.5 to 6 for use herein are citric acid (pKa1 = 3.06, pKa2 = 4.74), oxalic acid (pKa2 =
4.19), tartaric acid (pKa1 = 2.99, pKa2 = 4.34), phthalic acid (pKa1 = 2.89, pKa2 = 5.41), acetic acid (pKa = 4.74), benzoic acid (pKa = 4.20), formic acid (pKa = 3.76) and salicylic acid (pKa1 =
2.97). Particularly suitable pH buffers for use herein are citric acid / sodium citrate, citric acid / potassium citrate, oxalic acid / sodium oxalate, tartaric acid / potassium hydrogen tartrate, oxalic acid / potassium tetraoxalate dihydrate, phthalic acid Acid / potassium phthalate, acetic acid / sodium acetate, formic acid / sodium formate, benzoic acid / sodium benzoate and / or salicylic acid / sodium salicylate. Preferred pH buffers for use herein are citric acid / sodium citrate, citric acid / potassium citrate, oxalic acid / sodium oxalate, tartaric acid / potassium hydrogen tartrate, oxalic acid / potassium tetraoxalate dihydrate, and Most desirable are citric acid / sodium citrate and / or citric acid / potassium citrate. A highly desirable pH buffer for use herein is citric acid / sodium citrate. Citric acid is commercially available under its chemical name from Sigma Aldrich and Flucka Chemicals.

Perfume: As an essential component, the composition according to the invention comprises a perfume or a mixture thereof at a level of from 0.0001% to 5% by weight of the total composition. Desirably, the composition herein comprises from 0.0001% to 1%, more preferably from 0.001% to 1%, and most preferably from 0.01% to 0.5% by weight of the total composition or perfume. Consisting of a mixture of Of course, perfumes for use herein for the purposes of the present invention are stable to peroxide bleaches. By "stable" for peroxide bleaches is meant here fragrances which show odor stability after storage at 50 DEG C. for 10 days and do not affect the stability of the product. Perfumes suitable for use herein include substances that provide olfactory benefits and / or help mask "chemical" odors that the product may have. The main function of the small fractionation of the highly volatile, low boiling (having a low boiling point) scent in these perfumes is that the product's own scent rather than affecting the odor remaining on the surface being cleaned It is to improve. However, some of the less volatile, high boiling perfume ingredients give the surface a fresh and clean impression, and it is desirable that these ingredients be deposited and present on a dry surface. The perfume component can be readily solubilized in the composition, for example, by a non-ionic detersive surfactant. Perfume ingredients and compositions suitable for use herein are conventional as known in the art. The choice of perfume composition, or amount of perfume, is based primarily on sensory considerations.

Suitable fragrance compounds and compositions are described in US Pat. Nos. 4,145,184 issued March 20, 1979 to Brain and Cummins; 4,209,417 issued June 24, 1980 to Whyte. No. 4,515,705 issued May 7, 1985 to Moeddel; and No. 4,152,272 issued May 1, 1979 to Young, Here, all of the aforementioned patents are cited as references. In general, the degree of predominance of a perfume is roughly proportional to the percentage of the main perfume substance used. A relatively major flavor is at least about 1%, desirably at least about 1%.
Contains 0% of major perfume substances. The major perfume substances are scented compounds which deposit on surfaces throughout the course of washing and are detectable by persons with normal olfactory acuity. Such materials typically have a lower vapor pressure than that of the average perfume material. Also, they typically have a molecular weight of about 200 and above and are detectable at lower levels than those of the average perfume substance. The perfume ingredients useful herein, together with their odor properties and their physical and chemical properties such as boiling point and molecular weight, are hereby incorporated by reference but were published by the authors in 1969.
It is shown in Steffen Arctander's "Perfume and Flavor Chemicals (Aroma Chemicals)". Examples of high volatility, low boiling point perfume ingredients are: anethole, benzyl acetate, benzyl alcohol, iso-bornyl acetate, camphene, citronellol, citronellyl acetate, para-cymene, dihydrolinalool,
Dihydromyrcenol, dimethylphenylcarbinol, eucalyptol, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate , Alpha-methylionone, methylnonylacetaldehyde, methylphenylcarbinyl acetate,
Levo-menthyl acetate, menthone, iso-menthone, miculene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate,
Phenylethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate, and vertenex (para-tertiary butylcyclohexyl acetate)
. Some natural oils also contain a high percentage of highly volatile fragrance ingredients. For example,
Labandin contains as major components: linalool; linalyl acetate; geraniol; and citronellol. Both lemon oil and orange terpenes contain about 95% d-limonene.

Examples of slightly volatile fragrance ingredients are: amylcinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, sedren, cinnamon alcohol,
Dimethylbenzylcarbinyl acetate, ethyl crocodile, eugenol, iso-eugenol, floracetate, heliotropin, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tertiary butyl-alpha-methylhydrocinnamic aldehyde), gamma -Methylionone, nerolidol,
Patchouli alcohol, phenylhexanol, beta-selinen, triethyl citrate, crocodile, and veratraldehyde. Cedar terpenes consist primarily of alpha-sedrene, beta-cedrene and other C15H24 sesquiterpenes. Examples of less volatile, high boiling perfume ingredients are: benzophenone, benzyl salicylate, ethylene brassate, hexylcinnamic aldehyde, linal (4- (4-hydroxy-4-methylpentyl) -3-. Cyclohexene-10-carboxaldehyde), methyl sedrone, methyl dihydrojasmonate, methyl-beta-naphthyl ketone, and phenylethylphenyl acetate. The choice of a particular perfume ingredient is dictated primarily by sensory considerations.

[0013] The present invention provides a method for pre-treating a peroxide bleach comprising a composition having a pH of up to 7 before rinsing the clothes or washing the clothes and then rinsing the clothes. The drop in pH that occurs when applied as a stock solution and left to work (and evaporates) is based on the finding that pH buffers are reduced. In other words, the color damage of certain dyes (eg, blue and / or green dyes especially found in colored garments made from silk) is such that up to seven such dirty colored garments may When bleached with a composition containing a peroxide bleach and a pH buffer having a pH, the color change and / or bleaching observed when using the same composition without the pH buffer is reduced. This change in color and / or reduction in bleaching can be attributed to pre-treatment applications where the composition is left to dry or partially dry on soiled colored garments, which is typically 5 to 60 In the range of minutes.). Color damage to colored clothing can be assessed visually and / or HunterLab Tristimulu
Evaluation is made by side-by-side comparison of colored clothing bleached according to the invention with colored clothing bleached, for example, with a standard composition without a pH buffer, according to the instrumental method according to MINISCAN®. Advantageously, the presence of copper and / or iron and / or manganese and / or chromium on the garment surface, and / or the loss of tension caused by exposure to UV radiation by sunlight, may also result from the composition according to the invention. Less when bleaching and especially pre-treating garments soiled with water.

The loss of clothing tension is measured by using a tension method. The method comprises measuring the tension of a given garment by stretching the garment until it breaks. The force required to break a garment, expressed in Kg, is the "ultimate tension" and is measured on the Stress-Strain INSTRON Machine available from INSTRON. The loss of tension is the difference in tension between a garment taken as a standard, i.e., unbleached garment, and the same garment after being bleached. A loss of zero tension means that no damage to the garment is observed. Also, reduced garment loss of tension and / or reduced color damage can be obtained by the present invention without compromising bleaching or soil removal capabilities. Also an advantage of the compositions of the present invention is that they are physically and chemically stable upon long-term storage. More particularly, p in the composition according to the invention
The H buffer contributes to the excellent chemical stability of the composition on long-term storage. More specifically, the pH buffers used in the compositions herein, especially citric acid /
A second advantage of citrates is that they act as antioxidants, i.e. they absorb oxygen present in the environment in which they are bleached and thus oxidize present in the bleaching composition. Reduces oxidative degradation of sensitive components, ie, peroxide bleaches, fragrances, dyes and the like. The chemical stability of the compositions herein is assessed by measuring the available oxygen (often abbreviated as AvO2) concentration for a given shelf life after the composition is made.
The concentration of available oxygen can be measured by chemical titration methods known in the art, such as iodometric, thiosulfatimetric, permanganate and serimetric methods. The criteria for the selection of the above method and the appropriate method are, for example, “Hydrogen Peroxide”, WC Schumb, CN Satterfie
ld and RL Wentworth, Reinhold Publishing Corporation, New York, 19
1995 and “Organic Peroxides”, Daniel Swern, Editor Wiley Int. Scie
nce, 1970, described therein. By "physically stable" is meant here that no phase separation occurs in the composition at 50 ° C. for 14 days.

Optional Ingredients The composition herein may further comprise a surfactant, chelating agent, radical scavenger, antioxidant, builder, stabilizer, bleach activator, soil suspending agent, soil suspended polyamine. Consist of a variety of other optional ingredients such as polymers, polymerized soil release agents, catalysts, dye transfer agents, solvents, brighteners, perfumes, pigments, and dyes.

Surfactant: The composition according to the invention may comprise a surfactant or a surfactant as a highly desirable optional ingredient.
Consisting of these mixtures. Of course, surfactants are peroxide bleached for the purposes of the present invention.
Stable to agents. Typically, the compositions of the present invention comprise up to 60% by weight of the total composition, preferably 0.1%
To 30%, more preferably 0.5% to 15%, and most preferably 1% to 10% of a surfactant or mixture thereof. Surfactants suitable for use herein are nonionic, anionic and amphoteric.
And cationic and / or amphoteric surfactants. Surfactants that are particularly suitable for use herein are the alcohols described herein below.
Nonionic surfactants such as xylated nonionic surfactants and / or poly
Hydroxy fatty acid amide surfactants and / or amine oxides and / or
Is a zwitterionic surfactant such as a zwitterionic betaine surfactant. Suitable alkoxylated nonionic surfactants for use herein are of the formula RO-C _Two H_FourO)_nA nonionic surfactant ethoxylated with H, where R is C₆To C_{twenty two}Alkyl chain or C₆To C₂₈An alkylbenzene chain, where n is 0 to 20, preferably 1 to 15, and more preferably 2 to 15, and so on.
And most preferably from 2 to 12. The preferred R chain for use herein is C ₈ To C_{twenty two}Is an alkyl chain. Propoxylated nonionic surfactants and ethoxylated / propoxylated surfactants are also known as ethoxylated nonionic surfactants as defined herein above.
It may be used here instead of a surfactant or together with the above-mentioned surfactants.

Preferred ethoxylated nonionic surfactants are according to the above formula, and below 16
It preferably has an HLB (hydrophilic-hydrophobic balance) of 15 or less, more preferably 14 or less. These ethoxylated nonionic surfactants have been found to provide good grease removal properties. Therefore, suitable ethoxylated nonionic surfactants for use herein are Dobano
l (trade name) 91-2.5 (HLB = 8.1; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 2.5) or Lutensol (trade name) TO3 (HLB = 8; R is C ₁₃ alkyl chain, n is 3), or Lutensol (trade name) AO3 (HLB = 8; R is a mixture of C ₁₃ and C ₁₅ alkyl chains, n is 3), or Tergitol (trade name) 25L3 (H
LB = 7.7; R is an alkyl chain length ranging from C ₁₂ to C ₁₅ , n is 3), or Dob
anol (trade name) 23-3 (HLB = 8.1; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 3), or Dobanol (trade name) 23-2 (HLB = 6.2; R Is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 2) or Dobanol 45-7 (HLB = 11.6; R is a mixture of C ₁₄ and C ₁₅ alkyl chains, n is 7) , Dobanol (trade name) 23-6.5 (HLB = 11.9; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 6.5), or Dobanol (trade name) 25-7 (H
LB = 12; R is a mixture of C ₁₂ and C ₁₅ alkyl chains, n is 7) or Do
banol (trade name) 91-5 (HLB = 11.6; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 5), or Dobanol (trade name) 91-6 (HLB = 12.5;
R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 6), or Dobanol® 91-8 (HLB = 13.7; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 8) ), Dobanol (trade name) 91-10 (HLB = 14.2; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 10), or a mixture thereof. Desirable here are Dobanol (trade name) 91-2.5, or Lutensol (trade name) TO3, or Lutensol (trade name) AO3, or Tergitol (trade name) 25L3, or D
obanol (trade name) 23-3 or Dobanol (trade name) 23-2 or a mixture thereof. These Dobanol (R) surfactants can be purchased from SHELL. These Lutensol® surfactants are available from BASF and these Tergitol® surfactants are available from UNION CARBIDE.

A suitable chemical process for preparing the alkoxylated nonionic surfactant for use herein involves condensation of the corresponding alcohol with the alkylene oxide in the desired ratio. Such processes are well known in the art and have been widely described in the art. The compositions herein may desirably consist of one of these ethoxylated nonionic surfactants or a mixture of these ethoxylated nonionic surfactants with different HLB (hydrophilic-lipophilic balance). In a preferred embodiment, the compositions herein are ethoxylated nonionic surfactants according to the above formula and having an HLB of up to 10, preferably 10 or less, more preferably 9 or less (ie, so-called hydrophobic ethoxylated). A nonionic surfactant), and according to the above formula, and 10
Consisting of an ethoxylated nonionic surfactant having an HLB of from 1 to 16 and desirably from 11 to 14 (ie a so-called hydrophilic ethoxylated nonionic surfactant). In fact, in this preferred embodiment, the compositions of the present invention typically comprise from 0.01% to 15%, preferably from 0.5% to 10%, of a hydrophobic ethoxylated nonionic surfactant by weight of the total composition; And 0.01% to 15% by weight, preferably 0.5%
To 10% of a hydrophilic ethoxylated nonionic surfactant. Different HLB
Mixtures of such ethoxylated nonionic surfactants with different hydrophobicity /
This is desirable because it provides optimal oil wash removal capability for a wide range of oil stains having hydrophilic properties.

Other particularly suitable nonionic surfactants for use herein are those of the following structural formula
Including polyhydroxy fatty acid amide surfactants or mixtures thereof according to: R^Two-C (O) -N (R¹) -Z where R¹Is H or C₁-C_FourAlkyl, C₁-C_FourHydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R^TwoIs C_Five-C₃₁ A hydrocarbon, and Z is a straight-chain carbon having at least three hydroxyl groups directly attached to the side chain
Polyhydroxy hydrocarbons with hydrogenated chains or their alkoxylated derivatives
It is. Preferably R¹Is C₁-C_FourAlkyl, more preferably C₁Or C_TwoAlkyl, and most preferably methyl, R^TwoIs linear C₇-C₁₉Alkyl or a
Lucenyl, preferably linear C₉-C₁₈Alkyl or alkenyl, more preferably straight chain C₁₁-C₁₈Alkyl or alkenyl, and most preferably straight chain C ₁₁ -C₁₄Alkyl or alkenyl or a mixture thereof. Z is desired
Or from a reducing sugar by a reductive amination reaction;
It is Cytil. Suitable reducing sugars are glucose, fructose, maltose, lacto
Includes glucose, galactose, mannose, and xylose. As raw material, on
Not only the single sugars listed, but also high dextrose corn syrup, high fructo
Sucrose corn syrup and high maltose corn syrup can be used
You. These corn syrups may produce a mixture of sugar components for Z. other
It should be understood that no intention is made to exclude the appropriate ingredients of
It is. Z is preferably -CH_Two-(CHOH)_n-CH_TwoOH, -CH (CH_Two(OH)-(CHOH)_n-1-CH_TwoOH, -CH_Two-(CHOH)_Two(CHOR ') (CHO H) -CH_TwoOH, where n is an integer from 3 to 5 inclusive, and
R 'is H or a cyclic or aliphatic monosaccharide, and their alky!
It is a coxylated derivative. Most preferred is glycityl, where n is 4,
Especially CH_Two-(CHOH)_Four-CH_TwoOH. Formula R^Two-C (O) -N (R¹) -Z, R¹Is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl
Or N-2-hydroxypropyl. R^Two-CO-N <
Is, for example, cocamide, stearamide, oleamide, lauramide, myristamide
, Capricamide, Palmitamide, Tallowamide and the like
Wear. Z is 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymer
Rutile, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxy
It can be mannitol, 1-deoxymaltotriotityl and the like.
Wear. Suitable polyhydroxy fatty acid amide surfactants for use herein are Hoechs
It can be purchased under the trade name HOE (trade name) from t.

[0020] Methods for making polyhydroxy fatty acid amide surfactants are known in the art. Generally, they react alkylamines with reducing sugars in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamines, and then condense to form N-alkyl, N-polyhydroxy fatty acid amide products / Amidation step by reacting an N-alkyl polyhydroxyamine with an aliphatic ester or triglyceride. Processes for preparing compositions comprising polyhydroxyfatty acid amides are described in, for example, British Patent Specification published February 18, 1959 by Thomas Hedley & Co. Ltd., each of which is incorporated by reference. U.S. Pat. No. 2,965,576 issued to ER Wilson on Dec. 20, 1960; Mar. 1955.
U.S. Pat. No. 2,703,798 issued to Anthony. M. Schwartz on Aug. 8, 1;
It is disclosed in U.S. Patent No. 1,985,424 issued to Piggott on December 25, 934 and in WO 92/06070. Other suitable nonionic surfactants for use herein are those in which each R ₁ , R ₂ , and R ₃ is independently saturated or unsubstituted from 1 to 30 carbon atoms. And amine oxides having the following formula R ₁ R ₂ R ₃ NO which is a linear or branched hydrocarbon chain. Amine oxide surfactants desirable for use by the present invention 30 R ₁ is one to here, preferably 20 to 6, more 16 Nozomu Mashiku from eight, most preferably from 8 A hydrocarbon chain of 12 carbon atoms, wherein R ₂ and R ₃ are each independently substituted or unsubstituted, linear or branched, of 1 to 4, preferably 1 to 3 carbon atoms An amine oxide having the formula R ₁ R ₂ R ₃ NO which is a linear hydrocarbon chain, and more preferably a methyl group. R ¹ may be a saturated substituted or unsubstituted, straight or branched hydrocarbon chain. Suitable amine oxides for use herein are, for example, naturally occurring mixed C8-C10 amine oxides and also C12-C16 amine oxides, which can be purchased from Hoechst.

Another class of surfactants particularly suitable for use herein are cationic hydrophilic groups, ie, quaternary ammonium groups, and anionic hydrophilic groups on the same molecule over a relatively wide range of pH. And zwitterionic betaine surfactants containing both. Typical anionic hydrophilic groups are carboxylate and sulfonate, although other groups such as sulfates, phosphonates, and the like can be used. The general formula of the zwitterionic betaine surfactant for use 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, hydroxyalkyl or other substituted C ₁ -C ₆ alkyl group; R ₃ is C ₁ -C ₆ alkyl, hydroxyalkyl or also cyclic with N Other substituted C ₁ -C ₆ alkyl groups, or C ₁ -C ₆ carboxylic acid groups or C ₁ -C ₆ sulfonate groups, which can be attached to R ₂ to form a structure; R ₄ is hydrophilic X is a carboxylate or sulfonate, and is a residue that attaches a cationic nitrogen atom to the functional group, and is typically an alkylene, hydroxyalkylene, or polyalkoxy group containing from 1 to 10 carbon atoms. Hydrophilic group A group. Desirable hydrophobic groups R ₁ are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains which can contain linking groups such as amide groups, ester groups. More preferred R ₁ is an alkyl group containing 1 to 24, preferably 8 to 18, and more preferably 10 to 16 carbon atoms. These simple alkyl groups are desirable for cost and stability reasons. However, the hydrophobic group R ₁ can also be an amide group of the formula R _a —C (O) —NH— (C (R _b ) ₂ ) _m , where R _a is aliphatic or aromatic, saturated or An unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 to 20, preferably up to 18, more preferably up to 16 carbon atoms, wherein R _b is hydrogen and Is selected from the group consisting of hydroxyl groups, and m is from 1 to 4, preferably 2 to 3, more preferably 3, and does not have more than one hydroxyl group in any (C (R _b ) ₂ ) group. Desirable R ₂ is hydrogen or C ₁ -C ₃ alkyl, and more preferably methyl. Desirable R ₃ is a C ₁ -C ₄ carboxylic acid group, or a C ₁ -C ₄ sulfonate group, or a C ₁ -C ₃ alkyl, and more preferably methyl.
Desirable R ₄ is (CH ₂ ) _n , where n is an integer from 1 to 10, preferably 1 to 6, more preferably 1 to 3. Some general examples of betaines / sulfobetaines are incorporated herein by reference, but are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082. Have been.

Examples of particularly suitable alkyl dimethyl betaines are coconut dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N, N-dimethyl-ammonia) acetate, 2- (N-coco N, N -Dimethyl-ammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, for example coconut dimethyl betaine is available from Seppic under the trade name Amonyl 265 (trade name). Can be purchased from Albright & Wilson under the trade name Empigen BB / L (trade name) Examples of amide betaines are cocoamidoethyl betaine, cocoamidopropyl betaine or C10-C14 aliphatic acylamidopropylene (hydropropylene) For example, C10-C14 aliphatic acylamidopropylene (hydropropylene) sulfobetaine is available from Sherex Company under the trade name "Varion CAS (TM) sulfobetaine." Lauryl-imino-dipropionate, commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA, is a zwitterionic betaine surfactant that is particularly desirable for use herein is salt-free, The zwitterionic betaine surfactant feedstock contains less than 5%, preferably less than 2%, more preferably less than 1%, and most preferably 0.01% to 0.5% salt by weight. Here, “salt” refers to several cations (or positive molecular ions) and one or Any substance having an anion (or negative molecular ion) containing more halogen atoms is meant, such salts include sodium chloride, potassium chloride, sodium bromide and the like. Salt-free zwitterionic betaine surfactants can be obtained by conventional manufacturing processes such as reverse osmosis or fractional precipitation, for example, reverse osmosis is a zwitterionic betaine surfactant raw material (purchasable) ) For example acetate-
It is based on the theory of contacting polar solvents separated by a semipermeable membrane such as cellulose (it should be understood that such solvents are salt-free). Appropriate pressure is applied to the system to transfer the salt from the surfactant source material to the polar solvent phase. In this way, the zwitterionic surfactant raw material is purified,
That is, the salt is removed from the source material. Advantageously, the use of such a salt-free zwitterionic betaine surfactant is similar to that of a similar zwitterionic betaine surfactant containing a higher amount of salt. It has been surprisingly found that when bleaching garments with an oxide bleach-containing composition, they deliver improved garment safety and / or color safety. Thus, in its broadest aspects, the present invention also provides a salt-free zwitterionic betaine surfactant, peroxide bleaching, for bleaching soiled garments, especially for pre-treating soiled garments. Including the use of a composition comprising an agent and a pH buffering agent, thereby improving color safety (ie, reducing color damage / fading) and / or improving garment safety.

In a preferred embodiment, the surfactant present in the composition of the present invention is a mixture of an ethoxylated nonionic surfactant and a betaine zwitterionic surfactant. In fact, such betaine zwitterionic surfactants and ethoxylated nonionic surfactants provide improved bleaching ability to the liquid peroxide bleach-containing compositions of the present invention comprising them, (E.g., lipstick, olive oil, mayonnaise, vegetable oils, sebum, make-up) to work together to deliver excellent soil removal. In fact, remarkable cooperation has been found in a variety of applications such as particulate to non-particulate stains, hydrophobic to hydrophilic stains, especially in household applications, and especially in laundry applications to both hydrophilic and hydrophobic clothing. Stain, observed between these components to obtain optimal stain removal performance. Optimum soil removal and bleaching performance is achieved with ethoxylated nonionic surfactants and zwitterionic betaine surfactants from 0.01 to 20, preferably from 0.1 to 15,
More preferably, the book comprises a peroxide bleach (pH 7 or less) in a weight ratio of the ethoxylated nonionic surfactant to the zwitterionic betaine surfactant of 0.5 to 5 and most preferably 0.6 to 3. Obtained when present in the composition of the invention. Importantly, the advantages of improved stain removal and bleaching are delivered with liquid compositions that are clear and permeable compositions, such as water. The appearance of the composition can be evaluated by turbidity analysis. For example, the permeability of the composition can be evaluated by measuring the absorption at a wavelength of 800 nm with a spectrophotometer.

[0024] Less desirable than the surfactants mentioned above for their stain removal properties.
However, other surfactants may also be used in the compositions herein. The composition here
Suitable anionic surfactants for use in the polymer are of the formula ROSO_ThreeWater-soluble salt of M
Alternatively, it comprises an acid, wherein R is preferably C_Ten-C_{twenty four}Hydrocarbons, preferably C _Ten -C₂₀Alkyl or hydroxyalkyl having an alkyl moiety of
Or C₁₂-C₁₈And M is H
Alternatively, for example, an alkali metal cation (eg, sodium, potassium, lithium)
, Or ammonium or substituted ammonium (eg, methyl-, dimethyl-
And trimethylammonium cations, and tetramethyl-ammonium
And quaternary ammonium cations such as dimethylpiperidium cation and
Like ethylamine, diethylamine, triethylamine and mixtures thereof
Quaternary ammonium cations derived from various alkylamines and the like)
Such a cation. Typically, lower wash temperatures (eg, below about 50 ° C.)
For C_12-16And for higher wash temperatures (eg, above about 50 ° C.)_16-18Are preferred. Other suitable anionic surfactants for use herein are of the formula RO (A)_mSO_ThreeM
Is a water-soluble salt or acid, wherein R is C_Ten-C_{twenty four}Alkyl moieties
Kuha C₁₂-C₂₀Alkyl or hydroxyalkyl, more preferably C₁₂-C ₁₈ Unsubstituted C with alkyl or hydroxyalkyl_Ten-C_{twenty four}Alkyl or
Is a hydroxyalkyl group, A is an ethoxy or propoxy unit, and m is
Greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3.
And M is H or, for example, a metal cation (eg, sodium, potassium)
, Lithium, calcium, magnesium, etc.), ammonium or substituted ammonium
A cation that can be a ammonium cation. Alkyl ethoxylated
Also included are sulfates and also alkylpropoxylated sulfates. Place
Specific examples of substituted ammonium cations are methyl-, dimethyl-, trimethyl
Quaternary like monium and tetramethylammonium, dimethylpiperidium
Ammonium cation and ethylamine, diethylamine, triethylamine
Cations derived from alkanolamines such as, mixtures thereof and the like
including. An exemplary surfactant is C₁₂-C₁₈Alkyl polyethoxylate (1.0) sulfate, C₁₂-C₁₈E (1.0) M, C₁₂-C₁₈Alkyl polyethoxylate (2.25) sulfate, C₁₂-C₁₈E (2.25) M), C₁₂-C₁₈A
Alkyl polyethoxylate (3.0) sulfate, C12-C15 alkyl ethoxylate (3) sulfate, C₁₂-C₁₈Alkyl polyethoxylate (4
.0) Sulfate, C₁₂-C₁₈E (4.0) M, where M is appropriately
Selected from um and potassium.

Other anionic surfactants useful for cleaning purposes are also used herein
be able to. These are saponified salts (eg sodium, potassium, ammonium
And substituted ammonium such as mono-, di- and triethanolamine salts
Salt), C₉-C₂₀Linear alkyl benzene sulfonate, C₈-C_{twenty two}First grade
Or secondary alkane sulfonate, C₈-C_{twenty four}Olefin sulfonates such as citric acid as described in GB Patent Application No. 1,082,179
Sulfated polycarbohydrate produced by the sulfation of the pyrolysis products of Lucari earth metal salts
Acid, C₈-C_{twenty four}Alkyl polyglycol ether sulfate (containing up to 10 moles of ethylene oxide); C_14-16Alkyl ester sulfonates such as methyl ester sulfonate; acyl glycerol sulfonate, aliphatic oleate
Luglycerol sulfate, alkyl phenol ethylene oxide ether
Sulfate, paraffin sulfonate, alkyl phosphate, acyl isethio
Isethionates such as catenates, N-acyl taurates, alkyl sacsimine
And sulfosuccinates, monoesters of sulfosuccinates (especially saturated
And unsaturated C₁₂-C₁₈Monoesters), diesters of sulfosuccinates (especially
Saturated and unsaturated C₆-C₁₄Alkylpolysaccharides such as diesters) and sulfates of alkylpolyglucosides (nonionic non-sulfated compounds described below).
Callide sulfate, branched primary alkyl sulfate, formula RO (CH_TwoCH _Two O)_kCH_TwoCOO-M⁺Where R is C₈-C_{twenty two}Alkyl of k is from 0 to 10
An alkyl poly such as an integer and where M is a cation forming a soluble salt
Ethoxy carboxylate can be included. In tall oil or not
Is derived from rosin, hydrogenated rosin, and resinic acid and hydrogenated resinic acid.
Such resinic acids and hydrogenated resinic acids are also suitable. A further example is “Surfac
e Active Agents and Detergents ”(Vol.I by Schwartz, Perry and Berch
And II). Various such surfactants are disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin et al.
Column 58, line 29 to column 29, line 23 are also generally disclosed (see references and
Quoted). Other suitable anionic surfactants for use herein are also the acids and
Acyl sarcosinate or a mixture thereof in the form of a salt, preferably
Including a long chain acyl sarcosinate having the formula:

[0026]

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Wherein M is hydrogen or a cation residue and R is an alkyl group of 11 to 15 carbon atoms, preferably 11 to 13 carbon atoms. Desirable M is hydrogen and alkali metal salts, especially sodium and potassium. The acyl sarcosinate surfactants are derived from natural fatty acids and the amino acid sarcosine (N-methylglycine). They are suitable for use in their acid form as aqueous solutions of their salts or as powders. Being a derivative of natural fatty acids, the acyl sarcosinates are rapidly and completely biodegradable and have good skin compatibility. Accordingly, suitable long chain acyl sarcosinates for use herein are C ₁₂ acyl sarcosinates (ie, the above formula wherein M is hydrogen and R is an alkyl group of 11 carbon atoms) acyl sarcosinates) and C ₁₄ acyl sarcosinate according to (i.e., wherein M comprises an acyl sarcosinate) according to formula above hydrogen in it and R 1 is 13 carbon atom alkyl group. C ₁₂ acyl sarcosinate is commercially available, for example, as Hamposyl L-30 (trade name) supplied by Hampshire. C ₁₄ acyl sarcosinates can be purchased as e.g. HAMPOSYL M-30 to be subjected fed by Hampshire (trade name).

Chelating Agents: Accordingly, the compositions of the present invention comprise a chelating agent as a desirable optional ingredient.
Suitable chelators include phosphonate chelators, aminocarboxylate chelators, other carboxylate chelators, polyfunctionally-substituted aromatic chelators, ethylenediamine N, N'-disuccinic acid, or mixtures thereof. Any known in the art, such as selected from the group of: Chelating agents are desirable in the compositions of the present invention, particularly in the application of laundry pretreatment, as they contribute to reducing loss of clothing tension and / or color damage. In fact, chelators deactivate metal ions that are present on the surface of the garment and / or on the chelating composition (neat or diluted) and that contribute to the radical decomposition of peroxide bleach. Suitable phosphonate chelators for use herein are alkali metal ethane 1-hydroxydiphosphonate (HEDP), alkylene poly (alkylene phosphonate) and also aminoaminotri (methylene phosphonic acid) (ATMP),
Nitrilotrimethylene phosphonate (NTP), ethylenediaminetetramethylenephosphonate, and diethylenetriaminepentamethylenephosphonate (D
Aminophosphonate compounds, including TPMP). The phosphonate compounds may be present either in their acid form or as salts of some or all of their acidic functionalities with different cations. The preferred phosphonate chelating agent used herein is diethylenetriaminepentamethylenephosphonate (
DTPMP) and ethane 1-hydroxydiphosphonate (HEDP).
Such phosphonate chelating agents are available from Monsanto as DEQUEST (trade name).
It can be purchased under the trade name.

[0029] Polyfunctionally substituted aromatic chelators are also useful in the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974 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 or alkaline earth metal thereof, ammonium or a substituted ammonium salt thereof, or a mixture thereof.
Ethylenediamine N, N'-disuccinic acid, especially the (SS) isomer, is Hartman and Pe
No. 4,704,233, issued Nov. 3, 1987 to rkins. Ethylenediamine N, N'-disuccinic acid is, for example, Palmer Research L
It can be purchased from aboratories under the trade name of ssEDDS (trade name). Suitable aminocarboxylates for use herein are ethylenediaminetetraacetate, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotri-acetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaate. -Acetate, ethanol-diglycine, both including their acid forms or their alkali metal, ammonium and substituted ammonium salts in the form of propylenediaminetetraacetic acid (PDTA) and methylglycinediacetic acid (MGDA). Particularly suitable aminocarboxylates for use herein are diethylenetriaminepentaacetic acid, such as propylenediaminetetraacetic acid (PDTA) and methylglycine di-acetic acid (MGDA), which are available from BASF under the trade name Trilon FS. Further carboxylate chelators for use herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof. Other chelators for use herein are of the formula:

[0030]

Embedded image

Here, R ₁ , R ₂ , R ₃ , and R ₄ are each independently —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO ₂ , —C (O) R ′ R ′ is selected from the group consisting of —H, —OH, alkyl, alkoxy, aryl, and aryloxy; and R ′ is selected from the group consisting of: —SO ₂ R ″;
"Alkyl, alkoxy is selected from the group consisting of aryl and aryloxy;. Then _{R 5, R 6, R 7} , and R ₈ is selected from the group consisting of -H and alkyl each independently use herein Particularly preferred chelating agents for aminoaminotri (methylenephosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine N, N'-disuccinic acid, and Typically, the compositions according to the invention are up to 5% by weight of the total composition, preferably from 0.01% to 1.5% by weight, and more preferably from 0.01% to 0.5%. % Chelating agents or mixtures thereof.

Radical scavenger: The composition of the present invention may consist of a radical scavenger or a mixture thereof. Suitable radical scavengers for use herein include known substituted mono- and dihydroxybenzenes and their derivatives, alkyl and aryl carboxylates and mixtures thereof. Preferred such radical scavengers for use herein are di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, te
rt-butylhydroxyanisole, benzoic acid, toluic acid, catechol, t-
Contains butyl catechol, benzylamine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, n-propyl-gallate or mixtures thereof, and very desirable -Tert-butylhydroxytoluene. Such radical scavengers, such as N-propyl-gallate, are available from Nipa Laboratories under the trade name Nipanox S1. When used, the radical scavenger here typically comprises up to 10% by weight of the total composition.
Desirably, it is present in an amount ranging from 0.001% to 2%, and more preferably 0.001% to 0.5% by weight. The presence of the radical scavenger contributes to reducing the loss of garment tension and / or color damage when the composition of the present invention is used in laundry applications, especially in laundry pretreatment applications.

Antioxidants: The composition according to the invention may further comprise antioxidants or mixtures thereof.
Typically, the compositions herein will be up to 10% by weight of the total composition, preferably 0.002% to 5%, more preferably 0.005% to 2%, and most preferably 0.005% to 2%.
It consists of from 01% to 1% of antioxidants or mixtures thereof. Suitable antioxidants for use herein are organic acids such as ascorbic acid, adipic acid and sorbic acid, or amines such as lecithin, or amino acids such as glutamine, methionine and cysteine, or ascorbyl palmitate, Includes esters such as ascorbyl stearate and triethyl citrate or mixtures thereof. Preferred antioxidants for use herein are ascorbic acid, ascorbic palmitate, lecithin or mixtures thereof.

Bleach Activator: As an optional ingredient, the compositions of the present invention may comprise a bleach activator or mixtures thereof. Compounds which react with hydrogen peroxide by a "bleach activator" to form a peracid are meant herein. The peracid thus produced constitutes an activated bleach. Suitable bleach activators for use herein include those belonging to the class of esters, amides, imides or anhydrides. Examples of suitable compounds of this type are disclosed in British Patents GB 1 586 769 and GB 2 143 231 and methods for forming them into granular molds are described in European Patent Application EP-A-62.
523. Suitable examples of such compounds for use herein are tetraacetylethylenediamine (TAED), sodium-3,5,5-trimethylhexanoyloxybenzenesulfonate, such as US Pat. No. 4,818,
Diperoxide decanoic acid as described in U.S. Pat. No. 425, and nonylamide and n-nonanoyloxybenzenesulfonate of peroxyadipic acid as described, for example, in U.S. Pat. No. 4,259,201. NOBS). Also suitable are substituted or unsubstituted benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, butanoylcaprolactam, pentanoylcaprolactam Alternatively, it is an N-acylcaprolactam selected from the group consisting of mixtures thereof. A particular group of bleach activators of interest is disclosed in EP 624 154, and a particularly desirable member of that group is acetyltriethyl citrate (ATC). Acetyltriethyl citrate has the advantage of being environmentally friendly as it eventually breaks down into citric acid and alcohol. In addition, acetyltriethyl citrate has excellent hydrolytic stability in the product upon storage and is an effective bleach activator. Finally, it provides the composition with excellent structure-forming ability. The composition according to the invention may comprise from 0.01% to 20%, preferably from 1% to 10%, and more preferably from 3% to 7% by weight of the total composition of said bleach activator or mixtures thereof. May consist of

Foam-reducing system: The composition according to the invention may consist of a foam-reducing agent or a mixture thereof. Any suds reducing agent known in the art is suitable for use herein. In a preferred embodiment, a foam system comprising a fatty acid together with a substituted alkoxylated nonionic surfactant and / or silicone as defined herein below is used. Typically, the compositions herein may consist of% to 10%, preferably% to 5%, and more preferably% to 5% fatty acids or mixtures thereof by weight of the total composition. Typically, the compositions herein comprise from about 20%, preferably from about 10%, and more preferably from about 5% to about 5% by weight of the total composition of a substituted alkoxylated nonionic surfactant as defined herein. Agents or mixtures thereof. Typically, the compositions herein may comprise from 5% to 5%, preferably from 1% to 1%, and more preferably from 5% to 0.5%, by weight of the total composition, of silicone or a mixture thereof. Suitable fatty acids for use herein are the alkali salts of C ₈ -C ₂₄ fatty acids. Such alkali salts include salts completely saturated with metals, such as the sodium, potassium and / or lithium salts of fatty acids, and also ammonium and / or alkyl ammonium salts, preferably the sodium salt. Preferred fatty acids for use herein contain 8 to 22, preferably 8 to 20, and more preferably 8 to 18 carbon atoms. Suitable fatty acids are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and plant or animal esters such as palm oil, coconut oil, soybean oil, castor oil, tallow, peanut oil, whale oil and fish oil. and/
Or from a natural source such as babassu oil). For example, coconut fatty acid is available from UNICHEMA under the name PRIFAC 5900 (trade name).

A suitable substituted alkoxylated nonionic surfactant for use herein is according to the formula: R ₁ (O—CH ₂ —CH ₂ ) _n — (OR ₂ ) _m —O -R ₃ wherein R ₁ is a C ₈ -C ₂₄ linear or branched alkyl or alkenyl group, an aryl group, an alkaryl group, preferably R ₁ is a C ₈ -C ₁₈ alkyl or alkenyl group, more preferably C ₁₀ A C ₁₅ alkyl or alkenyl group, even more preferably a C ₁₀ -C ₁₅ alkyl group; wherein R ₂ is a C ₁ -C ₁₀ straight or branched chain alkyl group, preferably a C ₂ -C ₁₀ straight chain or branched-chain alkyl group, preferably a C ₃ group; wherein R ₃ is C ₁ -C ₁₀ alkyl or alkenyl group, preferably C ₁ -C ₅ alkyl group, more preferably methyl; and wherein n and m is Respectively independently from 1 to 20, preferably from 1 10,
More preferably, it is an integer in the range of 1 to 5; or a mixture thereof. These surfactants can be purchased from BASF under the trade name Plurafac (trade name), from HOECHST under the trade name Genapol (trade name), or from ICI under the trade name Symperonic (trade name). Preferred substituted nonionic alkoxylated surfactants of the above formula are available from Hoechst under the trade name Genapol® L2.5 NR, and P
lurafac (trade name) that can be purchased from BASF.

Suitable silicones for use herein include any silicone and silica
Also includes silicone mixtures. Silicones are commonly represented by alkylated polysiloxane materials, whereas silica is commonly used in a finely divided form, represented by silica aerogels and xylogels and various types of hydrophobic silica. it can. These materials can be incorporated as microparticles, in which the silicone can be advantageously released into a water-soluble or water-dispersible, virtually non-surfactant-impermeable carrier. It is captured. Alternatively, the silicone can be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other ingredients. In fact, in industrial practice, the phrase "silicone" has become a generic term encompassing various relatively high molecular weight polymers, including siloxane units and various types of hydrocarbon groups. In fact, silicone compounds are widely described in the art, for example, US Pat. No. 4,076,648, US Pat. No. 4,021,365,
U.S. Pat. No. 4,749,740, U.S. Pat. No. 4,983,316, European Patent No. 1
See U.S. Pat. No. 5,872, EP 217,501 and EP 499,364. The silicone compounds disclosed therein are suitable in the context of the present invention. In general, silicone compounds can be described as siloxanes having the following general structure:

[0038]

Embedded image

Where n is from 20 to 2000 and each R can independently be an alkyl or aryl group. Examples of such substituents are methyl, ethyl, propyl, isobutyl and phenyl. Preferred polydiorganosiloxanes have trimethylsilyl end-capping units and at 25 ° C. from 5 × 10 ⁻⁵ m ² / s to 0.1 μm.
It is a polydimethylsiloxane having a viscosity of 1 m ² / s, ie a value of n from 40 to 1500. These are desirable because of their availability and their relatively low cost. A desirable type of silicone compound useful in the compositions herein comprises a mixture of an alkylated siloxane of that type disclosed hereinabove and solid silica. The solid silica can be fumed silica, precipitated silica or silica produced by gel-forming techniques. Silica particles can be rendered hydrophobic by treating them with dialkylsilyl and / or trialkylsilane groups that are bound either directly on the silica or by a silicone resin. Preferred silicone compounds comprise hydrophobically silanized, most preferably trimethylsilanized silica having a particle size in the range of 10 mm to 20 mm and a specific surface area above 50 m ² / g. Used in the composition according to the invention suitably have an amount of silica in the range of from 1% to 30% by weight of the total weight (15% from 2.0 more desirably) a silicone compound, as a result 2x10 ^{- 4} The resulting silicone compound has an average viscosity in the range of m ² / s to 1 m ² / s. Desirable silicone compounds may have viscosities ranging from 5 × 10 ⁻³ m ² / s to 0.1 m ² / s. Particularly suitable are silicone compounds with a viscosity of 2x10 ^-2 m ² / s or 4.5x10 ^-2 m ² / s. Suitable silicone compounds for use herein can be purchased from various companies, including Rhone Poulenc, Fueller and Dow Corning. Examples of silicone compounds for use herein are Silicone DB 100 and Silicone Emulsion 2-3597, both available from Dow Corning. Other silicone compounds are disclosed in Bartollota et al., U.S. Pat. No. 3,933,672. Other particularly useful silicone compounds are disclosed in German Patent Application DTOS 2646126 published April 28, 1977. An example of such a compound is DC-544 (trade name), commercially available from Dow Corning, which is a siloxane-glycol copolymer. Typically, desirable silicone compounds are described in European Patent Application ED-A-573699.
It is described in. The composition may comprise a silicone / silica mixture in combination with a fumed non-porous silica, such as Aerosil.

Bleaching the Garment: In the present invention, the liquid bleaching composition of the present invention needs to be brought into contact with the garment to be bleached. This is the so-called "pre-treatment method" in which the liquid composition is applied in undiluted form on the garment before the garment is rinsed or washed and then rinsed, or the liquid composition is first diluted in a water bath. Garments are soaked and immersed in a water bath before they are rinsed, or a liquid composition is added in addition to the wash liquor formed by dissolution or dispersion of a typical laundry detergent It can be done by any of the "simultaneous washing methods". In both cases, it is also essential that the garment is rinsed after the garment contacts the composition before the composition has completely dried. In a pretreatment method, the step comprises applying the liquid composition on the garment or at least to the soiled portions of the liquid composition in its neat form and subsequently rinsing the garment Or washing and then rinsing. In this method, the undiluted composition may be used for a period ranging from 1 minute to 1 hour before the garment is rinsed or washed and then rinsed, unless the composition is left dry on the garment. Optionally left to act on clothing. Particularly for severe stains, it may be appropriate to further rub or brush the garment with a sponge or brush-like method or to rub two pieces of garment together.

In another method, generally referred to as the “dipping method”, the process involves diluting the liquid composition in a water bath in its neat form to form a diluted composition. It consists of stages. The dilution level of the liquid composition in the aquarium is typically 1:85
, Preferably up to 1:50, and more preferably up to 1:25 (composition:
Water). The garment is then contacted with a bath containing the liquid composition, and the garment is finally rinsed or washed and then rinsed. Desirably in that embodiment, the garment is soaked in a bath containing the liquid composition, and also desirably the garment is left soaked therein for a period ranging from 1 minute to 48 hours, preferably 1 hour to 24 hours. Furthermore, in another method, which is considered a sub-embodiment of the "dipping method" and is generally referred to as "washing bleaching method", the liquid composition is used as a so-called laundry additive. And in that embodiment, the water tub is formed by dissolving or dispersing a normal laundry detergent in water. The liquid composition in the form of a stock solution is placed in the aquarium, and the garment is then contacted with the aquarium containing the liquid composition. Finally, the clothes are rinsed. Depending on the end use envisioned, the compositions herein can be packaged in various containers, including conventional bottles, roll-on sponges, brushes, or spray bottles. Although the preferred application of the compositions described herein is in laundry applications and especially in laundry pretreatment, the compositions according to the invention are also used as household detergents for cleaning bathroom surfaces or kitchen surfaces. Is also good. The invention is further described by the following examples.

EXAMPLES The following compositions are prepared by mixing the listed ingredients in the listed proportions (% by weight unless otherwise specified).

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

HEDP is 1-hydroxy-ethanediphosphonate. DTPMP is diethylenetriaminepentamethylenephosphonate. BHT is di-tert-butylhydroxytoluene. The salt-free betaine is lauryl di-methyl betaine containing 0.3% by weight of sodium chloride. This betaine is commercially available lauryl di-methyl betaine GENAGE
Obtained by purification of N LAB (trade name) (Hoechst) (containing 7.5% sodium chloride). The perfume used in the above composition contains di-hydro-myrcenol and hexylcinnamic aldehyde as main ingredients. When used to bleach soiled colored garments, Compositions I through XXIII comprise:
They show excellent color safety to the garments bleached by them and also good garment safety. For example, in a pre-treatment method, compositions I to XXIII are applied neat to soiled parts of clothing and left for 5 minutes to act thereon. The garment is then washed with a conventional detergent and rinsed. Surprisingly, excellent color safety and also good garment safety are provided by these compositions, which furthermore allow them to act on the garments for a longer time before they are washed, For example, it is obtained when left for one hour. In the method of bleaching while washing, any of the compositions I to XXIII are contacted in a water bath formed by dissolving a conventional detergent in water. The garment is then contacted in a bath of liquid detergent and the garment is rinsed. They can also be used in the immersion method, where 100 ml of the liquid composition is diluted with 10 liters of water. The garment is then contacted in this aquarium containing the composition and soaked therein for 24 hours. The clothing is subsequently rinsed.

──────────────────────────────────────────────────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, 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. Inventor Junti, Stefano Italy, 61033 Fermignano, Via, Flaminia 19 (72) Inventor Scalamella, Roberto Italy, 00153 Rome, Piazza, San, Cosimato 63 F term (reference) 4H003 AC08 AD04 BA12 DA01 EB03 EB04 EB07 EB08 EB24 EB37 ED28 EE04 EE06 FA26 FA28

Claims (18)

[Claims] 1. A peroxide bleach having a pH of up to 7 and comprising a peroxide bleach, 0.1% to 10% by weight of the total composition and a perfume of 0.0001% to 5% by weight. A liquid composition suitable for pretreating clothing. 2. The peroxide bleaching agent is selected from hydrogen peroxide or percarbonates, persilicates, perborates, peroxy acids, hydroperoxides, aromatic and aliphatic diacyl peroxides and mixtures thereof. These are water-soluble raw materials, preferably hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-
Hydroperoxide, di-isopropylbenzene-monohydroperoxide, t
tert-amyl hydroperoxide, 2,5-dimethyl-hexane-2,5-dihydroperoxide, dilauroyl peroxide, didecanyl peroxide, dimyristoyl peroxide, benzoyl peroxide or a mixture thereof, and The composition according to claim 1, which is more preferably hydrogen peroxide. 3. It contains from 0.1% to 20%, preferably from 1% to 15%, and more preferably from 2% to 10% by weight of the total composition of said peroxide bleach or mixtures thereof. 3. A composition according to claim 1 or claim 2. 4. The method according to claim 1, wherein the pH buffer is 1.5 to 6.5, preferably 2 to 6,
The composition according to any one of claims 1 to 3, further comprising a weak acid having a pKa of 4 to 6 or one of the pKa and a conjugate base thereof. 5. The method according to claim 1, wherein the pH buffer is citric acid / sodium citrate, citric acid / potassium citrate, oxalic acid / sodium oxalate, tartaric acid / potassium hydrogen tartrate,
Oxalic acid / potassium tetraoxalate dihydrate, phthalic acid / potassium phthalate, acetic acid / sodium acetate, formic acid / sodium formate, benzoic acid / sodium benzoate and / or salicylic acid / sodium salicylate, and more preferably citric acid / Composition according to any one of claims 1 to 4, which is sodium citrate and / or citric acid / potassium citrate. 6. 0.2% to 8%, preferably 0.3% to 5%, more preferably 0.3% to 3%, and most preferably 0.3% to 2% by weight of the total composition. %
The composition according to any one of claims 1 to 5, comprising a pH buffer or a mixture thereof. 7. Perfume or 0.001% to 1% by weight of the total composition, more preferably 0.001% to 1%, and most preferably 0.01% to 0.5%. The composition according to any one of claims 1 to 6, comprising a mixture. 8. The composition according to claim 1, wherein said composition further comprises up to 60% by weight of the total composition, more preferably from 0.1% to 30%, most preferably from 0.5% to 15%, or a mixture thereof. A composition according to any one of claims 1 to 7, comprising: 9. The surfactant according to claim 1, wherein the surfactant is a nonionic surfactant and / or a zwitterionic surfactant, preferably a mixture of an alkoxylated nonionic surfactant and a zwitterionic betaine surfactant. Item 8. A composition according to Item 8. 10. The nonionic surfactant as defined above, wherein R is a C ₆ to C ₂₂ alkyl chain or a C ₆ to C ₂₈ alkyl benzene chain, and wherein n is 0 to 20, preferably 1 to 10. 15, more preferably 2 to 15, and most preferably an integer of 2 to 12 wherein _{RO- (C 2 H 4 O)} n H by ethoxylated non ion-type surfactant and / or amine oxide surfactant And / or a polyhydroxy fatty acid amide surfactant. 11. The amphoteric betaine surfactant according to the following formula: R ₁ -N ⁺ (R ₂ ) (R ₃ ) R ₄ X ^- wherein R ₁ is an amide group or an ester group. An aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain which can contain a linking group such as, preferably 1 to 24, preferably 8 to 18, and More preferably 1
An alkyl group containing 0 to 16 carbon atoms, or an amide group of the formula _Ra- C (O) -NH- (C ( _Rb ) ₂ ) _m , wherein _Ra is aliphatic or An aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 to 20, preferably up to 18, more preferably up to 16 carbon atoms; _b is selected from the group consisting of hydrogen and hydroxyl, and m is 1 to 4, preferably 2 to 3, more preferably 3, and one or more hydroxyl groups in any (C (R _b ) ₂ ) residue R ₂ is hydrogen, C ₁ -C ₆ alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ alkyl group; R ₃ is a cyclic structure with C ₁ -C ₆ alkyl, hydroxyalkyl or also N binds to R ₂ to form DOO can other substituted C ₁ -C ₆ alkyl group, there have is an C ₁ -C ₆ carboxylic acid group or C ₁ -C ₆ sulphonate group; R ₄ is bound to cationic nitrogen atom to the hydrophilic group And is typically an alkylene, hydroxyalkylene, or polyalkoxy group containing 1 to 10 carbon atoms; and X is a carboxylate or sulfonate group; or a mixture thereof. Composition according to claim 9 or 10. 12. The zwitterionic betaine surfactant is less than 5% by weight, desirably less than 3%, more desirably less than 2%, even more desirably less than 1%, and most desirably. The composition according to any one of claims 9 to 11, which is a salt-free zwitterionic betaine surfactant containing 0.01% to 0.5% salt. 13. The composition according to claim 1, wherein said composition further comprises up to 5% by weight of the total composition, preferably 0.01% to 1.5%, and more preferably 0.01% to 0.5%. Or a mixture thereof, wherein the chelating agent is desirably 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, and more preferably aminoaminotri (methylenephosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine N, N '-Disuccinic acid or a mixture thereof. A composition according to any one of the preceding claims. 14. The composition of claim 1, wherein said composition is aqueous and is typically formulated at a pH of from 1 to 6, and more preferably from 1.5 to 5.5. Composition. 15. A liquid composition according to any one of claims 1 to 14, diluted in the form of its neat liquid in a water tank, contacted with said garment in a water tank of said liquid composition, and subsequently A method of bleaching clothing comprising rinsing or washing and then rinsing said clothing. 16. Rinse the garment with the liquid composition according to any one of claims 1 to 14 in its neat form, preferably only on those soiled parts, or Pre-treating the garment comprising applying before washing the garment and then rinsing. 17. The method according to claim 17, wherein said garment is made of said liquid composition for 1 minute to 4 minutes.
16. The method according to claim 15, wherein the method is left soaked for a period of time ranging from 1 hour to 24 hours. 18. The method according to claim 15, wherein said tub is formed by dissolving or dispersing a conventional laundry detergent in water.