JP2002523613A - Uses of aliphatic-aromatic diacyl peroxides in bleaching compositions - Google Patents

Abstract

  (57) [Summary] Use of an aliphatic-aromatic diacyl peroxide in a bleaching composition to provide soil removal and improved fabric color safety.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to the use of aliphatic-aromatic diacyl peroxides in bleaching compositions.

BACKGROUND [0002] Peroxygen bleach-containing compositions, typically based on hydrogen peroxide, have been extensively described in laundry applications as laundry detergents, laundry additives or pre-wash agents.

[0003] An example of such a bleach is diacyl peroxide. Diacyl peroxides, including dialiphatic, diaromatic and aliphatic-aromatic diacyl peroxides, and compositions containing such compounds have been described in the art.

[0004] JP 1009601 (KAO) describes a composition comprising hydrogen peroxide, diacyl peroxide and a surfactant. The diacyl peroxide can be dialiphatic, diaromatic or aliphatic-aromatic. This composition is stated to have good storage stability.

[0005] WO 98/11189 (Procter & Gamble)
Gamble) describes a method for bleaching fabrics using a liquid composition comprising a dialiphatic peroxide. This document does not describe aliphatic-aromatic diacyl peroxides.

[0006] While diaromatic peroxides provide good soil removal, they are aggressive bleaches that cause fabric damage and thus cause poor fabric color safety.

It is conceivable that the radical decomposition of hydrogen peroxide occurs on the surface of the fabric, thus generating free radicals. This free radical generation can cause aggressive decomposition of certain dyes present in the fabric, thus causing chemical damage to the dye molecules, which can appear as discoloration and / or loss of color strength. Further speculation. Thus, while bleach performance and fabric color safety are somewhat conflicting requirements, both are required in a single bleach composition.

[0008] Accordingly, it is an object of the present invention to provide a bleaching composition that provides good stain removal and good fabric color safety.

[0009] EP-A-742,279 and EP-A-752,469 describe laundering containing chelators, radical scavengers and polyamides which are color and fabric safe. A bleaching composition is disclosed. The peroxygen bleaches disclosed in this patent include a peroxy acid such as diperoxide decandioic acid, but do not describe aliphatic-aromatic diacyl peroxides.

It has now been found that the above-mentioned objects can be achieved by using aliphatic-aromatic diacyl peroxides for treating soiled fabrics. In particular, when the mixed aliphatic-aromatic diacyl peroxide in the aqueous bleaching composition is compared to the use of the same composition without the aliphatic-aromatic diacyl peroxide or the same composition comprising a dialiphatic diacyl peroxide, Has just been found to provide good soil removal performance. In particular, the mixed aliphatic-aromatic diacyl peroxide in the aqueous bleaching composition is a different peroxygen bleach than the aliphatic-aromatic diacyl peroxide,
For example, it has also been found to reduce the color damage of colored fabrics when compared to the color damage observed with the same composition except that it comprises a diaromatic diacyl peroxide.

[0011] An advantage of the present invention is that the improved soil removal performance obtained is readily available to consumers for a variety of soils / stains, including enzyme stains such as blood, grass and especially carotenoid-type stains such as tomato sauce. To be noticed.

Thus, Applicants have also found that the diacyl peroxides of the present invention not only provide good soil removal, but also good fabric color safety.

SUMMARY OF THE INVENTION In accordance with the present invention, a general formula for providing soil removal and improved fabric color safety

[0014]

Embedded image

Wherein R 1 is an aliphatic group and R 2 is an aromatic group.

DETAILED DESCRIPTION OF THE INVENTION Diacyl peroxide The diacyl peroxide of the present invention has the general formula

[0017]

Embedded image

[0018]

In the formula, R1 is an aliphatic group, and R2 is an aromatic group. In a preferred embodiment of the present invention, R1 has 1 to 30 carbon atoms, more preferably 4 to 20 carbon atoms.
R1 can be linear, branched, cyclic, saturated, unsaturated, substituted, unsubstituted, or a mixture thereof. Preferably, R1 is straight-chain and has 8 to 1 carbon atoms.
6. If R1 is substituted, the carbon atom is preferably a halide or SO ₃ ⁻ , SO ₄ ⁻ , NO ₂ , NR ₃ ⁺ (where R = H or an alkyl chain)
And a sulfur-containing functional group or a nitrogen-containing functional group.

R 2 can be a mono- or polycyclic aromatic ring, a homoatom or heteroatom aromatic ring, a substituted or unsubstituted aromatic ring, and mixtures thereof. When R2 is substituted, the carbon atoms are preferably halides, sulfur-containing functional groups, nitrogen-containing functional groups or C1-20, most preferably 4-10 carbon atoms.
Is substituted with an alkyl chain. Suitable sulfur or nitrogen containing substituents include S
O ₃ ⁻ , SO ₄ ⁻ , NO ₂ , NR ₃ ⁺ (where R = H or an alkyl chain). Preferably, R2 is benzene. In a preferred embodiment of the invention, the diacyl peroxide is preferably a benzoylalkanoyl peroxide in which the alkanoyl group has from 8 to 18 carbon atoms. More preferably, the diacyl peroxide consists of benzoyl lauroyl peroxide, benzoyl decanoyl peroxide, benzoyl cetyl peroxide, para-alkyl benzoyl lauroyl peroxide, para-alkyl benzoyl decanoyl peroxide, para-alkyl benzoyl cetyl peroxide and mixtures thereof. Selected from the group. In a particularly preferred embodiment, the diacyl peroxide is benzoyl lauroyl peroxide.

The diacyl peroxides described herein are readily synthesized by those skilled in the art. See, for example, Organic Peroxides Vol. 1; pa
ge65, edited by Daniel Swern of Wiley
See Interscience.

The present invention also relates to the use of the bleaching compositions comprising the diacyl peroxides described herein. When the present invention relates to a bleaching composition, the diacyl peroxide is typically from 0.01% to 10%, preferably from 0.1% to 3%, more preferably from 0.3 to 2% by weight of the composition. %, Most preferably in the range 0.5-1%.

The composition used according to the present invention may further comprise, in addition to said aliphatic diacyl peroxide, another peroxygen bleach, hereinafter referred to as a “second” peroxygen bleach. It is. Other optional ingredients, such as bleach activators, surfactants, brighteners, chelating agents, radical scavengers, stabilizers, stain dispersing polymers, stain release agents, dye transfer inhibitors, solvents, coloring. Agents, flow improvers, foam inhibitors, catalysts, fragrances or mixtures thereof can be added to the composition. Preferred optional ingredients are described in more detail below.

In a preferred embodiment of the present invention, the use of a preferably aqueous bleaching composition comprising a diacyl peroxide as described herein and a second peroxygen bleach is described herein. It has been found that compared to the same composition but without the diacyl peroxide, it provides improved soil removal and bleaching performance while still ensuring good fabric color safety. Accordingly, the present invention also provides 0.05% to 10% by weight of the diacyl peroxide described herein and 0.01 to 10% by weight of a second peroxygen bleach based on the weight of the total composition. The use of a bleaching composition preferably comprising Further, in another preferred embodiment of the present invention, the composition also comprises a bleach activator. Such compositions provide much more effective bleaching performance, especially at room temperature.

The second peroxygen bleach used herein can be any peroxygen bleach known in the art, except for the diacyl peroxides described herein. . These peroxygen bleaches include hydrogen peroxide,
Water-soluble sources or mixtures thereof. Hydrogen peroxide is most preferred for use in the composition according to the invention. Furthermore, the presence of a second peroxygen bleach, preferably hydrogen peroxide, contributes to the excellent cleaning and bleaching benefits of the composition. As used herein, a hydrogen peroxide source refers to any compound that produces perhydroxyl ions upon contact with water.

[0026] Suitable aqueous sources of hydrogen peroxide for use herein include percarbonates,
Persulfates such as persilicate and monopersulfate, perborate, diperoxide decane diacid (DPDA), phthaloylaminoperoxycaproic acid (PAP), magnesium perphthalic acid, perlauric acid, perbenzoic acid and alkyl Peroxy acids such as perbenzoic acid, hydroperoxides such as t-butyl hydroperoxide and mixtures thereof.

[0027] The composition according to the present invention may comprise from 0.01 to 10%, preferably from 0.5 to 8%, more preferably from 2% to 8%, most preferably from 4% to 7% by weight of the composition. A second peroxygen bleach.

In a particularly preferred embodiment of the present invention, the bleaching composition comprises a diacyl peroxide as described herein and a surfactant. The surfactant can be a surfactant system comprising two or more surfactants.

The composition of the present invention is preferably an aqueous liquid composition. The aqueous composition,
Most preferably, it is blended so that the pH is 2-5. PH of the composition of the present invention
Can be adjusted by organic or inorganic acids known to those skilled in the art. Particularly suitable organic acids for use herein include aryl and / or alkyl sulfonates such as methanesulfonic acid or naphthalenedisulfonic acid, citric acid, succinic acid, tartaric acid, sulfamic acid, glutaric acid and adipic acid. Particularly suitable inorganic acids include sulfuric acid, phosphoric acid, and nitric acid. The composition used according to the method of the present invention is preferably an aqueous composition. The composition used herein has a pH of 0-12. The composition preferably has a pH between 0 and
10, more preferably 1 to 7, most preferably 2 to 4.

The term “improve color safety” means that the damage to dyes present on fabrics caused by the diacyl peroxides of the present invention is caused by other bleaching agents, especially diaromatic peroxides, such as dibenzoyl peroxide. It means a reduction compared to the damage caused. That is, improved fabric color security is equivalent to reduced fabric color damage. Damage caused to the dye is seen as a loss of color strength. Moreover, this reduction in color damage is seen even when the diacyl peroxides of the present invention remain in contact with the fabric, and thus the fabric dye, for an extended period of time, eg, 24 hours, prior to subsequently washing or rinsing the fabric. .

It can be seen that color safety is achieved due to the lower reactivity of the diacyl peroxides of the present invention compared to other bleaching agents known to cause fabric color damage, especially diaromatic diacyl peroxides. Guessed.

The stain removal performance and fabric color safety of diacyl peroxide can be evaluated by the following test methods. First, a composition comprising a diacyl peroxide according to the invention, but preferably comprising a diacyl peroxide, is applied to a fabric, preferably on a soiled portion of said fabric, and allowed to stand for 1 minute to 24 hours, preferably 5 minutes. ~ 1
Leave to work on it for 0 minutes, then wash the fabric by conventional washing conditions at a temperature of 30 ° C to 70 ° C for a time sufficient to bleach the fabric.

Comparing side-by-side colored fabrics pretreated with a diacyl peroxide composition or product according to the invention, eg, side-by-side with a standard containing the same composition without the peroxide of the invention Thereby, the stain removal performance can be evaluated. Typical for use in such soil removal test methods, such as grass, coffee, tomato sauce, dirty motor oil, cosmetics, barbecue sauce, blood, etc. on different substrates / fabrics, for example cotton (CW120) or polycotton (PCW28) Typical stains are WFK (Krefeld, Germany) or EMC (Empirica, Cincinnati, Ohio, USA).
1 Manufacturing Company)). A visual grading scale can be used to assign a panel score unit (psu) difference in the range of 0-4 for soil removal performance.

The stained colored fabric treated with the diacyl peroxide according to the invention may be a standard product, for example the same composition without the diacyl peroxide according to the invention, or one treated with a different bleach, for example a diaromatic peroxide By determining the color damage by side-by-side comparison, color safety can be evaluated. Technical coloring swatches / fabrics suitable for use in the color damage test method herein are Tecnotessile (Plat, Italy) or EMC (Empirical Manu) of Cincinnati, Ohio, USA.
Factoring Company)). Typical pigmented fabrics / swatches used are, for example, C83 Reactive Blue®, C102 Reactive Blue®, C65 Reactive
e Violet (registered trademark), C73 Direct Blue (registered trademark),
C105 Direct Brown (registered trademark), C111 Direct Re
d®, most sensitive to bleaching agents such as C40 Sulfur Green®. Visual grading and / or "Hunterlab"
The instrumental method according to Tristimulus MINISCAN can be used for color damage assessment.

It is contemplated that diacyl peroxide or a composition comprising diacyl peroxide can be used as a pre-treatment, as an additive or component of a detergent composition. When using diacyl peroxide as a pretreatment, it is preferable to wash the fabric to which diacyl peroxide is added later. "Washing" is understood herein as simply rinsing the fabric with water. That is, the fabric can be washed by a washing machine or simply by hand using a conventional detergent comprising at least one surfactant.

When diacyl peroxide is a component of the composition, the composition can be used in the form of a stock solution or in the form of a dilution. By "stock form" is understood the application of the composition directly onto the fabric without any dilution.

Optional Ingredients When the present invention relates to the use of a composition comprising a diacyl peroxide, the composition further comprises a bleach activator, a surfactant, a brightener, a chelating agent, a radical scavenger, a stabilizer, It can comprise any ingredient such as a stain dispersing polymer, stain release agent, dye transfer inhibitor, solvent, colorant, flow improver, foam inhibitor, catalyst, fragrance or mixtures thereof.

As an optional but highly preferred ingredient, the compositions of the present invention comprise a bleach activator or a mixture thereof. By "bleach activator" is meant herein a compound that reacts with hydrogen peroxide to produce a peracid. The peracid thus formed constitutes an activated bleach. Particularly suitable bleach activators for use herein include hydrophobic bleach activators, ie, bleach activators that are substantially and stably immiscible with water.

[0039] 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 a method for shaping them into globules is described in European published patent application EP- A-62523. Suitable examples of such compounds for use herein include tetraacetylethylenediamine (TEAD),
Sodium 3,5,5 trimethylhexanoyloxybenzenesulfonate, for example, diperoxide decandioic acid as described in US Pat. No. 4,818,425, for example, described in US Pat. No. 4,259,201 Nonylamide of peroxyadipic acid, n-nonanoyloxybenzenesulfonate (NOBS
)). From substituted or unsubstituted benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecanoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, butanoylcaprolactam, pentanoylcaprolactam or mixtures thereof N-acylcaprolactams selected from the group are also suitable. A particular family of bleach activators of interest was disclosed in EP 624 154. Acetyltriethyl citrate (ATC) is particularly preferred within the family. Acetyltriethyl citrate has the advantage of being environmentally friendly as it eventually breaks down into citric acid and alcohol. In addition, acetyltriethyl citrate is an effective bleach activator with good hydrolytic stability in the product upon storage. Finally, it brings good builder performance to the composition.

The composition according to the invention may contain from 0.01% to 30%, preferably from 0.5% to 10%, most preferably from 3% to 7%, of the bleach activator or the same, based on the weight of the total composition. It is possible to comprise a mixture.

[0041] The composition according to the invention can comprise a surfactant or a mixture thereof. Any surfactant known to those skilled in the art, including anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants and / or cationic surfactants, may be added to the total composition at 50%. It can be used herein at a level of sub-% by weight.

The composition according to the invention can be formulated as a solution, emulsion, microemulsion, suspension, paste or powder.

As mentioned above, the compositions according to the invention, which can typically comprise a bleach activator, are preferably, for reasons of stability, preferably water, an aliphatic diacyl peroxide,
Aqueous emulsion of said bleach activator in a matrix comprising a second peroxygen bleach and emulsifying surfactant system, or water, an aliphatic diacyl peroxide, a second peroxygen bleach and a hydrophilic surfactant Formulated as any of the microemulsions of the bleach activators in a matrix comprising the system.

The preferred peroxygen bleach-containing compositions herein contain at least two different surfactants, ie, HLB 9.5 or less, to emulsify the hydrophobic bleach activator, if present. It comprises an emulsified surfactant system of at least one hydrophobic surfactant or a mixture thereof and at least one hydrophilic surfactant or a mixture thereof greater than HLB10. Preferably, the two different surfactants herein have different HLB values (hydrophilic / lipophilic equilibrium) to form a stable composition, and preferably the two surfactants The difference between the HLB values of the activators is at least 1, preferably at least 2. Indeed, by properly mixing at least two of the above surfactants with different HLB in water, an emulsion is formed that does not substantially separate into separate layers when left at 40 ° C. for at least two weeks. .

Preferred compositions according to the invention comprise from 0.1% to 50%, more preferably from 1% to 20%, most preferably from 2% to 10% by weight of a surfactant. . Surfactants may be hydrophilic or hydrophobic.
Preferred compositions according to the invention comprise at least 0.01%, preferably at least 2%, more preferably at least 4% of a hydrophobic surfactant and at least 0.1%.
It comprises 01%, preferably at least 2%, most preferably at least 4% of hydrophilic surfactant.

The hydrophilic surfactant has an HLB greater than 10. The hydrophilic nonionic surfactant preferably has an HLB greater than 10, more preferably greater than 10.5. Preferred hydrophobic surfactants are hydrophobic nonionic surfactants. The hydrophobic nonionic surfactant has an HLB of 9.5 or less, preferably less than 9.5, more preferably less than 9. The hydrophobic nonionic surfactants used herein have excellent fat and oil dissolving properties. That is, they have a solvent effect that contributes to the removal of hydrophobic stains.

Nonionic surfactants suitable for use herein include alkoxylated fatty alcohols, preferably fatty alcohol ethoxylates and / or propoxylates. In fact, a wide variety of such alkoxylated fatty alcohols with very different HLB values (hydrophilic / lipophilic balance) are commercially available.
The HLB value of such an alkoxylated nonionic surfactant essentially depends on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and short-chain fatty alcohols, while hydrophobic surfactants tend to have a low degree of alkoxylation and long-chain fatty alcohols. A surfactant catalog is available that describes many surfactants, including nonionic surfactants, along with their respective HLB values.

A suitable chemical method for producing a nonionic surfactant for use herein involves condensing the corresponding alcohol and alkylene oxide in the required proportions. Such methods are well known to those skilled in the art and have been extensively described in the art. Alternatively, a variety of alkoxylated alcohols suitable for use herein are commercially available from various suppliers.

Preferred hydrophobic nonionic surfactants for use in the present invention are those having an HLB of 9 or less and having the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H. is there. In the formula, R is a C ₆ -C ₂₂ alkyl chain or C ₆ -C ₂₈ alkyl benzene chain, n + m is 0.5 to 5, n is 0-5, m is 0-5, Preferably, n + m is 0.5-4.5, and n and m are 0-4.5. Preferred R chains for use herein are C ₈ -C ₂₂ alkyl chains. Therefore,
Suitable hydrophobic nonionic surfactants for use herein include Dob
anol® 91-2.5 (HLB = 8.1; R is a mixed chain of C ₉ and C ₁₁ alkyl chains, n is 2.5 and m is 0), Lutensol (
R) TO3 (HLB = 8; R is mixed chain of C ₁₃ and C ₁₅ alkyl chains,
n is 3 and m is 0), Tergitol® 25L3 (HL
B = 7.7; R ranges from C _{12 to} C ₁₅ alkyl chain length, n is 3 and m is 0), Dobanol® R23-3 (HLB = 8.1; R is
A mixed chain of C ₁₂ and C ₁₃ alkyl chains, n is 3 and m is 0), or Dobanol® R23-2 (HLB = 6.2; R is C ₁₂ and C ₁₃ A mixed chain of alkyl chains, n is 2 and m is 0), or a mixture thereof. Dobanol® 23-3, Dobanol® 23-2, Lutensol® TO3 or mixtures thereof are preferred herein. These Dobanol® surfactants are commercially available from Shell. These Lutensol® surfactants are commercially available from BASF and their Tergi
Tol® surfactant is available from Union Carb.
ide). Other suitable hydrophobic nonionic surfactants for use herein include nonalkoxylated surfactants. Doba as an example
No. 23 (HLB <3).

Preferred hydrophilic nonionic surfactants for use herein include those having an HLB greater than 10 and having the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H. is there. In the formula, R is a C ₆ -C ₂₂ alkyl chain or a C ₆ -C ₂₈ alkylbenzene chain, n + m is 5-11, n is 0-11, m is 0-11, and preferably In the formula, n + m is 6 to 10, and n and m are 0 to 10. Throughout this description, n and m refer to the average degree of ethoxylation / propoxylation. Preferred R chains for use herein are C ₈ -C ₂₂ alkyl chains. Accordingly, as suitable hydrophilic nonionic surfactants for use herein, Dobanol® 23-6.5 (HLB = 11.9; R:
A mixed chain of C ₁₂ and C ₁₃ alkyl chains, n is 6.5 and m is 0), D
obanol® 25-7 (HLB = 12; R is a mixed chain of C ₁₂ -C ₁₅ alkyl chains, n is 7 and m is 0), Dobanol® 45-7 (HLB = 11.6; R is a mixed chain of C ₁₄ and C ₁₅ alkyl chains,
n is 7 and m is 0), Dobanol® 91-5 (HLB
= 11.6; R is a mixed chain of C ₉ -C ₁₁ alkyl chains, n is 5 and m is 0), Dobanol® 91-6 (HLB = 12.5; R Is
A mixed chain of C ₉ -C ₁₁ alkyl chains, n is 6 and m is 0), Dob
anol® 91-8 (HLB = 13.7; R is a mixed chain of C ₉ -C ₁₁ alkyl chains, n is 8 and m is 0), or Dobanol® 91-10 (HLB = 14.2; R is a mixed chain of C ₉ -C ₁₁ alkyl chains, n is 10 and m is 0), or a mixture thereof. In the present specification, Dobanol® 91-10, Dobanol® 45-7, Dobanol® 23-6.5 or mixtures thereof are preferred. These Dobanol® surfactants are available in shell (
(Shell).

In addition to the hydrophilic nonionic surfactant, anionic surfactants described below and
/ Or formula R^Two-C (O) -N (R¹) -Z polyhydroxy fatty acid amide field
Other hydrophilic surfactants such as surfactants or mixtures thereof may also be present in the compositions of the present invention.
Can be used. Where R¹Is H or C₁~ C_FourAlkyl, C₁~ C _Four Hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or
A mixture of these,^TwoIs C_Five~₃₁A hydrocarbyl, wherein Z is at least
Also have a linear hydrocarbyl chain with three hydroxyls directly attached to the chain.
Lihydroxyhydrocarbyl or an alkoxylated derivative thereof.

Preferably, R ¹ is C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably methyl, and R ² is linear C ₇ -C ₁₉ alkyl or alkenyl, preferably Is a linear C ₉ -C ₁₈ alkyl or alkenyl, more preferably a linear C ₁₁ -C ₁₈ alkyl or alkenyl, most preferably a linear C ₁₁ -C ₁₄ alkyl or alkenyl, or a mixed group thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, in addition to the above-mentioned industrial sugars, high dextrose corn syrup, high fructose corn syrup and high maltost corn syrup can also be used. These corn syrups can produce a mixture of sugar components for Z. It is to be understood that no other suitable ingredients are intended to be excluded. Z _{preferably, -CH 2 - (CHOH) n} -CH 2 O
_{H, -CH (CH 2 OH)} - (CHOH) n + 1 -CH 2 OH, -CH 2 - (CHOH
_{) 2 - (CHOR ') (} CHOH) is selected from the group consisting of -CH ₂ OH. Wherein n is an integer from 3 to 5 and R ′ is H or cyclic or aliphatic monosaccharide and its alkoxylated derivative. n is 4 glucitol, particularly _{-CH 2 - (CHOH) 4 -CH} 2 OH are most preferred.

In the formula R ² —C (O) —N (R ¹ ) —Z, R ¹ is, for example, N-methyl, N
-Ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl. R ² -C
(O) -N <is, for example, cocamide, stearamide, oleamide, lauramide,
It can be myristamide, capncamide, palmitamide and tallowamide and the like. Z is 1-deoxyglycityl, 2-deoxyfructyl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymanityl, 1-deoxymaltotriotyl and the like. It is possible.

Suitable polyhydroxy fatty acid amide surfactants for use herein are commercially available from Hoechst under HOE®.

Methods for making polyhydroxy fatty acid amide surfactants are known in the art. Generally, an alkylamine is reacted with a reducing sugar in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine, and then
Producing a polyhydroxy fatty acid amide surfactant by reacting an N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation / amidation step to produce an N-alkyl, N-polyhydroxy fatty acid amide product can do. Methods for producing compositions containing polyhydroxy fatty acid amides are described, for example, in Thomas Hedley.
& Co. Ltd. GB Patent Specification 809, issued February 18, 1959,
U.S. Pat. No. 2,965,576, issued Dec. 20, 1960 to Wilson, ER Wilson, Anthony MS.
U.S. Pat. No. 2,703,79 issued Mar. 8, 1955 to
No. 8, US Pat. No. 1,985,424 issued Dec. 25, 1934 to Piggot and WO 92/06070.
Each of these is incorporated herein by reference.

In a particularly preferred embodiment of the invention, wherein the composition comprises acetyltriethyl citrate as bleach activator, a suitable surfactant system is, for example, Dobano
1 comprises a hydrophobic nonionic surfactant having an HLB of 6, such as 1®23-2, and a hydrophilic nonionic surfactant having an HLB of 15, such as, for example, Dobanol® 91-10. Other suitable nonionic surfactant systems are, for example, Dob
anol (registered trademark) 23-6.5 (HLB about 12) and Dobanol (registered trademark) 23 (less than HLB6) or Dobanol (registered trademark) 45-7 (HL
B = 11.6) and Dobanol® 23-3 (HLB = 8.1).

[0057] In embodiments of the invention where the composition is formulated as an emulsion, the composition is opaque. In the centrifugal test, the emulsified liquid in the present specification was 6000 rpm
It was observed that after 15 minutes at m no phase separation was shown. Under microscopic examination, the emulsion appeared as a dispersion of droplets in the matrix.

In an embodiment of the present invention, wherein the composition of the present invention is formulated as a microemulsion,
The bleached microemulsions according to the invention comprise a hydrophilic surfactant system comprising at least two different surfactants, such as a nonionic surfactant and an anionic surfactant.

[0059] Suitable hydrophilic surfactants for use herein are the hydrophilic surfactants mentioned herein. An important factor for stably incorporating a bleaching activator in the microemulsion, for example, is that at least one of the surfactants in the hydrophilic surfactant system has an HLB value different from the HLB value of the bleaching activator. That's what you have to do. In fact, all said surfactants have the same HL value as the HLB value of the bleaching activator.
With a B value, a continuous single phase could be formed, thus reducing the chemical stability of the bleach / bleach activator system. Preferably, at least one of the surfactants has an HLB value that differs from the HLB value of the bleach activator by at least 1.0 HLB units, preferably by 2.0.

[0060] Suitable anionic surfactants for use herein include those of the formula ROSO_ThreeM also
Is RSO_ThreeM water-soluble salts or acids. Wherein R is preferably C_Ten~
C_{twenty four}Hydrocarbyl, preferably C_Ten~ C₂₀Alkyl with an alkyl component or
Hydroxyalkyl, more preferably C₁₂~ C₁₈Alkyl or hydroxyal
And M is H or a cation, such as an alkyl metal cation (eg,
, Sodium, potassium, lithium) or ammonium or substituted ammonium
(Eg, methyl-, dimethyl-, trimethylammonium cation,
And tetramethylammonium and dimethylpiperidinium cations
And alkylamines such as ethylamine, diethylamine and triethylamine.
Quaternary ammonium cations such as quaternary ammonium cations derived from
And mixed cations thereof). Typically, C₁₂~ C₁₆The alkyl of
Cations are preferred for lower wash temperatures (eg, less than about 50 ° C.) ₁₆ ~₁₈Alkyl chains are preferred for higher wash temperatures (eg, above about 50 ° C.).
Good.

Other anionic surfactants suitable for use herein include compounds of formula RO
(A) There is a water soluble salt or acid of _m SO ₃ M. Wherein, R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl group having a C ₁₀ -C ₂₄ alkyl component, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl Or hydroxyalkyl, wherein A is an ethoxy or propoxy unit, and m is greater than 0, typically between about 0.5 and about 6, preferably about 0.5.
Between 5 and about 3, M is H or a cation that can be, for example, a metal cation (eg, sodium, potassium, lithium), ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are contemplated herein. Particular examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium,
And quaternary ammonium cations such as tetramethylammonium, cations derived from dimethylpiperidium, and alkanolamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof. Exemplary surfactants are, C ₁₂ -C ₁₈ alkyl polyethoxylate (1.
0) sulfate _{(C 12 ~C 18 E (1.0} ) M), C 12 ~C 18 alkyl polyethoxylate (2.25) sulfate _{(C 12 ~C 18 E (2.25} ) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate (C ₁₂ -C ₁₈ E (3.0) M, and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate (C ₁₂ To C ₁₈ E (4.0)
M) wherein M is conveniently selected from sodium and potassium.

Other anionic surfactants useful for cleaning purposes may be used herein.
Can be. These include soap salts (eg, sodium, potassium, ammonia).
And substituted ammonium such as mono-, di- and triethanolamine salts
Salt), C₉~ C₂₀Linear alkylbenzene sulfonate, C₈~ C_{twenty two}First or second
Alkane sulfonate, C₈~ C_{twenty four}Olefin sulfonates, e.g. UK patent
Alkaline earth metal quenches as described in specification 1,082,179
Sulfonated polycarboxylates produced by sulfonation of pyrolysis products of phosphates
Acid, C₈~ C_{twenty four}Alkyl polyglycol ether sulfate (less than 10 moles of ethyl
Oxides), C₁₄~ C₁₆Alkyl ethers such as methyl ether sulfonate
-Ter sulfonate, acylglycerol sulfonate, fatty oleyl glycer
Roll sulfate, alkylphenol ethylene oxide ether sulfate, paraffin
Isethionates such as sulfonates, alkyl phosphates, acyl isethionates
, N-acyl taurates, alkyl succinates and sulfo
Succinates, monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂~ C ₁₈ Monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C₆
~ C₁₄Diesters), alkyl polysaccharides such as alkyl polyglucoside sulfates, etc.
Sulphate of kalide (non-ionic non-sulphated compound described below), branched primary alkyl
Sulphate, formula RO (CH_TwoCH_TwoO)_kCH_TwoCOO^-M⁺(Where R is C₈~ C_{twenty two}A
Alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation)
It is possible to mention alkyl polyethoxycarboxylates such as B
Gin, hydrogenated rosin, and present in or from tall oil
Resin acids and hydrogenated resin acids such as derived resin acids and hydrogenated resin acids are also suitable.
I do. Another example is "Surface Active Agents and D
etergents "(Vol. I and II by Schwartz,
Perry and Berch). Various such interfaces
Activators are generally described by Laughlin et al. On December 3, 1975.
U.S. Pat. No. 3,929,678 issued on day 0, column 23, line 58 to column 29, line 2
3 (which is incorporated herein by reference).

Particularly suitable anionic surfactants for use in the compositions described herein are alkali or alkaline earth metal paraffin sulfonates, preferably sodium paraffin sulfonate (eg, Hoechst
) Or NaPS available from Huls).

Other suitable anionic surfactants for use herein include acyl sarcosinates in acid and / or salt form or mixtures thereof, preferably of the formula

[0065]

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Wherein M is hydrogen or a cation moiety and R is an alkyl group having 11 to 15 carbon atoms, preferably 11 to 13 carbon atoms. Can be Preferably, M is hydrogen and alkali metal salts, especially sodium and potassium. The acyl sarcosinate surfactant is derived from natural fatty acids and the amino acid sarcosine (N-methylglycine). They are suitable for use as aqueous solutions of their salts or as powders in the form of their acids. Since the acyl sarcosinate is a derivative of a natural fatty acid, it is rapidly and completely biodegradable and has good skin compatibility.

Accordingly, particularly preferred long chain acyl sarcosinates for use herein include C ₁₂ acyl sarcosinates (ie, where M is hydrogen in the formula above,
R is acyl sarcosinates) and C ₁₄ acyl sarcosinate (i.e. an alkyl group having a carbon number of 11, M is hydrogen in the above-mentioned formulas, R is an alkyl group having a carbon number of 13 Ashirusarukoshi Nate). C ₁₂ acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied by Hampshire. C14
Acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied by Hampshire.

[0068] Other hydrophilic nonionic surfactants suitable for use herein in the microemulsion include hydrophilic nonionic surfactants as previously defined for the emulsion.

A preferred preparation of the microemulsion of the present invention comprises premixing a surfactant with water,
Thereafter, it involves adding other ingredients including other ingredients such as aliphatic diacyl peroxide, a second peroxygen bleach, eg, hydrogen peroxide, and bleach activator if present. Regardless of this preferred order of addition, relatively high stirring energy during mixing of the raw materials, preferably at 750 rpm for 30 minutes, most preferably at 1000 rpm
It is important to keep the microemulsion constantly under stirring based on m for 30 minutes.

In an embodiment of the invention in which the composition is formulated as a microemulsion, the composition is microscopically transparent in the absence of opacifiers and colorants. In centrifugation, it was observed that the microemulsions herein did not show phase separation after 15 minutes at 6000 rpm. Under microscopic examination, the microemulsion appeared as a dispersion of droplets in the matrix. We have observed that the particles have a size that is typically less than about 3 micrometers in diameter.

Thus, the bleaching composition of the present invention can be packaged for long periods of time in the containers / bottles upon standing without compromising the stability of a given deformable container / bottle comprising the bleaching composition. It is possible.

Suitable chelators for use herein include chelating agents selected from the group consisting of phosphonate chelators, aminocarboxylate salt chelators, polyfunctionally substituted aromatic chelators, and glycine; Other chelating agents such as salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof. When chelating agents are used, they are typically used herein from 0.001% to 5%, preferably from 0.05% to 2% by weight of the total composition.
It is present in an amount in the range of weight percent.

Suitable phosphonate chelators for use herein include aminophosphonate compounds, including ethydronic acid and aminoalkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxydiphosphonate, nitrilotrimethylene phosphonate, ethylenediamine tetraethylene Mention may be made of methylene phosphonate, and diethylenetriaminepentamethylene phosphonate. In a preferred embodiment, the phosphonate chelating agent is an alkali metal ethane 1-hydroxydiphosphonate (HEDP). Phosphonate compounds can be in the form of an acid of a different cation in some or all of their acidic functional groups or exist as salts. A preferred phosphonate chelating agent for use herein is diethylenetriaminepentamethylenephosphonate. Such phosphonate chelators are commercially available from Monsanto under the trade name DEQUEST®.

The most preferred phosphonate chelator used herein is aminotri (methylene phosphonic acid), referred to herein as ATMP. Indeed, ATMP into a liquid composition of the present invention, ie, the formula

[0075]

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The addition of a compound of the formula (1) significantly reduces the damage associated without pre-treatment of fabrics with compositions containing peroxygen bleach, especially fabrics containing metal ions such as copper, iron, chromium and manganese. It was found to decrease.

[0077] Polyfunctionally substituted aromatic chelators may also be useful in the compositions herein. U.S. Pat. No. 3, issued May 21, 1974 to Connor et al.
See 812,044. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use herein include ethylenediamine N, N′-disuccinic acid, or an alkali metal, alkaline earth metal, ammonium or substituted ammonium salt thereof, or a mixture thereof. is there.
Ethylenediamine N, N'-disuccinic acid, especially the (S, S) isomer, was obtained by Hartman and Perkins, 1987 Nov.
This is widely described in U.S. Pat. Ethylenediamine N, N'-disuccinic acid can be obtained, for example, from Palmer Research Laboratories (Pa
ssED from lmer Research Laboratories)
It is commercially available under DS (registered trademark).

Suitable aminocarboxylates for use herein include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid in the form of acids or in the form of alkali metal, ammonium and substituted ammonium salts. (DTPA), N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetic acid, ethanoldiglycine, propylenediaminetetraacetic acid (PDTA
), And methylglycine diacetate (MGDA). Particularly suitable aminocarboxylates for use herein are diethylenetriaminepentaacetic acid, such as propylenediaminetetraacetic acid (PDTA) commercially available under the trade name Trilon FS® from BASF, and methylglycine diacetate ( MGDA).

[0080] Another preferred chelating agent for use herein is of the formula

[0081]

Embedded image

Is a chelating agent. Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO ₂ ,
It is selected from the group consisting of C (O) R 'and -SO ₂ R''. Where R 'is
-H, -OH, alkyl, alkoxy, aryl and aryloxy are selected from the group consisting of alkyl, alkoxy, aryl and aryloxy. R _5, R _6, R ₇ and R ₈ are independently selected from the group consisting of -H and alkyl.

Particularly preferred chelating agents for use herein are ATMP, diethylenetriamine methylene phosphonate, ethylene N, N′-disuccinic acid, diethylenetriaminepentaacetic acid, glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof. And ATMP is highly preferred.

Suitable radical scavengers for use herein include the well-known substituted monohydroxybenzenes and dihydroxybenzenes and their analogs, alkyl and aryl carboxylates, and mixtures thereof. Preferred such radical scavengers for use herein include di-t-butylhydroxytoluene (BHT), hydroquinone, di-t-butylhydroquinone, mono-t-butylhydroquinone, t-butyl-hydroxyanisole, benzoate. Acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or a salt thereof And mixtures thereof.
t-Butylhydroxytoluene is highly preferred. When using a radical scavenger,
They are typically present herein in an amount ranging from 0.001% to 2%, preferably 0.001% to 0.5% by weight of the total composition.

The presence of chelating agents, in particular ATMP and / or radical scavengers, makes the safety properties of the compositions according to the invention suitable for pretreating soiled colored fabrics with a long contact time prior to washing said fabrics. To contribute to

[0086] Other stabilizers, such as inorganic stabilizers, can be used herein. Examples of inorganic stabilizers include sodium stannate and various alkali metal phosphates such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate.

The composition according to the present invention can further comprise a foam inhibitor such as a 2-alkylalkanol or a mixture thereof as an optional ingredient. An alkyl chain having 6 to 16, preferably 8 to 12 carbon atoms, which is substituted at the α-position by an alkyl chain having 1 to 10, preferably 2 to 8, more preferably 3 to 6 carbon atoms. A 2-alkyl alkanol having a chain and a terminal hydroxy group is
Particularly suitable for use in the present invention. Such suitable compounds include, for example, I
sofol® 12 (2-butyloctanol) or Isofol (
It is commercially available in the Isofol® series, such as ® 16 (2-hexyldecanol). Typically, the compositions of the present invention comprise no more than 2%, preferably 0.05% to 1.5%, more preferably 0.1% to 0% by weight of the total composition.
. 8% of a 2-alkyl alkanol or a mixture thereof.

The composition according to the invention can further comprise, as an optional ingredient, a stain-dispersible polymer or a mixture thereof. Any stain dispersing polymer known to those skilled in the art may be used herein. Polyamine polymers such as polyalkoxylated polyamines are particularly suitable. These materials are a repeating unit

[0089]

Embedded image

And

[0091]

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Wherein R is a hydrocarbyl group, usually having 2 to 6 carbon atoms, R ¹ is a C ₁ -C ₂₀ hydrocarbon, alkoxy groups are ethoxy and propoxy, Is from 2 to 30, most preferably from 10 to 20, n is an integer of at least 2, preferably from 2 to 20, most preferably from 3 to 5, and X- is a halide or a methyl sulfate or the like. Which is an anion and results from a quaternization reaction).

The most highly preferred polyamines for use herein are y = 2-3
General formula when 0,

[0094]

Embedded image

Are so-called ethoxylated polyethyleneamines, ie, the polymerization reaction products of ethylene oxide and ethyleneimine. Ethoxylated polyethyleneamine,
In particular, ethoxylated tetraethylenepentamine and quaternized ethoxylated hexamethylenediamine are particularly preferred for use herein.

It has been surprisingly found that the stain dispersible polyamine polymer contributes to the advantages of the present invention. That is, when added in addition to the aliphatic diacyl peroxides, they further improve the soil removal performance of the compositions comprising them, especially under pre-laundering treatment conditions as described herein. In fact, they make it possible to improve the soil removal performance not only on bleachable soils but also on a variety of soils including greasy soils, enzymatic soils, soil / mud soils.

The composition will typically not exceed 10%, preferably 0.1%, by weight of the total composition.
% To 5%, more preferably 0.3% to 2%, of a soil-dispersible polyamine polymer or a mixture thereof.

[0098] The compositions herein can also comprise other polymeric stain release agents known to those skilled in the art. These polymeric stain release agents include hydrophilic segments that render the surface of hydrophobic fibers such as polyester and nylon hydrophilic, and deposited on the hydrophobic fibers and remain attached to the hydrophobic fibers throughout the wash and rinse cycle. And thus has both hydrophobic segments that act as fixing media for the hydrophilic segments. This makes it possible to more easily clean up dirt generated after treatment with the stain remover in a subsequent cleaning procedure.

The polymeric stain release agents useful herein include, in particular, (a) (i) a polyoxyethylene segment having a degree of polymerization of at least 2 or (ii) oxypropylene or polyoxy having a degree of polymerization of 2-10. A propylene segment (in which case the hydrophilic segment does not contain any oxypropylene units if the hydrophilic segment is not connected to an adjacent moiety at each end by an ether linkage), or (i.
ii) a mixed unit of an oxyethylene unit and an oxyalkylene unit containing 1 to about 30 oxypropylene units (in this case, the mixed unit is a compound in which the hydrophilic component indicates the hydrophilicity of a conventional polyester synthetic fiber surface. A sufficient amount of oxyethylene units to have sufficient hydrophilicity to deposit and simultaneously enhance the stain release agent on the surface), preferably at least about For such a hydrophilic component having 25% oxyethylene units, more preferably about 20-30 oxypropylene units, at least about 50
% Oxyethylene units, or one or more hydrophilic segments comprising (b)
(I) C ₃ oxyalkylene terephthalate segment (where the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is less than about 2: 1 if the hydrophobic component also comprises oxyethylene terephthalate)
, (Ii) a C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene segment or a mixed segment thereof, (iii) a poly (vinyl ester segment) having a degree of polymerization of at least 2, preferably poly (vinyl acetate), or ( iv) C _1-
C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituent or a mixture thereof (wherein the substituent is in the form of a C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivative or a mixture thereof). These cellulose derivatives are amphoteric and thus are deposited on conventional polyester synthetic fiber surfaces and, once attached to such conventional synthetic fiber surfaces, retain sufficient levels of hydroxyl to increase the hydrophilicity of the fiber surface having sufficient levels C ₁ -C ₄ alkyl ether and / or C ₄ having a hydroxyalkyl ether units) to comprise one or more hydrophobic components comprising of for, or (a) and the combination component (b), And a stain remover.

Typically, the polyoxyethylene segment of (a) (i) has a degree of polymerization of about 1
From about 200, preferably from 3 to about 150, more preferably from 6 to about 100. However
And higher levels can be used. Suitable oxy C_Four~ C₆Alkylene sparse
The aqueous segment includes Gosselink's January 1988
MO as disclosed in U.S. Pat. No. 4,721,580 issued Aug. 26, _Three S (CH_Two)_nOCH_TwoCH_TwoO- (wherein M is sodium and n is 4-6
End-caps of polymeric stain release agents, such as integers).
But not limited to them.

Polymeric stain release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, and copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate. Such agents are commercially available and include hydroxy ethers of cellulose such as METHOCEL (Dow). Cellulose stain release agents for use herein also include those selected from the group consisting of C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkyl cellulose. See U.S. Patent No. 4,000,093, issued December 28, 1976 by Nicol et al.

Stain release agents characterized by poly (vinyl ester) hydrophobic segments include graft copolymers of poly (vinyl ester), for example, C1 -C grafted onto a polyalkylene oxide backbone, such as a polyethylene oxide backbone. C6 vinyl esters, preferably poly (vinyl acetate). Kud
. See European Patent Application No. 0,219,048, issued Apr. 22, 1987, et al. Commercially available stain release agents of this type include BASF (BASF)
(West Germany), such as SOKALAN type materials, such as SOKAL
AN HP-22.

[0103] One type of preferred stain release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of the polymeric stain release agent ranges from about 25,000 to about 55,000. U.S. Pat. No. 3, issued May 25, 1976 to Hays
No. 959,230 and July 8, 1975 by Basadur.
See U.S. Pat. No. 3,893,929, issued to Japan.

Another preferred polymeric stain release agent is an ethylene terephthalate unit 10 derived from polyoxyethylene glycol having an average molecular weight of 300 to 5,000.
Polyester having a repeating unit of ethylene terephthalate unit containing -15% by weight together with 90-80% by weight of polyoxyethylene terephthalate unit. Examples of this polymer include the commercially available materials ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857 issued Oct. 27, 1987 by Gosselink.

Another preferred polymeric stain release agent is the sulfonation of a substantially linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and a terminal moiety covalently bonded to the backbone. Product. These stain release agents are described in detail in U.S. Pat. No. 4,968,451 issued Nov. 6, 1990 by JJ Schebel and EP Gosselink. Other suitable polymeric stain release agents include terephthalate polyesters of U.S. Pat. No. 4,711,730 issued Dec. 8, 1987 by Gosselink et al., Published Jan. 26, 1988 by Gosselink. U.S. Pat.
No. 721,580, and US Pat. No. 4,7, issued Oct. 27, 1987 to Gosselink.
No. 02,857.

Preferred polymeric stain release agents also include the stain release agent of US Pat. No. 4,877,896 issued Oct. 31, 1989 by Maldonado et al., Which is anionic, especially sulfoalloyl, Disclosed are end-terminated terephthalate esters.

Yet another preferred stain remover is an oligomer having repeating units of terephthaloyl, sulfoisoterephthaloyl, oxyethyleneoxy and oxy-1,2-propylene units. This repeating unit forms the backbone of the oligomer and is preferably terminated with a modified isethionate end-capping moiety.
Particularly preferred stain release agents of this type are about one sulfoisophthaloyl unit,
Five terephthaloyl units, two endblocks of oxyethyleneoxy and oxy-1,2-propyleneoxy units and sodium 2- (2-hydroxyethoxy) -ethanesulfonate in a ratio of about 1.7 to about 1.8. Stop unit.
The stain release agent is preferably a crystal-reducing stabilizer selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof, also from about 0.5% to about 20% by weight of the oligomer. %. See U.S. Patent No. 5,415,807 issued May 16, 1995 to Gosselink et al.

If stain removers are used, they will generally be from about 0.01% to about 10.0%, typically from about 0.1% to about 10.0%, by weight of the detergent composition herein. About 5%,
Preferably, it comprises about 0.2% to about 3.0%.

The compositions of the present invention can also include one or more materials that are effective to inhibit the transfer of dye from one stain surface to another during the cleaning process. Generally, such dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures thereof. If these agents are used, they are typically from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably about 0.1%, by weight of the composition. From about 0.5% to about 2%.

More particularly, preferred polyamine N-oxide polymers for use herein comprise units having the structural formula R-Ax-P. Wherein P is a polymerizable unit, wherein an N—O group can be attached to the polymerizable unit, or the N—O group forms part of the polymerizable unit, or It is a polymerizable unit capable of bonding an NO group to both units. A has the structure -NC (O)-, -C (O)-,-
S-, -O-, and -N =. x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any mixture thereof, wherein the nitrogen of the NO group is Can be combined or NO
The groups are part of these groups. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine and derivatives thereof.

The NO group has the general structure

[0112]

Embedded image

Can be represented by In the formula, R ₁ , R ₂ and R ₃ are an aliphatic, aromatic, heterocyclic or alicyclic group or a mixed group thereof, x, y and z are 0 or 1; The nitrogen of the group can be attached to the group described above, or can form part of any of the groups described above. The amine oxide units of the polyamine N-oxide have a pKa of less than 10, preferably a pKa of less than 7, more preferably pKa
Ka is less than 6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones include polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixed backbones thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers are typically from 10: 1 to 1: 1,000,000.
It has a ratio of amine to amine N-oxide of 00.

However, the number of amine oxide groups present in the polyamine oxide polymer is
It can be varied by a suitable copolymerization or by a suitable degree of N-oxidation. Polyamine oxides can be obtained with almost any degree of polymerization. The average molecular weight is typically in the range of 500 to 1,000,000, more preferably 1,
In the range of 000 to 500,000, most preferably 5,000 to 100,000
Is within the range. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxides useful in the detergent compositions herein are poly (4-vinylpyridine) having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about 1: 4. —N-oxide).

[0116] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPVI" by class) are also preferred for use herein. PVPVI preferably has an average molecular weight of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000.
２０20,000 (the average molecular weight range is from Barth, et al., Ch.
electronic Analysis, Vol. 113, "Modern Meth
It is measured by light scattering as described in "of of Polymer Characterization". The disclosure of which is incorporated herein by reference). The PVPVI copolymer typically has a 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1 N
-Having a molar ratio of vinylimidazole to N-vinylpyrrolidone. These copolymers can be either linear or branched.

The compositions of the present invention have an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, and most preferably about 5,000 to about 50,000.
000 polyvinylpyrrolidone ("PVP") can also be used. PV
P is known to those skilled in the detergent art. For example, EP-A-26
See 2,897 and EP-A-256,696. These patents are incorporated herein by reference. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000. The ratio of PEG to PVP by ppm delivered in the wash solution is preferably from about 2: 1 to about 50: 1.
, More preferably from about 3: 1 to about 10: 1.

If high foaming is desired, a foam enhancer such as a C ₁₀ -C ₁₆ alkanolamine can be incorporated into the composition, typically at a level of 1% to 10%. C ₁₀ -C ₁₄ mono- and diethanolamine show a typical class of such suds boosters. The use of such foam enhancers in combination with foaming co-surfactants such as the amine oxides, betaines and sultaines mentioned above is also advantageous. If necessary to provide additional foam and enhance grease removal performance, e.g.
It can be added to the soluble magnesium salts such as MgCl ₂ and MgSO ₄ at 1-2% level.

[0119] Any optical brightener, fluorescent whitening agent or other whitening agent or whitening agent known in the art may be a detergent composition herein when designed for fabric treatment or laundering. Typically from about 0.05% to about 1.
It can be incorporated into the composition at a level of 2%. Commercial optical brighteners that may be useful in the present invention can be divided into subgroups, which include stilbenes, pyrazolines, coumarins, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxide, azoles Derivatives of, but are not limited to, 5-membered and 6-membered heterocyclic brighteners. This list is illustrative and not restrictive. An example of such a brightener is "The Production and Applicat."
ion of Fluorescent Brightening Agent
s ", M.S. Zahrdnik, Published by John Wi
and Son, New York (1982).

Specific examples of optical brighteners useful in the present invention include Wixon (
U.S. Pat. No. 4,790,85 issued Dec. 13, 1988 to Wixon).
There are those identified in No. 6. These brighteners include Verona (Ve
Rona) 's Brightener series from PHORWHITE. Other optical brighteners disclosed in this document include Ciba-Gei.
gy) available from Tinopal UNPA, Tinopal CBS and Tinopal 5BM, Hilton Davis, Italy.
Vis) and Artic White CC and Artic Wh
item CWD, 2- (4-styryl-phenyl) -2H-naphthol [1,2
-D] triazole, 4,4'-bis- (1,2,3-triazol-2-yl) -stilbene, 4,4'-bis (styryl) bisphenyl and aminocoumarin. Specific examples of these brighteners include 4-methyl-7-diethyl-amino-coumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 2,5-bis (benzoxazol-2-yl). Yl) thiophene, 2-styryl-naphtho- [1,2-d] oxazole, and 2- (stilben-4-yl)-
2H-naphtho- [1,2-d] triazole. Hamilton (Hami
See also U.S. Pat. No. 3,646,015 issued Feb. 29, 1972 by Iton). Anionic brighteners are typically preferred herein.

If desired, the compositions herein can further comprise a catalyst or accelerator to further improve bleaching or stain removal. Any suitable bleaching catalyst can be used. For detergent compositions used at a total level of from about 1,000 to about 5,000 ppm in water, the composition is typically present in the wash liquor at a level of about
. The catalyst species is delivered at a concentration of 1 ppm to about 700 ppm, more preferably about 1 ppm to about 50 ppm or less.

[0122] Bleaching catalysts can also be used herein. Typical bleach catalysts are transition
Metal complexes, such as ligands for metal coordination, are among them completely instability-resistant
Deposits less metal oxide or metal hydroxide under typical alkaline cleaning conditions
A transition metal complex. Such catalysts include US Patent No. 5,246,
No. 621, US Pat. No. 5,244,594, US Pat. No. 5,194,416.
U.S. Pat. No. 5,114,606; EP 549,271 A1, 549,272.
Manga disclosed in A1, 544, 440A2 and 544, 490A1
Catalysts. Preferred examples of these catalysts include Mn^IV _Two(Μ-O)_Three(
TACN)_Two− (PF₆)_Two, Mn^III _Two(Μ-O)₁(Μ-OAc)_Two(TACN)_Two (ClO_Four)_Two, Mn^IV _Four(Μ-O)₆(TACN)_Four(ClO_Four)_Four, Mn^IIIMn^IV _Four -(Μ-O)₁(Μ-OAc)_Two-(TACN)_Two− (ClO_Four)_Three, Mn^IV− (T
ACN)-(OCH_Three)_Three(PF₆)₆And mixtures thereof. Where:
TACN is trimethyl-1,4,7-triazacyclononane or an equivalent macrocycle.
Compound. However, other metal coordination ligands and mononuclear complexes are also possible.
, Monometallic, bimetallic and polymetallic atomic complexes and iron or
Complexes of other metals such as ruthenium are all within the scope of the invention. Other metal-based
No. 4,430,243 and US Pat. No. 5,114,243.
No. 611. Various complexions to enhance bleaching
The use of manganese with body ligands has also been described in US Pat. Nos. 4,728,455, 5,
Nos. 284,944, 5,246,612, 5,256,779, and 5,
Nos. 280,117, 5,274,147, 5,153,161 and
No. 5,227,084.

The transition metal can be pre-chelated or chelated in situ with a suitable donor ligand selected in relation to the choice of metal, its oxidation state and ligand density. It is. Another complex that may be included in the present invention is the complex of US patent application Ser. No. 08 / 210,186, filed Mar. 17, 1994.

[0124]

【Example】

 The present invention is further described by the following examples.

The following examples were made in accordance with the present invention. All amounts are given in weight percent of the total composition.

Composition 1 Dobanol 45-7 5% NaPS 1% Benzoyllauroyl peroxide 0.5% H2O2 6.8% Water and by-products pH 4

Composition 2 Dobanol 45-7 5% NaPS 1% Isopar M 1.5% Benzoyl lauroyl peroxide 2% Water and by-products Remaining pH 4

Composition 3 Dobanol 45-7 3% NaPS 3% Isopar M 1.5% Benzoyllauroyl peroxide 0.5% H2O2 6.8% Water and by-products Remaining pH 4

Composition 4 Dobanol 45-7 5% NaPS 1% Isopar M 1.5% Benzoyllauroyl peroxide 0.5% HEDP 0.16% H2O2 6.8% Water and by-products Remaining pH 5

Composition 5 Dobanol 45-7 5% NaPS 1% Isopar M 1.5% p-pentyl-benzoyllauroyl peroxide 0.5% H2O2 6.8% Water and by-products Remaining pH 4

Composition 6 NaPS 2.7% Dobanol 23-3 2.5% Dobanol 91-10 2.6% Isopar M 1.5% Benzoyllauroyl peroxide 0.5% H2O2 6.8% Water and by-products Remaining pH 4

Composition 7 Dobanol 23-6.5 7.0% Dobanol 23-3 1.5% Dobanol 91-10 1.6% NaPS 1.7% Isopar M 1.5% Benzoyl lauroyl peroxide 0.5% H2O2 6. 8% water and by-products remaining pH 4

──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicants ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Schalla, Stefano Italy, 00128 Rome, Viale, Dei, Caduit, Nella, Italy Guerra, di, liberazione 131 (72) Inventor Zanazzi, Sylvia Italy, 006123 Perugia, Via, Emme, Bonaparte, Ventini 45 F-term (reference) 4H003 AB14 AC08 BA09 BA12 DA01 DA03 EB10 ED02 EE04 FA08 FA15 FA28 FA42

Claims (8)

[Claims] 1. A general formula in a bleaching composition to provide soil removal and improved fabric color safety. Wherein R1 is an aliphatic group and R2 is an aromatic group. 2. R1 is an aliphatic group having 1 to 30, preferably 4 to 20 carbon atoms, and is a linear, branched, cyclic, saturated, unsaturated, substituted, unsubstituted aliphatic group or a mixture thereof. The use according to claim 1, wherein the use is selected from any of the groups: 3. The method according to claim 1, wherein R2 is an aromatic group selected from a monocyclic or polycyclic ring, a homoatom or a heteroatom, a substituted or unsubstituted aromatic group, or a mixture thereof. Use according to 2. 4. R1 and R2 independently represent a halide, a sulfur-containing functional group, a nitrogen-containing functional group, or an alkyl chain having 1 to 20, preferably 4 to 13 carbon atoms.
Or substituted with an alkyl chain having a range of or a mixed group thereof.
3. The use according to any one of 3. 5. The diacyl peroxide is a benzoylalkanoyl peroxide, wherein the alkanoyl group has 8 to 18 carbon atoms.
Use according to any one of the preceding claims. 6. The diacyl peroxide is benzoyl lauroyl peroxide, benzoyl decanoyl peroxide, benzoyl cetyl peroxide, para-alkyl benzoyl lauroyl peroxide where alkyl is preferably pentyl, para-alkyl benzoyl decanoyl peroxide, para-alkyl benzoyl set. The use according to any one of claims 1 to 5, wherein the use is selected from the group consisting of il peroxide and mixtures thereof. 7. The use according to any one of claims 1 to 6, wherein the bleaching composition is aqueous. 8. The use according to claim 1, wherein the bleaching composition comprises at least one surfactant.