JP2002529582A - Bleach-containing detergent composition - Google Patents

Abstract

A detergent composition comprising a bleach-sensitive component and a hydrogen peroxide source, wherein the hydrogen peroxide source is present in a particulate component having an average particle size, by weight, of from 700 microns to 1100 microns, preferably from 750 microns to 1000 microns, whereby at least 80% by weight of the particulate component comprising the hydrogen peroxide source has a particle size of between 70% to 130% of the of the average particle size. The compositions preferably comprise a bleach activator of a specified average particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a detergent composition comprising a bleach sensitive component and a hydrogen peroxide source having a particular particle size.

BACKGROUND bleach-containing detergent compositions of the invention generally oxygen-based bleaching agent, typically comprises a perborate or percarbonate to release the hydrogen peroxide in the wash water, the bleach activator or Often contains precursors. In solid detergent compositions, these compounds are typically mixed as separate granules with the base composition.

[0003] Detergents are also sensitive to bleaches and also contain certain components that can react with the bleaches during manufacture or storage or use. Therefore, these bleach sensitive ingredients,
Their performance may be impaired when present in bleach-containing compositions. For example, fragrances, enzymes, dyes and brighteners are bleaches, especially when these components are present as a top sprayed component or as a mixed component.
It may react especially with percarbonate and perborate bleaches. Various techniques for protecting components that are sensitive to bleach are known, such as coating these components. However, there is a need to further improve the stability of bleach sensitive components.

Here, the present inventors have found that this problem can be alleviated by incorporating a special, large-particle-size, narrow-particle-size hydrogen peroxide supply source into a solid detergent composition. I found it. This is because the hydrogen peroxide source with a large particle size, per unit weight,
Therefore, it is considered that the surface area per active oxygen or available oxygen is small. That is, the total surface area per unit amount of active oxygen bleach that may come into contact with bleach sensitive components in the composition is small. This reduces the likelihood that the bleach sensitive component will react with the percarbonate or perborate upon contact. In particular, in compositions where the bleach-sensitive component is present as admixed granules, or where the bleach-sensitive component is sprayed onto detergent particles, including percarbonate, hydrogen peroxide The large particle size of the source of the present invention has been found to be advantageous for bleach sensitive components.

Generally, the larger the particle size of a particle, the lower the rate at which the particle dissolves in water. Therefore, it is expected that the particulate hydrogen peroxide supply source also has a low rate of dissolving in water.
Surprisingly, however, we have found that large particle sizes of hydrogen peroxide sources, especially percarbonates, can be reduced to smaller sources, for example having an average particle size of about 600, or even 500
It has been found to have a water solubility comparable to that of a percarbonate, which is micron. The present inventors have also surprisingly found that the bleaching performance of a detergent composition containing a hydrogen peroxide source and a bleaching activator is always sufficient after storage, even if the bleaching agent is stable. I also discovered that it is not limited. The inventors have also discovered that bleaching performance can vary from batch to batch of product.

[0006] Here, the inventors have found that this is due in particular to the fact that the components of the hydrogen peroxide source in the granular product segregate during manufacture or storage and that the hydrogen peroxide source component and / or the bleach activator component Has been found to be due to non-uniform distribution of.

[0007] We believe that the bleach activator component, or a portion thereof, also has a large average particle size, preferably an average particle size equivalent to the hydrogen peroxide source component, and that these components in the product It has been found that it is advantageous to reduce segregation. Preferably, the base granules of the composition also have an average particle size comparable to that of the hydrogen peroxide source component and preferably the bleach activator component.

SUMMARY OF THE INVENTION The present invention comprises a bleach sensitive component and a hydrogen peroxide source, wherein the hydrogen peroxide source has a weight average particle size of 700 microns to 1100 microns, preferably 700 microns to 1000 microns. At least 80% by weight of the particulate component present in the particulate component having a micron and comprising a hydrogen peroxide source comprises at least 60% of the average particle size.
A solid composition having a particle size of ~ 140% is provided. Preferably, the composition comprises one or more bleach activators.

[0009] DETAILED DESCRIPTION peroxide sources peroxide sources invention are present in the particulate component of the composition, preferably with the other detergent ingredients, preferably of different granular components of the composition In form, they are mixed. The particulate component containing the hydrogen peroxide source preferably has an average particle size of 700 microns to 1000 microns.
Microns, more preferably 750 microns or more, or 800 microns to 950
Microns, or even 820-920 microns.

Wherein at least 80% by weight of the particulate component comprising a hydrogen peroxide source,
Preferably at least 90% by weight, even at least 95% by weight, or substantially 100% by weight, is from 60% to 140% of the weight average particle size, preferably from 70% to 130% of the weight average particle size, more preferably the weight 80% to 120% of the average particle size
Having a particle size of

At least 70% or at least 80%, more preferably at least 90% or at least 95% by weight of the component comprising the hydrogen peroxide source
Preferably have a particle size of 600 microns or more, or 710 microns to about 1180 microns, preferably 710 microns to 1000 microns.

Here, particles having a particle size of less than 425 microns, even less than 600 microns, are preferably less than 10% by weight, or less than 6% by weight, more preferably less than 4% by weight.

[0013] Here, particles having a particle size of more than 1400 microns, more preferably more than 1180 microns are preferably less than 10% by weight, or less than 6% by weight, more preferably less than 4% by weight.

[0014] Preferably, the weight distribution of the particle sizes of the components comprising the hydrogen peroxide source is very narrowly distributed around one intermediate, or average or median.

For example, it is preferable that the weight average particle diameter is 800 microns, the particle diameter less than 600 microns is 5% by weight or less, and the particle diameter exceeding 1180 microns is less than 2% by weight. It is also preferable that the weight average particle diameter is 800 microns, the particle diameter less than 425 microns is 3% by weight or less, and the particle diameter exceeding 1400 microns is less than 5% by weight.

As used herein, the average particle size is the weight average particle size, and the particle size of the product sample is sieved by any conventional method known in the art, for example, through a series of specific mesh size sieves, It is determined by measuring the weight fraction of the material left on and / or passed through the sieve. Maximum and minimum particle sizes can also be measured by sieving a particular mesh size by methods known in the art.

Preferred sources of hydrogen peroxide are perhydrate bleaching agents, such as metal peroxymonopersulfates, more preferably metal perborates, most preferably metal percarbonates, especially their potassium, more preferably Is a sodium salt.

In particular, the percarbonate used here may be coated. Suitable coatings are known in the art and are, for example, hydrophobicizing agents such as waxes, inorganic salts such as magnesium salts, sulfates, and carbonates and silicates or mixtures thereof.

The hydrogen peroxide source, and preferably the component comprising it, is such that 75% of the theoretical maximum available oxygen (AvO) of the component is less than 10 minutes, preferably less than 8 minutes, more preferably 6 minutes. It has a solubility of 10 ° C. such that it is released below. Preferably, at least 50% of the theoretical maximum available oxygen is released in less than 5 minutes, preferably in less than 4 minutes.

The solubility is determined by adding 5.0 grams of the hydrogen peroxide source or its containing components to Tergotom.
eter ERWEKA, Model DT6R In a plastic beaker of model DT6R, add 1 liter of deionized water containing 50 ml of acetic acid at 10C, mix the water-hydrogen peroxide source mixture with a paddle at a speed of 150 rpm and take a 15 ml sample when needed The available oxygen in the sample can be determined by titration, for example, by measuring with 0.1 N thiosulfate using an automatic Mettler DL titrator.

Bleach Sensitive Components As used herein, bleach sensitive components can be incorporated into a detergent composition and used during the manufacture, storage or use of the composition. Any component known in the art that may react with the hydrogen peroxide source or hydrogen peroxide during the washing or washing operation performed may be used.

For the purposes of the present invention, the bleach-sensitive components or parts thereof can be present, in particular, in the form of components that are sprayed onto the granules of the solid detergent composition of the present invention.
However, the bleach-sensitive ingredients or some of them may be present in other forms, for example as mixed granules, or the bleach-sensitive ingredients or some of them may be It may be contained inside.

Preferred bleach-sensitive ingredients comprise fragrances, enzymes, brighteners, dyes, photobleaches, dispersants, soil release agents, in particular oxidizable functional groups,
For example, a component comprising an alkenyl group, an aldehyde group or an amine group.
Bleach sensitive components suitable for use in the present invention are described below.

Detergent Composition The detergent composition of the present invention is preferably a solid laundry, dishwashing or hard surface cleaning composition, most preferably a laundry or dishwashing composition. The compositions are preferably in the form of granules, but here tablets, bars and flakes, preferably made from the particulate components, are also contemplated.

The composition preferably comprises granules, at least 60% by weight of the granules, more preferably at least 80% by weight, comprising from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns, even 750 to 1000 microns. It has an average particle size of microns. Less than 300 microns, even less than 425 microns, or even less than 600 microns of particles in the composition should be less than 20%, even less than 10%, or even less than 5% by weight of the particulate component. Preferably 170
Preferably, particles greater than 0 microns, even greater than 1400 microns, or even greater than 1180 microns, are less than 20%, even less than 10%, and even less than 5% by weight of the composition.

The composition can be made by any known method, including agglomeration and / or spray drying, wherein the particular components can be mixed or sprayed as described herein. The composition comprises mixing all or part of the granules (including granules produced by agglomeration or spray drying), followed by the addition of a binder, and mixing or agglomerating the granules and the binder, preferably agglomerated detergent. By forming granules,
It is preferably manufactured. These granules have the required particle size or can be sieved to obtain the required particle size. Here, it is preferable that the component containing the mixed hydrogen peroxide source is not mixed and aggregated with other granules and a binder.

The composition is preferably a solid detergent, preferably having a density of at least 350 g /
Liter, more preferably at least 500 g / liter, even more preferably at least 580 g / liter.

[0028] The compositions of the present invention can also include other detergent components. The exact nature of these other ingredients and their loading will depend on the physical form of the composition or ingredient and the nature of the washing operation using the composition.

Very preferably, one or more bleach activators as described below are present.

In one embodiment of the present invention, the detergent composition of the present invention preferably comprises one or more anionic surfactants and an aluminosilicate builder, wherein a small amount of an aluminosilicate Only the builder and the anionic surfactant, ie less than 50%, even less than 30% of the total amount of anionic surfactant, and less than 50%, even less than 30%, of the total amount of aluminosilicate are tight. Preferably it is in a mixture, more preferably the anionic surfactant and the aluminosilicate builder are not substantially intimately mixed. For example, the composition preferably comprises at least two additional particles comprising either an anionic surfactant or an aluminosilicate. "Intimate mixture" means for the purposes of the present invention 2
It means that one or more components are substantially homogeneously divided in the components or particles. Thereby, the solubility and / or delivery properties of the composition are improved. In another embodiment of the invention, the composition is at a very low level, for example 10% by weight of the composition
Preferably, the composition comprises less than 5% by weight of an aluminosilicate builder, wherein the composition is highly soluble, such as sodium citrate or citric acid, carbonate, and / or crystalline. It is preferable to comprise a layered silicate.

When the composition as a builder system or as part of a builder system, 0.5 to 80% by weight of a crystalline layered silicate, preferably NaSKS-6, and 10 to 70% by weight
Preferably comprises an agglomerate comprising a surfactant, preferably an anionic surfactant, wherein less than 10% by weight of the agglomerate is free water, more preferably 30% by weight. -60% by weight is a crystalline layered silicate,
% By weight is the anionic surfactant.

The intumescent detergent composition preferably comprises an intumescent component comprising an acid source and an alkali source which react with each other upon contact with water to form a gas, especially organic carboxylic acids. It is highly preferred that carbon dioxide gas be formed by the reaction of the carbon dioxide gas with the carbonate source. For the purposes of the present invention, the intumescent components can be present in an intimate mixture with one another, preferably in the form of granules, or in separate particles.

The intumescent component is preferably a particulate component having a weight average particle size of 700 to 1400 microns, preferably 750 to 1100 microns, and preferably comprising an acid source and an alkali source.

It is preferred that the effervescent component is substantially anhydrous and that water is not intimately mixed with the effervescent component or a portion thereof, or that there is no water other than the raw material itself.
Typically, the amount of water in the intimate mixture with the intumescent component is less than 5%, preferably less than 3%, more preferably less than 1.5% by weight of the total granule, preferably dry Obtained by powder compression or pressure agglomeration.

With these preferred dry intumescent particles, carbon dioxide is formed very rapidly,
Accordingly, dispersion and dissolution of the granular composition are promoted. The granular composition comprising the dry effervescent granules of the present invention, as described herein, provides low levels of total effervescent particles /
With the material, the granular composition can be supplied and dissolved in water in a short time, and the detergent component can be more quickly and more efficiently introduced into the washing liquid.

[0036] Acids suitable for use herein include solid organic, mineral or inorganic acids, salts or derivatives thereof, or mixtures thereof. Preferably, the acid is a mono-, di-, or tri-protic acid. Such acids include mono- or polycarboxylic acids, preferably citric, adipic, glutaric, triketoglutaric,
Citramaric acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are preferably used in their acid form, preferably in their anhydrous form, or in mixtures thereof. Derivatives also include esters of acids.

The effervescent component or source preferably comprises a carbonate source, including carbonates, bicarbonates and percarbonates, especially bicarbonates and / or carbonates. Suitable carbonates for use herein include carbonates and bicarbonates such as potassium, lithium, sodium and the like, among which sodium and potassium carbonates are preferred. Bicarbonates suitable for use herein include alkali metal bicarbonates, such as lithium, sodium, potassium, and the like, among which:
Sodium and potassium bicarbonates are preferred. Bicarbonate is preferred over carbonate because it is more weight efficient, ie, at equivalent weight, bicarbonate is a larger CO ₂ store than carbonate. However, the carbonates or bicarbonates or mixtures thereof in the dry effervescent granules may be present in the aqueous medium in which the dry effervescent granules dissolve
H is selected according to H. For example, a relatively high pH (eg, pH 9
. If greater than 5) is desired, carbonate alone may be used, or a combination of carbonate and bicarbonate, wherein the level of carbonate is higher than the level of bicarbonate, typically carbonate and bicarbonate. It is preferred to use combinations in which the weight ratio of the salts is between 0.1 and 10, more preferably between 1 and 5, most preferably between 1 and 2.

[0038] Such intumescent granules can also comprise a binder, including surfactants, such as anionic and nonionic surfactants.

The intumescent component is present in the composition of the present invention, preferably at 0.5 to 60% by weight of the composition.
Preferably, the acid component is present in an amount of from 2 to 50%, more preferably from 5 to 45%, preferably from 0.3 to 40%, more preferably from 1.0 to 35%, by weight of the composition. More preferably it is present in an amount of from 2 to 25% by weight, even more preferably up to 15% by weight.

The bleach activator composition preferably comprises a bleach activator, preferably a bleach activator comprising an organic peracid bleach precursor. Preferably, the composition comprises at least two peracid bleach precursors, at least one hydrophobic peracid bleach precursor and at least one hydrophilic peracid bleach precursor as defined herein. It preferably comprises a substance. In this case, the organic peracid is formed by the in situ reaction of the precursor and the hydrogen peroxide source.

Alternatively, or in addition, the bleach activator can comprise a preformed peracid bleach.

[0042] The bleach activator is preferably present in the particulate component of the composition of the present invention.
The bleach activator is preferably present in separate, mixed particles. Alternatively, the bleach activator, or a portion thereof, can be present in the base detergent particles.

Preferably, at least one bleach activator, preferably a peracid bleach precursor,
Is present in the particulate component having a weight average particle size of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. More preferably,
All of the activator is present in one or more particulate components having a defined weight average particle size.

Here, at least 80%, preferably at least 90%, even at least 95% and even substantially 100% of the components comprising the bleach activator are 300%
It has a particle size between 1 micron and 1700 microns, preferably between 425 microns and 1400 microns.

The hydrophobic peracid bleach precursor preferably comprises a compound having an oxy-benzenesulfonate group, preferably NOBS, DOBS, LOBS and / or NACA-OBS as described herein.

[0046] The hydrophilic peracid bleach precursor preferably comprises a TAED as described herein.

The peracid bleach precursor peracid bleach precursors react with hydrogen peroxide in par hydro lysis (perhydrolysis) reaction is a compound which forms peracetic acid. Generally, the peracid bleach precursor is represented as O ＯX-C-L, where L is a leaving group and X is the structure of the peracid formed by perhydrolysis, O が X-C-L. Substantially all functional groups such as OOH.

For the purposes of the present invention, the hydrophobic peracid bleach precursor forms a peracid of the above formula wherein X has at least 6 carbon atoms, and the hydrophilic peracid bleach precursor comprises In the above equation,
A peracid bleach having 1 to 5 carbon atoms of X is formed.

The peracid bleach precursor compound is preferably present in an amount of 0.5 to 20%, more preferably 1 to 15%, most preferably 1.5 to 10% by weight of the detergent composition. The ratio of hydrophilic bleach precursor to hydrophobic bleach precursor, if present, is preferably from 10: 1 to 1:10, more preferably from 5: 1 to 1: 5, and even more preferably from 3: 1 to 1: 1.
: 3.

Suitable peracid bleach precursor compounds typically contain one or more N- or O-acyl groups, and these precursors can be selected from a wide range of groups. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials falling into these categories are described in GB-A-1586789. Suitable esters are described in British Patent Nos. GB-A-836988, GB-A-864798,
These are described in GB-A-1147871, GB-A-2143231 and EP-A-0170386.

The leaving group leaving group (hereinafter, referred to as L group) should have an optimum time frame (e.g., the wash cycle) sufficient reactivity as par hydro lysis reaction occurs in the. However, if the reactivity of L is too high, the activator becomes difficult to stabilize for use in bleaching compositions.

Preferred L groups are selected from the group consisting of the following substances, and mixtures thereof:

Embedded image In the formula, R ¹ is an alkyl, aryl, or alkaryl group having 1 to 14 carbon atoms, R ³ is an alkyl chain having 1 to 8 carbon atoms, R ⁴ is H or R ³ , Y is H or a group imparting solubility. Any of R ¹ , R ³ and R ⁴ may be substituted by substantially all functional groups including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

A group that imparts a preferred solubility is —SO₃ ⁻M⁺, -CO₂ ⁻M⁺, -SO₄ ⁻ M⁺, -N⁺(R³)₄X⁻And O <-N (R³)₃And most preferably
Is -SO₃ ⁻M⁺And -CO₂ ⁻M⁺And R³Represents an alkyl group having 1 to 4 carbon atoms.
M is a cation that confers solubility to the bleach activator, and X is a bleach chain.
An anion that imparts solubility to the whitening agent active. Preferably M is an alkali metal,
Ammonium or substituted ammonium cations, sodium and potassium
X is most preferably halide, hydroxide, methyl sulfate or aluminum.
It is a acetate anion.

Alkyl percarboxylic acid bleach precursor The alkyl percarboxylic bleach precursor forms percarboxylic acid by perhydrolysis. Preferred precursors of this type form peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds are N-, N, N ¹ N ¹ tetraacetylated alkylenediamines having 1 to 6 carbon atoms in the alkylene group, particularly 1 in the alkylene group. 2 and 6. Tetraacetylethylenediamine (TAED) is particularly preferred as the hydrophilic peracid bleach precursor.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium sulfonate (ABS) and pentaacetylglucose.

Amide-Substituted Alkyl Peracid Precursors Amide-substituted alkyl peracid precursors are preferred herein and include those having the general formula:

Embedded imageWhere R¹Is an aryl or alkaryl group having 1 to 14 carbon atoms; ² Is an alkylene, arylene, or alkarylene group having 1 to 14 carbon atoms
And R⁵Is H or an alkyl, aryl, or alkenyl having 1 to 10 carbon atoms.
A lucaryl group, wherein L can be substantially any leaving group. R¹Is preferably charcoal
The prime number is about 6-12. R²Preferably has 4 to 8 carbon atoms. R¹Is linear
Branched or branched alkyl, substituted aryl or alkylaryl, branched
, Substituted or both, synthetic sources or natural including, for example, tallow fat
It can be obtained from a source. R²Similar structural variants are possible with respect to. R ² Includes alkyl and aryl;²Is halogen, nitrogen, sulfur and other
Typical substituents or organic compounds can also be included. R⁵Is preferably H
Is methyl. R¹And R⁵Should not exceed 18 in total.
Amide-substituted bleach activator compounds of this type are described in EP-A-01.
70386. R¹And R⁵Is a source of nitrogen and carbon
In some cases, it is preferable to form a ring structure together.

Preferred examples of bleach precursors of this type include EP-A-01
(6-Octanamido-caproyl) as described in US Pat.
Oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and highly preferred (6-nonanamido-caproyl) oxybenzenesulfonate, and mixtures thereof.

Perbenzoic acid precursor The perbenzoic acid precursor gives perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyl oxybenzenesulfonates, and products of benzoylation of sorbitol, glucose, and all saccharides with benzoylating agents, and Examples include imide-type perbenzoic acid precursor compounds including N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Cationic Peracid Precursor The cationic peracid precursor compound forms a cationic peracid by perhydrolysis.

Typically, the cationic peracid precursor comprises a peracid moiety of a suitable peracid precursor compound, wherein the peracid moiety is a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group. , And is formed by substitution. Cationic peracid precursors are typically included in solid detergent compositions in suitable anions,
For example, it exists as a salt with a halide ion.

[0062] The peracid precursor compound so cationically substituted may be perbenzoic acid or a substituted derivative thereof, a precursor compound as described above. Alternatively, the peracid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peracid precursor described below.

Cationic peracid precursors are described in US Pat. Nos. 4,904,406 and 4,751.
No. 015, No. 4,988,451, No. 4,397,757, No. 5,269
No. 5,962, 5,127,852, 5,093,022, 5,106
No. 528, British Patent 1,382,594, European Patent 475,51.
No. 2, 458, 396 and 284, 292, and Japanese Patent No. 87
-318, 332.

Examples of preferred cationic peracid precursors are described in UK Patent Application No. 9407944.9.
Nos. 08 / 298,903; 08 / 298,650;
Nos. 8 / 298,904 and 08 / 298,906. Suitable cationic peracid precursors include all ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactam, and monobenzoyl tetraacetylglucose benzoyl peroxide. Preferred cationic peracid precursors of the N-acylated caprolactam group include trialkyl ammonium methylene benzoyl caprolactam and trialkyl ammonium methylene alkyl caprolactam.

Benzoxazine organic peracid precursors such as EP-A-332,294 and EP-A
Also suitable are benzoxazine-type precursor compounds as described in -482,807, especially compounds having the formula:

Embedded image Wherein R ₁ is H, alkyl, alkaryl, aryl, or arylalkyl.

The preformed organic peracid detergent composition may comprise, in addition to or instead of the organic peracid bleach precursor, a preformed organic peracid, typically 1 to 15 parts of the composition. % By weight, more preferably 1 to 10% by weight.

A preferred class of organic peracid compounds are amide substituted compounds having the general formula:

Embedded image Wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, and R ⁵ is H Or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Such amide-substituted organic peracid compounds are described in EP-A-0170386.

Other organic peracids include diacyl and tetraacyl peroxides, especially diperoxidedecandionic acid, diperoxytetradecandionic acid and diperoxyhexadecandionic acid. Mono- and diperazelaic acids, mono- and diperbracyl acids and N-phthaloylaminoperoxycaproic acid are also suitable for the present invention.

Dyes Preferred components for the compositions of the present invention are dyes and dyed particles or speckles that are sensitive to bleach. The dyeing material used here can be a dye or an aqueous or non-aqueous solution of a dye. The dyeing material is preferably an aqueous solution comprising a dye such that a dye solution at a level of up to 2% by weight, more preferably up to 0.5% by weight of the dyed particles is obtained as described above. The dye may be mixed with a non-aqueous carrier material, such as a non-aqueous liquid material including a non-ionic surfactant.

If desired, the dye may comprise other ingredients, such as an organic binding material, which may also be a non-aqueous liquid,
Also comprises.

The dye may be any suitable dye. Specific examples of suitable dyes include E104-Food Yellow 13 (quinoline yellow), E110-Food Yellow 3 (Sunset Yellow FCF), E131-Food Blue 5 (Patent Blue V), Ultra Mari
ne blue (trade name), E133-food blue 2 (brilliant blue FCF),
E140-Natural Green 3 (chlorophyll and chlorophyllin), E1
41 and Pigment Green 7 (chlorinated Cu phthalocyanine).
Preferred dyes are Monastral Blue BV paste (trade name) and / or Pigmaso
l Green (trade name) may be used.

The dyed detergent particles preferably comprise up to 10% by weight, more preferably 2% by weight,
It further comprises up to 1% by weight of dyed particles.

Perfume Another preferred ingredient of the compositions of the present invention is a perfume or perfume composition. Here, any perfume composition can be used. Flavors can also be encapsulated.

Preferred perfumes comprise at least one volatile component having a low molecular weight, for example from 150 to 450, preferably 350.

Preferably, the fragrance component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Suitable aliphatic ketones are, for example, -2,7,8-trimethyl-1-acetyl-cyclododeca-2,5,7-triene-7-acetyl-1,1,6,7-tetramethyl-1 , 2,3,4,5,6,7
, 8-octahydronaphthalene-isolongifolane-gamma-ylone-alpha-vetibon.

Suitable aromatic ketones are, for example, -4 (p-hydroxyphenyl) -butan-2-one-1,1,2,4,4,7-hexamethyl-6-acetyl-tetralin-benzophenone-methylnaphthyl Ketone.

Suitable aliphatic aldehydes are, for example, -2-methylhendecanal-undecanal-4 (4′-methyl-4′-hydroxypentyl) -cyclohex-3-encarbaldehyde-7- (formyl-5) -Isopropyl-2-methyl-bicyclo [2.2.2] oct-2-ene-4- (tricyclo [5.2.1.0 {2,6}] decylidene-8) -butanal-4- (4 '-Methylpent-3-enyl) -cyclohex-3-encarbaldehyde.

Suitable aromatic aldehydes are, for example, -alpha-hexylcinnamaldehyde-anisaldehyde-heliotropin-2-phenylpropanal-dihydrocinnamaldehyde-3- (p-tert-butylphenyl) -2-methylpropanal It is.

Suitable aldehyde and amine condensation products are, for example, -methyl N- (2,4-dimethyl-3-cyclohexenyl) methylidene-anthranilate-methyl N- (3,7-dimethyl-7-hydroxy (Acetylidene) -anthranilate-methyl N- (4- (4'-methyl-4'-hydroxypentyl) cyclohex-3-enyl] methylidene anthranilate.

A suitable macrocyclic lactone mask is, for example, -ethylene dodecandioate-11-oxahexadecanolide-cyclopentadecanolide.

A preferred perfume here is high impact accord (“HIA”) perfume oil particles contained in a modified starch capsule. Preferred HIA perfume oils include the following: 4- (2,2,6-trimethylcyclohex-1-enyl) -2-en-4-one 2,4-decadienoic acid, ethyl ester (E, Z) -6- (and-8) isopropylquinoline acetaldehyde Phenylethylpropyl acetal acetic acid, (2-methylbutoxy)-, 2-propenyl ester acetic acid, (3-methylbutoxy)-, 2-propenyl ester 2,6,10-trimethyl-9-undecenal glycolic acid, 2-pentyloxy Allyl ester hexanoic acid, 2-propenyl ester 1-octen-3-ol transanethole isobutyl (z) -2-methyl-2-butenoate anisaldehyde diethyl acetal benzenepropanal, 4- (1,1-dimethylethyl)- 2,6-nonadiene-1-ol 3-methyl -5-propyl-cyclohexen-1-one butanoic acid, 2-methyl, 3-hexenyl ester, (Z) -acetaldehyde [(3,7-dimethyl-6-octenyl) oxy] -lauronitrile 2,4-dimethyl- 3-cyclohexene-1-carbaldehyde 2-buten-1-one, 1- (2,6,6-trimethyl-1,3-cyclohexadien-1-yl) -2-buten-1-one, 1- ( 2,6,6-trimethyl-2-cyclohexene-
1-yl)-, (E)-gamma-decalactone trans-4-decenal decanal 2-pentylcyclopentanone 1- (2,6,6-trimethyl-3-cyclohexen-1-yl) -2-butene-1-
On) 2,6-dimethylheptane-2-ol benzene, 1,1'-oxybis-4-penten-1-one, (5,5-dimethyl-1-cyclohexen-1-yl) -butanoic acid, 2- Methyl-, ethyl ester ethyl anthranilate 2-oxabicyclo [2.2.2] octane, 1,3,3-trimethyl-eugenol 3- (3-isopropylphenyl) butanal methyl 2-octinoate 4- (2,6 , 6-Trimethyl-1-cyclohexen-1-yl-3-butene-
2-one pyrazine, 2-methoxy-3- (2-methylpropyl) -quiniline, 6-secondary butyl isoeugenol 2H-pyran-2-one, tetrahydro-6- (3-pentenyl) -cis-3- Hexenyl methyl carbonate linalool 1,6,10-dodecatriene, 7,11-dimethyl-3-methylene-, (E)
2,6-dimethyl-5-heptenal 4,7 methanoindane 1-carboxaldehyde, hexahydro 2-methylundecanal methyl 2-noninonate 1,1-dimethoxy-2,2,5-trimethyl-4-hexene benzoic acid, -Hydroxy, methyl ester 4-penten-1-one, 1- (5,5-dimethyl-1-cyclohexene-1-
Yl) 2H-pyran, 3,6-dihydro-4methyl-2- (2-methyl-1-propenyl) -2,6-octadienenitrile, 3,7-dimethyl-, (Z) -2,6- Nonadienal 6-nonenal, (Z) -nonanal octanal 2-nonenenitrile acetic acid, 4-methylphenyl ester gamma undecalactone 2-norpinene-2-propionaldehyde 6,6 dimethyl 4-nonanolide 9-decene-1-ol 2H-pyran , Tetrahydro-4-methyl-2- (2-methyl-1-propenyl) -5-methyl-3-heptanone oxime octanal, 3,7-dimethyl-4-methyl-3-decene-5-ol 10-undecene -1-al pyridine, 2- (1-ethylpropyl) -spiro [furan-2 (3H), 5 '-[4, ] Methano [5H] indane, decahydro - further, the perfume can be fragrance precursors including.

The perfume precursor can form a perfume component having the above characteristics when exposed to laundry conditions. Preferably, the perfume precursor forms a perfume component by hydrolysis under aqueous conditions.

Preferred perfume precursors here are nonionic or anionic esters of allyl alcohol perfume having the formula:

Embedded image In the formula, n is an integer of 1 or more, and R is a C ₁ -C ₃₀ , preferably C ₁ -C ₂₀ linear, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group. And represents a group added to the carboxylate functional group of the carboxylic acid used in the production of the fragrance ester. Each R ',
R ″, and each R ′ ″, is selected from the group consisting of hydrogen, C ₁ -C ₂₀ linear, branched, or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl groups. R ', R "and R'" are selected such that the molecular weight of the allyl alcohol is between 150 and 350.

In a most preferred embodiment, R ′ and R ″ are hydrogen, one R ′ ″ is hydrogen, methyl or ethyl, and the other R ′ ″ is linear, branched or cyclic. C ₁ is a -C ₁₀ alkyl or alkenyl group. (also referred to as Z / E) cis / trans at the double bond of the structure shown on a stereoisomer isomers and the structures possible.

[0086] Preferred perfume ingredients can be selected from the group comprising esters of geraniol and / or nerol. Geraniol and nerol have the formula HO-
It is a trans / cis structural isomer of a molecule having CH ₂ —CH ＝ C (CH ₃ ) —CH ₂ —CH ₂ —CH ＝ C (CH ₃ ) ₂ (at a double bond at the 2,3-position).

Heavy Metal Ion Sequestering Agent The detergent composition of the present invention preferably contains a heavy metal ion sequestering agent or a keyant or chelating agent as an optional ingredient. The heavy metal ion sequestering agent means a component that sequesters (chelates) heavy metal ions. These components may have the ability to chelate calcium and magnesium, but have the selectivity to preferentially bind heavy metal ions such as iron, manganese and copper. Heavy sequestrants generally comprise from 0.005 to 10% by weight of the composition or component,
Preferably it is present in an amount of 0.1-5% by weight, more preferably 0.25-7.5% by weight, most preferably 0.3-2% by weight.

[0088] Suitable heavy metal ion sequestering agents for use herein include organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-
Hydroxydiphosphonate, and nitrilotrimethylenephosphonate.

Preferred among the above substances are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane Diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.

Other heavy sequestering agents suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinate. An acid or any salt thereof is included.

[0091] Other suitable heavy sequestering agents for use herein are iminodiacetic acid derivatives, such as EP-A-317,542 and EP-A-39.
2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid as described in US Pat. No. 9,133. Sequestration of iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516,102. Agents are also suitable here. European Patent EP-A-5
Also preferred are the β-alanine-N, N′-diacetic acid, aspartic acid-N, N′-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinate sequestering agents described in JP-A-09,382. It is.

European Patent EP-A-476,257 describes suitable amino sequestering agents. European Patent EP-A-510,331 describes suitable sequestering agents derived from collagen, keratin or casein. European Patent EP-A-528,859 describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2
-Phosphonobtan-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N′-disuccinic acid (GADS), ethylenediamine-NN′-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-NN′-disuccinic acid (HPDDS) are also suitable.

Diethylenetriaminepentaacetic acid, ethylenediamine-N, N′-disuccinic acid (EDDS), 1,1-hydroxyethanediphosphonic acid or an alkali metal, alkaline earth metal, ammonium, or substituted ammonium salt thereof, or a mixture thereof Is particularly preferred.

In particular, chelating agents comprising amino or amine groups may be sensitive to bleach and are suitable for the compositions of the present invention.

Enzymes Another preferred ingredient useful in the present compositions is one or more additional enzymes.

Preferred additional enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally formulated in detergent compositions. Suitable enzymes are described in U.S. Patent Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include Alcalase, Savinase, Primase, Dura
an enzyme sold by Novo Industries A / S (Denmark) under the trade names zym and Esperase, an enzyme sold by Gist-Brocades under the trade names Maxatase, Maxacal and Maxapem, an enzyme sold by Genencor International, And enzymes sold by Solvay Enzymes under the trade names Opticlean and Optimase. The protease enzyme is present in the composition of the present invention in an amount of 0.000% of the composition.
It can be incorporated in an amount of 1 to 4% by weight active enzyme.

Preferred amylases are described, for example, in GB 1,269,839 (Nov
o) includes α-amylases obtained from special strains of B. licheniformis, described in more detail. Preferred commercially available amylase is, for example, by Gist-Brocades
Enzyme sold under the trade name Rapidase and trade name by Novo Industries A / S
Includes enzymes sold under Termamyl, Duramyl and BAN. Highly preferred amylase enzymes are described in PCT / US 9703635 and in International Patent WO
95/26397 and WO96 / 23873.

The amylase enzyme is incorporated into the compositions of the present invention in an amount of 0.0001 to 2% active enzyme by weight of the composition.

The lipolytic enzyme is present at 0.0001 to 2% by weight of the composition, preferably at 0.001 to 2%.
It can be present in an amount of 1% by weight, most preferably 0.001 to 0.5% by weight of active lipolytic enzyme.

The lipase may be of fungal or bacterial origin, for exampleHumicola sp., Thermomyces sp. orPseudomonas pseudoalcaligenes OrPseudomas fl uorescens EncompassesPseudomonas It is obtained from a lipase-producing strain of sp. this
Lipases from chemically or genetically modified mutants of these strains
Useful here. Described in European Patent EP-B-0218272
Have beenPseudomonas pseudoalcaligenes A lipase derived from is preferred. Another lipase preferred here is European Patent Application No. EP-A-02580.
As described in the specification of No. 68,Humicola lanuginosa The gene obtained from
Loan and hostAspergillus oryza By expressing the gene in
Lipolase trade name from Novo Industri A / S, Bagsvaerd, Denmark,
It is commercially available at This lipase is disclosed in US Pat. No. 4,810,414,
It is also described in Huge-Jensen et al., Promulgated March 7, 1989.

Optical Brightener The compositions of the present invention can also optionally contain from about 0.005 to 5% by weight of certain hydrophilic optical brighteners.

The hydrophilic optical brighteners useful in the present invention include those having the following structural formula:

Embedded image Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, and R ₂ is N-2-bis-hydroxyethyl, N-2-
Selected from hydroxyethyl-N-methylamino, morpholino, chloro and amino, M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation, eg, sodium, the brightener is
4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyethyl)-
s-Triazin-2-yl) amino] -2,2'-stilbene disulfonic acid and disodium salt. This special brightener is available from Ciba-Geigy Corporation
It is marketed under the trade name Tinopal-UNPA-GX. Tinopal-CBS-X and Tinopal-
UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation, for example, sodium, the brightener is 4, 4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2
, 2'-stilbene disulfonic acid disodium salt. This special brightener is commercially available from Ciba-Geigy Corporation under the trade name Tinopal 5BM-GX.

In the above formula, when R ₁ is anilino, R ₂ is morpholino, and M is a cation, for example, sodium, the brightener is 4,4′-bis [(
4-anilino-6-morpholino-s-triazin-2-yl) amino] -2,
2'-Stilbene disulfonic acid, sodium salt. This special brightener is commercially available from Ciba-Geigy Corporation under the trade names Tinopal-DMS-X and Tinopal AMS-GX.

Photobleaching Compounds Photobleaching agents are preferred components of the compositions of the present invention. Preferred photobleaches here are compounds having a porphine or porphyrin structure.

Although porphine and porphyrin are used as synonyms in the literature, porphine usually means the simplest porphyrin without substituents, and porphyrin is a subgroup of porphine. The meaning of porphine in the present application includes porphyrin.

The porphine structure is preferably a metal element or a cation, preferably Ca, M
g, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si
Or, it comprises Ga, more preferably Al, most preferably Zn.

The photobleaching compound or component may be an alkyl group such as methyl, ethyl, propyl,
t-butyl groups, and aromatic ring systems such as pyridyl, pyridyl-N-oxide,
It may be preferred to be substituted with a substituent selected from phenyl, naphthyl and anthracyl moieties.

The photobleaching compounds or components can have solubilizing groups as substituents. Alternatively, or in addition, the photobleach may comprise a polymeric component capable of solubilizing the photobleaching compound, such as PVP, PVNP, PVI or copolymers thereof or mixtures thereof. it can.

Very preferred photobleaching compounds are those having a phthalocyanine structure, preferably having the above-mentioned metal elements or cations.

The metal phthalocyanines and their derivatives have the structure shown in FIG. 1 and / or FIG. 2 in which the atomic positions of the phthalocyanine structure are numbered as usual.

Phthalocyanines are represented by atomic positions 1-4, 6, 8-11, 13, 15-18, 20
, A substituted phthalocyanine structure at one or more positions of 22 to 25 and 27.

Surfactants The detergent compositions of the present invention preferably comprise anionic, nonionic, cationic, amphoteric, amphoteric and zwitterionic surfactants and mixtures thereof. Including.

For a listing of anionic, nonionic, amphoteric, and zwitterionic systems and a typical listing of these surfactant varieties, see US Pat. No. 3,929,678, 19
Promulgated in Laughlin and Heuring on December 30, 1975. Other examples include Surface Active Agents and Detergents (Vol.I and II, Schwartz
, Perry and Berch). A list of suitable cationic surfactants is described in U.S. Pat. No. 4,259,217, issued Mar. 31, 1981 to Murphy.

When present, amphoteric, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants. You.

Anionic Surfactants The compositions of the present invention preferably comprise an additional anionic surfactant. Virtually all anionic surfactants useful for cleaning purposes can be incorporated into the present detergent compositions. These surfactants include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants, such as sodium, potassium, ammonium, and substituted ammonium salts, such as mono-, di- and triethanolamine salts. Can be Anionic sulphate surfactants are preferred.

Sulfonate and sulfate surfactants, preferably linear or branched alkyl benzene sulfonates and alkyl ethoxy sulfates as described herein, are preferably combined with cationic surfactants as described herein. Surfactant systems comprising, in combination, are highly preferred.

Other anionic surfactants include isethionates, such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates ( specially saturation, and desaturated a _C 12 _{-C 18} monoesters), diesters of sulfosuccinate (especially saturated reduction, and desaturated a _C 6 _{-C 14} diesters), N- acyl Sarcosinate. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactants Suitable anionic sulfate surfactants for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleates. oil glycerol sulfates, alkyl phenol ethylene oxide ether _sulfates, C 5 _{-C 17} acyl -N- _(C 1 ~C ₄ alkyl) and -N- _(C 1 ~C ₂ hydroxyalkyl) glucamine sulfates, and alkyl polysaccharides sulfates, e.g. Sulfates of alkyl polyglucosides (nonionic non-sulfated compounds described herein).

The alkyl sulphate surfactant is preferably a linear and branched primary
Grade _C 10 _{-C 18} alkyl sulfates, more preferably selected from branched alkyl sulfates and _C 12 _{-C 14} linear alkyl sulphate _C 11 _{-C 15.}

The alkyl ethoxy sulphate surfactants are preferably present in an amount of 0,1 per molecule.
Selected from the group consisting of _C 10 _{-C 18} alkyl sulfates ethoxylated with 5-20 moles of ethylene oxide. More preferably, the alkyl ethoxysulfate surfactant, per 0.5-7 moles molecule, preferably _C 11 _{-C 18} ethoxylated with 1-5 moles of ethylene oxide, most preferably _{C 11} ~
Is a C ₁₅ alkyl sulfates.

In a particularly preferred embodiment of the invention, a mixture of the preferred alkyl sulphates and / or sulphonates and alkyl ethoxy sulphate surfactants is used. Such mixtures are described in PCT Patent Application No. WO 93/18124.

[0124]Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include C₅~ C ₂₀ Linear alkyl benzene sulfonate, alkyl ester sulfonate, C₆ ~ C₂₂Primary or secondary alkane sulfonate, C₆~ C₂₄Olefins
Rufonate, sulfonated polycarboxylic acid, alkyl glycerol sulfonate,
Fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfonate
, And mixtures thereof.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"), especially The particular secondary soaps mentioned are mentioned.

Suitable alkylethoxycarboxylates include those having the formula:

RO (CH₂CH₂O)_xCH₂COO⁻M⁺ Where R is C₆~ C₁₈An alkyl group, x is 0 to 10,
Are distributed such that the amount of the substance with x = 0 is less than 20% by weight, and M is positive.
It is an ion. Suitable alkyl polyethoxy polycarboxylate surfactants are
, Surfactants having the formula: RO- (CHR₁-CHR₂-O) -R₃ Where R is C₆~ C₁₈An alkyl group, x is 1 to 25,₁And R ₂ Represents hydrogen, methyl acid group, succinic acid group, hydroxysuccinic acid group, and
Selected from the group consisting of mixtures,₃Is hydrogen, substituted or substituted
Selected from the group consisting of hydrocarbons having 1 to 8 carbon atoms, and mixtures thereof.
Selected.

Suitable soap surfactants include secondary soap surfactants that include a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octane. A water-soluble substance selected from the group consisting of acids and water-soluble salts of 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam inhibitors.

Alkali Metal Sarcosinate Surfactants Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOM wherein R is a C ₅ -C ₁₇ linear or branched alkyl or alkenyl group, R ¹ is a C ₁ -C ₄ alkyl group, and M is It is an alkali metal ion.
Preferred examples are myristyl and oleylmethyl sarcosinate in the form of the sodium salt.

Alkoxylated nonionic surfactants Virtually all alkoxylated nonionic surfactants are preferred here.
Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants are alkylphenols, nonionic ethoxylated alcohols, nonionic condensates of nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylates / propoxylates with propylene glycol It can be selected from the group of condensates and non-ionic ethoxylate condensation products with propylene oxide / ethylenediamine adducts.

Nonionic alkoxylated alcohol surfactants Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and / or propylene oxide, are preferred for use herein. The alkyl chain of the aliphatic alcohol may be linear or branched, primary or secondary, and generally has from 6 to 22 carbon atoms. A condensation product of an alcohol having an alkyl group having 8 to 20 carbon atoms and 2 to 10 moles of ethylene oxide per mole of alcohol is particularly preferred.

[0133]Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein have the following structural formula:
Substance. R²CONR¹In the formula, R1 is H, C₁~ C₄Hydrocarbyl, 2-hydroxyethyl, 2-hydr
Loxypropyl, ethoxy, propoxy, or mixtures thereof, preferably C
1-C4 alkyl, more preferably C₁Or C₂Alkyl, most preferably C₁ Alkyl (ie, methyl);₂Is C₅~ C₃₁Hydrocarbyl, preferred
Or linear C₅~ C₁₉Alkyl or alkenyl, more preferably linear
C₉~ C₁₇Alkyl or alkenyl, most preferably linear C₁₁~ C ₁₇ Alkyl or alkenyl, or a mixture thereof, wherein Z is at least
Having a hydrocarbyl straight chain with three hydroxyls directly attached to the chain
Roxyhydrocarbyl or their alkoxylation (preferably ethoxyl)
Or propoxylation) derivatives. Z is preferably reduced by an amination reaction
Obtained from sugars, more preferably Z is glycityl.

Nonionic Fatty Acid Amide Surfactants Suitable fatty acid amide surfactants include those having the formula: R ⁶ CON (R ⁷ ) _{2 In the} formula, R ⁶ is an alkyl group having 7 to 21, preferably 9 to 17 carbon atoms,
Each R ⁷ is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and — (C ₂ H ₄ O) _x H, where x is an integer of 1-3.

Nonionic Alkyl Polysaccharide Surfactants Suitable alkyl polysaccharides for use herein are described in US Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. Has 6 carbon atoms
And a hydrophilic group of a polysaccharide having 1.3 to 10 saccharide units, for example, a polyglycoside.

A preferred alkyl polyglycoside has the following formula: R ² O (C _n H _2n O) t (glycosyl) _{x wherein} R ² is a group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl having 10 to 18 carbon atoms in the alkyl group, and a mixture thereof. Wherein n is 2 or 3, t is 0-10, and x is 1.3-8. Glycosyl is preferably derived from glucose.

Amphoteric Surfactants Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphoteric carboxylic acids.

[0138] Suitable amine oxides include compounds having the formula: R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) _{2 wherein} R ³ is selected from alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl groups having 8 to 26 carbon atoms, or a mixture thereof. , R ⁴ is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms, or a mixture thereof, x is 0 to 5, preferably 0 to 3, and each R ⁵ is
It is an alkyl or hydroxyalkyl group containing 1 to 3 or a polyethylene oxide group having 1 to 3 ethylene oxide groups. C ₁₀ -C ₁₈ alkyl dimethyl amine oxides, and _{C 10-18} acylamido alkyl dimethylamine oxide.

A good example of an alkyl amphoteric dicarboxylic acid is Miranol® C2M Conc. Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant The detergent composition of the present invention can also contain a zwitterionic surfactant.
These surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be roughly described as:
Betaine and sultaine surfactants are representative of the zwitterionic surfactants used herein.

Suitable betaines are compounds having the formula: ^{_{R (R ') 2 N +}} R 2 COO - wherein, R is _C 6 _{-C 18} hydrocarbyl group, each ^{R 1} is typically _C 1 ~
A C ₃ alkyl, ^{R 2} is _C 1 -C ₅ hydrocarbyl group. Preferred betaines are _{C 12-18} dimethyl - an ammonio hexanoate and _{C 10-18} acylamido propane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants Suitable cationic surfactants for use in the detergents of the present invention include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactants are the mono _C 6 _{-C 16,} preferably _C 6 _-C 10 N-alkyl or alkenyl ammonium surfactants, the remaining N positions are methyl, hydroxyethyl or hydroxypropyl groups Has been replaced by Monoalkoxylated and bis-alkoxylated amine surfactants are also preferred.

Another preferred group of cationic surfactants that can be used in the detergent compositions or components thereof of the present invention are cationic ester surfactants. The cationic ester surfactant is preferably dispersed in water, having surfactant properties, comprising at least one ester (i.e., -COO-) linkage and at least one cationically charged group. It is a compound that can be used.

Suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260.
No. 529, each specification.

In a preferred embodiment, the ester linkage and the cationically charged group are at least 3 atoms (ie, 3 atom chain length), preferably 3 to 8 atoms, more preferably 3 to 5 atoms, within the surfactant molecule. Are separated from each other by spacer groups consisting of a chain comprising atoms, most preferably 3 atoms. The atoms forming the chain of the spacer group are
Selected from the group consisting of carbon, nitrogen and oxygen atoms and mixtures thereof,
However, any nitrogen or oxygen in the chain is bonded only to the carbon in the chain.
Thus, for example, -OO- (i.e., peroxide), -NN-, and -N-
The spacer group having O- bonds but are excluded, for example, _-CH 2 -O-CH ₂ -
And _{-CH 2} -NH-CH 2 - spacer group having a bond are included. In a preferred embodiment, the chain of the spacer group comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic mono-alkoxylated amine surfactants Highly preferred surfactants here are cationic mono-alkoxylated amine surfactants having the following general formula I:

Embedded image Wherein R ¹ is an alkyl or alkenyl moiety having about 6 to about 18, preferably 6 to about 16, most preferably about 6 to about 14 carbon atoms, and R ² and R ³ are each independently , alkyl group with a carbon number from 1 to about 3, preferably methyl, most preferably both R ² and R ³ are methyl groups, R ⁴ is hydrogen (preferred), is selected from methyl and ethyl , X ^- is an anion to provide electrical neutrality, for example chloride, bromide, methyl sulfate, sulfate, etc., a is an alkoxy group, especially an ethoxy, propoxy or butoxy group, p is 0 It is about 30, preferably 2 to about 15, and most preferably 2 to about 8.

Preferably, ApR ⁴ in the formula is a hydroxyalkyl group having p = 1 and having 6 or less carbon atoms, wherein the —OH group is 3 atoms from the quaternary ammonium nitrogen atom.
Separated by no more than carbon atoms. A particularly preferred ApR ⁴ group is —CH ₂ C
_{H 2 OH, -CH 2 CH 2} CH 2 OH, -CH 2 CH (CH 3) OH and -C
H _(CH 3) a _{CH 2 OH, -CH 2 CH 2} OH is particularly preferred. Preferred R ¹ groups are linear alkyl groups. A linear R ¹ group having 8 to 14 carbon atoms is preferred.

[0148] Another highly preferred cationic mono-alkoxylated amine surfactant for use herein is a material having the formula:

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is a charge-balancing agent. An anion, preferably chloride or bromide.

As mentioned above, compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (E
O) is, butoxy, isopropoxy _{[CH (CH 3) CH 2} O] and _{[CH 2 CH (CH 3 O} ] units (i-Pr) or n- propoxy units (Pr), or EO and / or Pr and And / or compounds replaced by a mixture of i-Pr units.

The amount of the cationic mono-alkoxylated amine surfactant used in the detergent composition of the present invention is preferably 0.1 to 20% by weight of the composition, more preferably 0.2 to 20% by weight.
7% by weight, most preferably 0.3-3.0% by weight.

Cationic bis-alkoxylated amine surfactant The cationic bis-alkoxylated amine surfactant preferably has the following general formula II:

Embedded image Wherein R ¹ is an alkyl or alkenyl moiety having from about 8 to about 18, preferably from about 10 to about 16, most preferably from about 10 to about 14, and R ² has from 1 to 3 carbon atoms. An alkyl group, preferably methyl, wherein R ³ and R ⁴ can be independently varied and are selected from hydrogen (preferred), methyl and ethyl;
X ⁻ is an anion sufficient to provide electrical neutrality, such as chloride, bromide, methyl sulfate, sulfate, and the like. A and A ′ can be independently varied and are each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie, —CH ₂ CH ₂ O—), propoxy, butoxy and mixtures thereof, and p is 1 To about 30, preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are those having the formula:

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is a convenient negative for charge balancing. Ions, preferably chloride. Respect general cationic bis alkoxylated amine structure noted above, since in a preferred compound R ¹ is derived from (coconut) C ₁₂ -C ₁₄ alkyl fraction fatty acids,
R ² is methyl, ApR ³ and A'qR ⁴ are each monoethoxy.

[0153] Other cationic bisalkoxylated amine surfactants suitable for use herein include compounds having the formula:

Embedded imageWhere R¹Is C₁₀~ C₁₈Hydrocarbyl, preferably C₁₀~ C₁₄Archi
Independently p is 1 to about 3, q is 1 to about 3, R²Is C₁~ C ₃ X is an alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
It is romide.

Other compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (EO),
Butoxy (Bu), isopropoxy _{[CH (CH 3) CH 2} O] and _{[CH 2 CH (CH 3 O} ] units (i-Pr) or n- propoxy units (Pr), or EO and / or Pr and / Or a compound replaced by a mixture of i-Pr units.

The bleach catalyst detergent composition can include a transition metal containing bleach catalyst. Suitable types of bleach catalysts include transition metal cations having defined bleach catalytic activity, such as copper, iron or manganese cations, and auxiliary metal cations having little or no bleach catalytic activity, such as zinc or aluminum. Catalytic system comprising a cation and a sequestering agent having a defined stability constant for the catalyst and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts It is. Such catalysts are described in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes described in US Pat. No. 5,246,621 and US Pat. No. 5,244,594. Other catalysts are described in published European patent application 549,272. The bleach catalyst useful herein can be appropriately selected in the present invention. See U.S. Pat. Nos. 4,246,612 and 5,227,084 for examples of suitable bleaching catalysts. Mononuclear manganese (IV) complexes, such as Mn (1
, 4,7-trimethyl-1,4,7-triazacyclononane) - (OCH _{3) 3} -
Referring (PF _6), U.S. Pat. No. 5,194,416, which discloses.

Yet another type of bleaching catalyst described in US Pat. No. 5,114,606 is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. A water-soluble complex of manganese (III) and / or (IV) containing a strontium. Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof. U.S. Pat. No. 5,114,611 discloses a bleaching catalyst comprising a complex of a transition metal, including Mn, Co, Fe or Cu, with a non- (large) cyclic ligand. The ligand has the following formula:

Embedded image Wherein R ¹ , R ² , R ³ and R ⁴ are each H, such that R ¹ -N ＝ CR ² and R ³ -C ＝ NR ⁴ form a 5- or 6-membered ring, respectively. , Substituted alkyl and aryl groups. The ring may be further substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C ＝ O, wherein R ⁵ , R ⁶ and R ⁷ are each H, substituted or unsubstituted It may be an alkyl or aryl group containing groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. If desired, the ring may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Ligand 2,2
'-Bispyridylamine is particularly preferred. Preferred bleach catalysts include Co, Cu
, Mn, Fe, -bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co (2,2′-bispyridylamine) Cl ₂ ,
Di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ O ₂ ClO ₄ , bis (2 There are 2'-bispyridylamine) copper (II), tris (di-2-pyridylamine) iron (II) perchlorate, and mixtures thereof.

Other examples include N ₄ Mn ^III (u—O) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^{II I} (u—O) ₂ Mn ^IV Bipy ₂ ] — (ClO ₄ ) ₃ . The 4-N-locus and 2-
Includes binuclear Mn complexes with N-dentate ligands.

Other bleaching catalysts are, for example, published European patent applications 408,131 (cobalt complex catalysts), published European patent applications 384,503 and 306,0.
No. 89 (metallo-porphyrin catalyst), U.S. Pat. No. 4,728,455 (manganese / polydentate ligand catalyst), U.S. Pat. No. 4,711,748 and published European patent application 224,952 (aluminosilicate). US Pat. No. 4,601,845 (aluminosilicate support and manganese and zinc or magnesium salts), US Pat. No. 4,626,373 (manganese / ligand catalyst) No. 4,119,557 (ferric complex catalyst), German Patent 2,054,019 (cobalt chelate catalyst), Canadian Patent 866,1.
No. 91 (transition metal-containing salts), US Pat. No. 4,430,243 (chelates with manganese cations and non-catalytic metal cations), and US Pat.
No. 28,455 (manganese gluconate catalyst).

The bleach catalyst is typically used in the compositions and methods of the present invention in a catalytically effective amount. By "catalytically effective amount" is meant an amount that is sufficient to bleach and remove the soil of interest from the target substrate using any of the comparative test conditions. The test conditions are
It depends on the type of washing equipment used and the habits of the user. Some users use very hot water for the washing operation, while others use hot or cold water. Of course, the catalytic performance of the bleaching catalyst is affected by such conditions, and the amount of bleaching catalyst used in a well-formulated detergent composition and bleaching composition can be adjusted as appropriate. As a practical matter, but not by way of limitation, the compositions and methods of the present invention provide at least on the order of 10 parts per million of active bleach catalyst material in the wash water, preferably from about 1 ppm to about 200 ppm. Can be adjusted to be provided in the washing liquid. To further illustrate this point, under European conditions using perborates and peracids, manganese catalysts are effective at 40 ° C., pH 10, on the order of 3 micromoles. Under US conditions, concentrations would need to be increased 3-5 fold to achieve the same result.

Water-soluble builder compounds The compositions of the present invention are typically present in detergent compositions in an amount of from 1 to 80%, preferably from 10 to 60%, most preferably from 15 to 40% by weight of the composition. It is preferred to include a water-soluble builder compound present in

The detergent composition of the present invention is preferably 0.5 to 60% by weight, more preferably 5 to 60% by weight.
Comprising a phosphate-containing builder material present in an amount of 50% by weight, more preferably 8-40% by weight.

[0163] The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate, more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, wherein the polycarboxylic acid is , Containing at least two carboxyl groups separated from each other by no more than 2 carbon atoms), borates, and mixtures of any of the above.

The carboxylate or polycarboxylate builder may be monomeric or oligomeric, but monomeric polycarboxylates are generally preferred for cost and performance reasons.

Suitable carboxylate salts containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic, malonic, (ethylenedioxy) diacetate, maleic, diglycolic, tartaric, tartronic and fumaric acids,
And ether carboxylate and sulfinyl carboxylate.
Polycarboxylates containing three carboxy groups or their acids include, in particular, water-soluble citrates, aconitates and citraconic acid salts, and succinate derivatives, such as GB 1,379,241. The carboxymethyloxysuccinate described in the specification, the lactoxysuccinate described in GB 1,389,732, and the Dutch application 72058073 are described. Amino succinate and oxypolycarboxylate materials such as 2-oxa-1,1,1 described in GB 1,387,447.
3-propanetricarboxylate. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present in an amount of 0.1 to 15%, more preferably 0.5 to 8% by weight of the composition.

Polycarboxylates containing four carboxy groups are described in GB 1,261,8
No. 29, oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1
, 2,3-propanetetracarboxylate. Polycarboxylates containing sulfo substituents include those in British Patent Nos. 1,398,421 and 1,398,42.
No. 2, and US Pat. No. 3,936,448, and the sulfosuccinate derivatives described in US Pat. No. 3,936,448, and the sulfonated pyrolytic citric acid described in GB 1,439,000. Salts. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially citrates.

The parent acid of the monomeric or oligomeric polycarboxylate chelating agent or a mixture of these acids and their salts, such as citric acid or a citrate / citric acid mixture, are also considered as useful builder components. Can be

[0169] Borate builders, as well as builders that include borate-forming materials capable of forming borate under detergent storage or washing conditions, are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders include alkali metal tripolyphosphates, pyrophosphates of sodium, potassium and ammonium, pyrophosphates of sodium and potassium and ammonium, orthophosphates of sodium and potassium, polymerization Polymeta / sodium phosphate with a degree of about 6-21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compounds The detergent compositions of the present invention typically comprise 0.5 to 60%, preferably 5 to 50%, most preferably 8 to 40% by weight of the composition. It may include a partially soluble or insoluble builder compound present in an amount of weight percent.

Examples of builders with very low water solubility include sodium aluminosilicate. As noted above, in one embodiment of the present invention, it is preferred that very small amounts of aluminosilicate builders are present.

Suitable aluminosilicate zeolites have the following unit cell formula: _{Na z [(AlO 2) z} (SiO 2) y]. xH in ₂ O formula, z and y are at least 6, the molar ratio of z and y is 1.0-0.5, x is at least 5, preferably from 7.5 to 276, more preferably 10 to 26
4. The aluminosilicate material is in a hydrated form, preferably crystalline, and contains 10% to 28%, more preferably 18% to 22%, of water in bound form. The aluminosilicate zeolite may be a naturally occurring material, but a synthetic product is preferred. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof. Zeolite A has the following formula: Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. xH ₂ O In the formula, x is from 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. 276H has a ₂ O.

Another preferred aluminosilicate zeolite is a zeolite MAP builder. Zeolite MAP can be present in an amount of 1 to 80%, more preferably 15 to 40% by weight of the composition.

Zeolite MAP is described in EP 384070A (Unilever). This material is defined as a zeolite P-type alkali metal aluminosilicate having a silicon to aluminum ratio of 1.33 or less, preferably 0.9 to 1.33, more preferably 0.9 to 1.2. I have.

Zeolite M having a ratio of silicon to aluminum of 1.15 or less, especially 1.07 or less
APs are particularly important.

[0177] In a preferred embodiment, builders zeolite MAP _detergent particle size, expressed as _{the d 50} value is 1.0 to 10.0 micrometers, more preferably 2.0 to 7.0 micrometers, and most preferably 2 0.5-5.0 micrometers.

The d ₅₀ value indicates that 50% by weight of the particles have a smaller diameter than that value. The particle size can in particular be measured using conventional analytical techniques, for example microscopy using a scanning electron microscope, or using a laser granulometer. Other methods of determining the d ₅₀ value is described in EP 384070A.

Organic Polymeric Compound The organic polymeric compound is a preferred additional component of the composition, preferably present as a constituent of all the particulate components, wherein the particulate components are combined Can act as if As used herein, the term "organic polymeric compound" refers to substantially all polymeric organic compounds commonly used as dispersants and anti-redeposition and soil dispersants in detergent compositions, where clay agglomeration is used. It includes all of the high molecular weight organic polymeric compounds described as agents, and includes the quaternized ethoxylated (poly) amine clay soil removal / redeposition inhibitor of the present invention.

The organic polymeric compound is present in the detergent compositions of the present invention, typically at 0.01% of the composition.
-30% by weight, preferably 0.1-15% by weight, most preferably 0.5-10% by weight.

Examples of organic polymeric compounds are water-soluble organic homopolymers or copolymers in which the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms. Polycarboxylic acids or their salts. Polymers of the latter type are described in GB-A-1,596,756. Examples of such salts are polyacrylates having a molecular weight of 1000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2
000 to 100,000, especially 40,000 to 80,000.

Polyamino compounds, including compounds derived from aspartic acid, as described in EP-A-305282, EP-A-305283 and EP-A-351629, may be used. Useful here.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially 5,000-10,000 average molecular weight
000 terpolymers are also suitable here.

Other organic polymeric compounds suitable for incorporation in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of from 1,000 to 10,000, especially from 2,000 to 8,000, most preferably about 4,000.

Highly preferred polymeric components here are described in US Pat. No. 4,968,451, Scheibel et al. And US Pat. No. 5,415,807, Goseelin.
cotton and non-cotton soil release polymers according to K et al., and in particular according to US patent application Ser. No. 60/051517.

Other organic compounds which are preferred clay dispersants / anti-redeposition agents for use herein are ethoxylated cationic monoamines and diamines having the formula:

Embedded image In the formula, X, H, a C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and non-ionic group selected from the group consisting of mixtures thereof, a is 0 to 20, preferably 0 4 (e.g., ethylene, propylene, hexamethylene), b is 1 or 0, and for cationic monoamines (b = 0), n is at least 16, typically 20-35; For cationic diamines (b = 1), n is at least 12, typically about 12
~ 42.

Other dispersants / anti-redeposition agents used herein are described in European Patent EP-B-0.
No. 11,965, U.S. Pat. No. 4,659,802 and U.S. Pat. No. 4,664,848.

Foaming Inhibition System The detergent composition of the present invention, when formulated for a machine cleaning composition, contains 0.01% of the composition.
-15% by weight, preferably 0.02-10% by weight, most preferably 0.05-3%
Comprising a foam control system present in an amount of weight percent.

[0189] Suitable foam control systems for use herein can comprise substantially all known antifoam compounds, including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds. .

By defoaming compound is meant here all compounds or mixtures of compounds which act by means of a solution of the detergent composition, in particular the foaming or foaming which occurs when the solution is stirred.

Particularly preferred antifoam compounds for use herein are the silicone antifoam compounds defined herein as all antifoam compounds that include a silicone component. Such silicone antifoam compounds typically also include a silica component. The term "silicone" as generally used in the present invention and throughout the industry encompasses a variety of relatively high molecular weight polymers containing various types of siloxane units and hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl endblock units.

[0192] Other suitable antifoam compounds include monocarboxylic fatty acids and their soluble salts. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Monocarboxylic fatty acids and their salts used as foam inhibitors generally have 10 to 24 carbon atoms,
It preferably has a hydrocarbyl chain of 12-18. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg, stearone), N-alkylated aminotriazines E.g. tri- to hexa-alkylmelamine or di-tetra-alkyldiamine formed as a reaction product of cyanuric chloride with 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms having 1 to 24 carbon atoms Chlorotriazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal (eg, sodium, potassium, lithium) phosphates and phosphates are mentioned.

Preferred foam control systems include (a) an antifoam compound, preferably a silicone antifoam compound, most preferably (i) an amount of 50-99%, preferably 75-95%, by weight of the silicone antifoam compound. A silicone antifoam compound comprising (ii) a silica / silica antifoam compound in an amount of from 1 to 50% by weight, preferably from 5 to 25% by weight of the silicone / silica antifoam compound. Is incorporated in an amount of 5 to 50% by weight, preferably 10 to 40% by weight), (b) a dispersant compound in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight, most preferably A silicone glycol rake copolymer having a polyoxyalkylene content of 72 to 78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1 (this Particularly preferred silicone glycol rake copolymers are commercially available from DOW Corning under the trade name DCO544), (c) an inert carrier fluid compound (A) in an amount of 5 to 80% by weight, preferably 10 to 70% by weight. most preferably ethoxylated degree 5 to 50, preferably comprise comprising _C 16 _{-C 18} ethoxylated alcohol is 8-15).

Highly preferred particulate foam control systems are described in EP-A-02107.
No. 31, the silicone antifoaming compound and a melting point of 50 ° C. to 8
The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain having 12 to 20 carbon atoms. EP-A-0210721 discloses another preferred particulate foam control system wherein the organic carrier material comprises a fatty acid or alcohol having a carbon chain of 12 to 20 carbon atoms, or a mixture thereof. A melting point of 4
5 ° C to 80 ° C.

Other highly preferred foam control systems comprise mixtures of polydimethylsiloxane or silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic acid polymers, such as copolymers of laic and acrylic acid. .

Polymeric Dye Transfer Inhibitor The present composition can also comprise 0.01 to 10% by weight, preferably 0.05 to 0.5% by weight of a polymeric dye transfer inhibitor.

The polymeric dye transfer inhibitor is preferably a polyamine N-oxide polymer, N-
It is selected from a copolymer of vinylpyrrolidone and N-vinylimidazole, a polyvinylpyrrolidone polymer or a combination thereof, wherein these polymers may be crosslinked polymers.

Polymeric Soil Release Agent A polymeric soil release agent (hereinafter referred to as “SRA”) can be used in the present composition, if desired. If used, the SRA will typically be from 0.01 to 1 of the composition.
0.0% by weight, typically 0.1-5% by weight, preferably 0.2-3.0% by weight
Occupy.

Preferred SRAs are hydrophilic moieties for imparting hydrophilicity to the surface of hydrophobic fibers, such as polyester and nylon, and are deposited on the hydrophobic fibers and adhered thereto through a washing and rinsing cycle. It generally has a hydrophobic part that acts as an anchor for the sexual part. As a result, dirt generated after the treatment with SRA is more easily washed in a later washing step.

Preferred SRAs are oligomeric terephthalic acids typically prepared by processes involving at least one transesterification / oligomerization (often using metal catalysts such as titanium (IV) alkoxides) And esters. Such esters are of course made using additional monomers that can be incorporated into the ester structure through one, two, three, four or more positions, without forming a tightly crosslinked overall structure. be able to.

Suitable SRAs are described, for example, in terephthaloyl and oxyalkyleneoxy repeats, as described in US Pat. No. 4,968,451, issued Nov. 6, 1990 to JJ Scheibel and EP Gosselink. Includes a substantially linear ester oligomer sulfonation product comprising an oligomeric ester backbone of units and a sulfonated end moiety derived from allyl covalently attached to the backbone. Such ester oligomers can (a) ethoxylate allyl alcohol and (b) convert the product of (a) to dimethyl terephthalate ("DMT") and 1
, 2-propylene glycol ("PG") in a two-stage transesterification / oligomerization step, and reacting the products of (c) and (b) with sodium metabisulfite in water. it can. Another SRA is disclosed in U.S. Pat.
711,730, Dec. 8, 1987, Gosselink et al., Nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters such as poly (ethylene glycol) methyl ether, DMT, P
Includes materials made by transesterification / oligomerization of G and poly (ethylene glycol) ("PEG"). Other examples of SRA include U.S. Pat.
, 721,580, Jan. 26, 1988, Gosselink, partially and fully anionic end-capped oligomeric esters such as ethylene glycol ("EG"), PG, DMT and Na-3, Oligomers derived from 6-dioxa-8-hydroxyoctanesulfonate, U.S. Pat.
857, Oct. 27, 1987, Gosselink, Nonionic capped block polyester oligomeric compounds such as DMT, methyl (Me)
Materials made from capped PEG and EG and / or PG, or DMT, EG and / or PG, a combination of Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and US Pat. No. 4,877, No. 896, Oct. 31, 1989, Maldonado, Gosselink et al., There is an anionic system, especially sulfoalloyl end-capped terephthalates, the latter being useful in both laundry and fabric conditioning products. A typical material for SRA, an example is an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, but optionally, but preferably, an added PEG, such as PEG3400. Further comprising.

SRA includes ethylene terephthalate or propylene terephthalate and poly
Simple copolymerization of ethylene oxide or polypropylene oxide terephthalate.
Body Block (US Pat. No. 3,959,230, Hays, May 2, 1976)
5th, and U.S. Pat. No. 3,893,929, Basadur, July 1975
On March 8), cellulosic derivatives such as those commercially available from Dow as METHOCEL.
Droxy ether cellulose polymer, C₁~ C₄Alkyl cellulose and C ₄ Hydroxyalkyl cellulose (US Pat. No. 4,000,093,
Nicocol, et al., December 28, 976), and anhydroglucose alone.
The average degree of substitution (methyl) per position is about 1.6 to about 2.3.
Cell having a solution viscosity of about 80 to about 120 centipoise measured at 20 ° C.
Loose ethers are also included. Such materials are manufactured by Shin-Etsu Chemical Co., Ltd.
METROLOSE SM100 and ME, trade names of methylcellulose ethers being manufactured
Available as TOLOSE SM200.

Another group of SRAs are (I) nonionic terephthalates which use a diisocyanate coupling agent to link the polymeric ester structure (US Pat. No. 4,201,8).
No. 24, Violland et al. And U.S. Pat. No. 4,240,918, Lagasse et al.), And (II) trimellitic anhydride is added to a known SRA, and the terminal hydroxyl group is trimellitate. And SRA containing carboxylic acid ester end groups. By selecting an appropriate catalyst, trimellitic anhydride forms a bond at the end of the polymer through an isolated carboxylic acid ester of trimellitic anhydride, rather than opening an anhydride bond. Either nonionic or anionic SRAs can be used as starting materials, as long as they have an esterifiable hydroxyl end group. U.S. Pat. No. 4,525,524, Tu
See ng et al. Other types include (III) SRA based on anionic terephthalate having various urethane bonds (US Pat. No. 4,201,824, Vi
olland et al.).

Other Optional Ingredients Other optional optional ingredients suitable for incorporation in the compositions of the present invention include colorants and filler salts, with sodium sulfate being the preferred filler salt.

Highly preferred compositions comprise about 2 to about 10% by weight of an organic acid, preferably citric acid. Also, preferably in combination with carbonates, small amounts (eg, less than about 20% by weight) of neutralizing agents, buffers, phase modifiers, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, Antioxidants, bactericides and dyes, such as U.S. Pat.
285,841, Barrat et al., Promulgated August 25, 1981, incorporated herein by reference.

Composition Form The compositions of the present invention can be prepared by various methods, including dry mixing, coagulation, compression, or spray drying of the various compounds contained in the detergent components, and combinations of these techniques. it can.

The compositions of the present invention can take a variety of physical forms, including liquids, but preferably solid forms, such as tablets, flakes, pastels and bars, with granular forms being preferred.

The compositions of the present invention can also be used in or in combination with bleach additive compositions, for example, compositions comprising chlorine bleaches.

The chlorine-based bleach detergent composition can include, as an additional component, a chlorine-based bleach. However, since the preferred detergent compositions of the present invention are solids, most liquid chlorine-based bleaching are not suitable for these detergent compositions, and only granular or powdered chlorine-based bleaching agents are preferred.

Alternatively, the detergent composition is compatible with the chlorine bleach and should be formulated so that the user can add the chlorine bleach to the detergent composition at or during the start of washing. Can also.

[0212] Chlorine bleach is a material from which hypochlorite is formed in an aqueous solution. Hypochlorite ions are represented chemically by the formula OCT.

Bleaches that form hypochlorite in aqueous solution include hypochlorites of alkali metals or alkaline earth metals, hypochlorite addition products, chloramine, chlorimine,
Chloramide, and chlorimide. Specific examples of such compounds include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, Potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5
-Dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichlorami
ne T, chloramine B and Dichloramine B. Preferred bleaches for the compositions of the present invention are sodium hypochlorite, potassium hypochlorite, or mixtures thereof. A preferred chlorine bleach is Triclosan®.

Most of the above-described hypochlorite-forming bleaches are available in solid or concentrated form and dissolve in water in making the compositions of the present invention. Some of the above materials are commercially available as aqueous solutions.

Washing Methods Machine washing methods typically involve treating soiled laundry in a washing machine with an effective amount of a washing solution in which a mechanical laundry detergent composition of the present invention has been dissolved or supplied. To do. An effective amount of the detergent composition is 10 g to 300 g dissolved or dispersed in a washing solution having a volume of 5 to 65 liters, which is a typical product usage amount and a washing solution volume generally used in a normal machine washing method. Means the product. A preferred washing machine may be a so-called low-fill washing machine.

In a preferred mode of use, the detergent composition is formulated to be suitable for hard surface cleaning or manual washing. In another preferred use, the detergent composition is a pre-treatment or dip composition used to pre-treat or soak soiled, stained fabrics.

In the abbreviation detergent compositions used in the examples of granular detergents , the abbreviated components have the following meanings.

LAS: sodium linear C11-13 alkyl benzene sulfonate TAS: sodium tallow alkyl sulfate CxyAS: sodium C1x to C1y alkyl sulfate C46SAS: sodium C14 to C16 secondary (2,3) alkyl sulfate CxyEzS: condensation with z mole of ethylene oxide Sodium C1x-C1y alkyl sulfate CxyEz: C1x-C1y predominantly linear primary alcohol condensed with an average z mole of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH), R2 = C12-C14 QAS1: R2.N + (CH3) 2 (C2H4OH), R2 = C8-C11 APA: C8-C10 amidopropyldimethylamine Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS: sodium toluene sulfonate CFAA: C12-C14 (coco) alkyl N-methylglucamide TFAA: C16-C18 alkyl N-methylglucamide TPKFA: C16-C18 topped whole cut fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate Zeolite A: hydrated sodium aluminosilicate of the formula Na12 (AlO2 SiO2) 12.27 H2 O, primary particle size 0.1 to 10 micrometers (weight is expressed as anhydride) NaSKS-6: crystallinity of the formula d-Na2 Si2 O5 Layered silicate Citric acid: anhydrous citric acid Borate: sodium borate Carbonate: anhydrous sodium carbonate, particle size 200 μm to 900 μm Bicarbonate: anhydrous sodium bicarbonate, particle size distribution 400 μm to 1200 μm Silicate: amorphous Sodium silicate (SiO2: Na2O = 2.0: 1) Sulfate: anhydrous sodium sulfate Mg sulfate: anhydrous magnesium sulfate Citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution 42
5 μm to 850 μm MA / AA: maleic acid / acrylic acid 1: 4 copolymer, average molecular weight about 70,0
MA / AA (1): maleic acid / acrylic acid 4: 6 copolymer, average molecular weight about 1
000 AA: sodium polyacrylate polymer, average molecular weight 4,500 CMC: sodium carboxymethyl cellulose Cellulose ether: methyl cellulose ether, degree of polymerization 650, manufactured by Shin-Etsu Chemical Protease: proteolytic enzyme, active enzyme 3.3% by weight, Savinase Sold by NOVO Industries A / S under the trade name Protease I: Proteolytic enzyme, 4% by weight of active enzyme, International Patent WO95
/ 10591, sold by Genencor Int. Inc. Alcalase: proteolytic enzyme, active enzyme 5.3% by weight, sold by NOVO Industries A / S Cellulase: cellulolytic enzyme, active enzyme 0.23% by weight, NOVO Industries
Amylase: starch-degrading enzyme, active enzyme 1.6% by weight, NOVO Industries A / S
Lipase: Lipolytic enzyme, active enzyme 2.0% by weight, NOVO Industries A / S to Li
Lipase (1): Lipolytic enzyme, active enzyme 2.0% by weight, NOVO Industries A / S
Endolase: Endoglucanase enzyme, active enzyme 1.5% by weight, NOVO Industries
Sold from A / S PB4: Nominal Formula Particles Containing Sodium Perborate Tetrahydrate of NaBO2.3H2O, Weight Average Particle Size 950 Micron, 85% of the Particles Have 850-950 Micron Particle Size PB1: Nominal Formula NaBO2. Particles containing anhydrous sodium perborate bleach of H2O2, weight average particle size 800 microns, 85% of the particles having a particle size of 750-950 microns Percarbonate: particles containing sodium percarbonate of nominal formula 2Na2CO3.3H2O2 NOBS: Nonanoyloxybenzenesulfonate in the form of a sodium salt, wherein 5% or less of the particles have a weight average particle diameter of 850 microns and a particle diameter of less than 600 microns is 2% or less. NAC-OBS: particles comprising (6-nonamidocaproyl) oxybenzenesulfonate, weight average particle size 825 microns to 875 microns TAEDI: particles comprising tetraacetylethylenediamine Weight average particle size 70
0 micron to 1000 micron TAEDII: tetraacetylethylenediamine, particle size 150 micron to 600
Micron DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylenetriaminepenta (methylene phosphonate), Monsanto
Sold under the trade name Dequest 2060 Photoactivated bleach (1): sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer Photoactivated bleach (2): encapsulated in dextrin soluble polymer Sulfonated aluminozinc phthalocyanine brightener 1: disodium 4,4'-bis (2-sulfostyryl) biphenyl brightener 2: disodium 4,4'-bis (4-anilino-6-morpholino-1,3,5 -Triazin-2-yl) amino) stilbene-2: 2'-disulfonate EDDS: ethylenediamine-N, N-disuccinic acid, (S, S) isomer, sodium salt form HEDP: 1,1-hydroxyethanedi Phosphonic acid PEGx: polyethylene glycol, molecular weight x (typically 4,000) PEO: polyethylene glycol Sid, average molecular weight 50,000 TEMPAE: tetraethylene pentaamine ethoxylate PVI: polyvinyl imidazole, average molecular weight 20,000 PVP: polyvinyl pyrrolidone polymer, average molecular weight 60,000 PVNO: polyvinyl pyridine N-oxide polymer, average molecular weight 50 2,000 PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole, average molecular weight 20,000 QEA: bis ((C2H5O) (C2H4O) n) (CH3) -N + -C6H12-N +-(CH3) bis ((
C2H5O)-(C2H4O)) n, n = 20-30 SRP1: Anionically end-capped polyester SRP2: Diethoxylated poly (1,2 propylene terephthalate) short block polymer PEI: Polyethyleneimine, average molecular weight 1800, average Ethoxylation degree nitrogen 1
7 ethyleneoxy residues per unit Silicone defoamer: polydimethylsiloxane foam control agent containing siloxane-oxyalkylene copolymer as dispersant, ratio of foam control agent to dispersant 10
: 1 to 100: 1 Opacifier: aqueous monostyrene latex mixture, sold under the trade name Lytron 621 by BASF Corporation Wax: paraffin wax

In the examples below, all amounts are given as% by weight of the composition. Table 1

The following compositions are in accordance with the invention.

[Table 1] Table II

The following compositions are according to the invention

[Table 2] Table III

The following high-density bleach-containing detergent compositions are in accordance with the present invention.

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/50 C11D 3/50 17/06 17/06 D06L 3/02 D06L 3/02 (81) Designated countries 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, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, C R, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, 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, ZA, ZW (71) Applicants ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA ( 72) Inventor: Allison, Leslie, Maine, Tyne, Ande, Ware, Whitley, Bay, St. Pauls, Gardens, 12 (72) Richard, Te Imosy, Hartshawn Northumberland, Wylham, Dane, Lord, UK, 139 (72) Inventor Tiffany, Alice, Hensman, Newcastle, UK, upon, Tyne, Jesmond, Selborne, Gardens, Deanside, Court, 39 F-term (reference) 4H003 AB04 AB19 AB27 AB28 AB31 AC03 AC08 AE02 AE06 BA10 DA01 EA09 EA10 EA12 EA15 EA16 EA18 EA24 EA28 EB02 EB08 EB13 EB16 EB19 EB22 EB24 EB25 EB28 EB30 FA02 EB34 EB12 FA26 FA42

Claims (10)

[Claims] 1. A solid detergent composition comprising a bleach sensitive component and a hydrogen peroxide source, wherein the hydrogen peroxide source has a weight average particle size of 700 microns to 1100 microns, preferably 700 microns. At least 80% by weight of the particulate component present in the particulate component having a hydrogen peroxide source of from 60% to 140%, preferably of the weight average particle size, 70% to 130%,
A solid detergent composition having a particle size of 2. The solid component of claim 1, wherein the hydrogen peroxide source comprises a percarbonate. 3. The percarbonate is such that 75% of the theoretical maximum available oxygen (AvO) of the percarbonate is released in less than 10 minutes, preferably in less than 6 minutes. 3. The solid detergent composition according to 2. 4. The solid detergent composition according to claim 1, wherein the hydrogen peroxide source has an average particle size of 800 to 950 microns. 5. A composition comprising one or more bleach activators, preferably at least one of the bleach activators.
A solid detergent composition according to any of the preceding claims, wherein the seed is present in a particulate component having a weight average particle size of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. 6. A hydrophobic organic peracid bleach precursor and a hydrophilic organic peracid bleach precursor, wherein the hydrophilic organic peracid bleach precursor preferably comprises TAED. The substance is preferably an oxybenzenesulfonate group, preferably NACA-
The solid detergent composition according to claim 5, comprising OBS or NOBS or a mixture thereof. 7. The composition according to claim 1, which is a granular composition, wherein at least 80% of the composition has a weight-average particle size of from 700 to 1400 microns, preferably from 750 to 1000 microns. A solid detergent composition as described. 8. The bleach-sensitive component comprises a fragrance, a soil release polymer, a dispersant, a chelating agent, a dye, a photobleach or a brightener or a mixture thereof.
A detergent composition according to any one of claims 7 to 10. 9. A detergent composition according to any one of claims 1 to 8, comprising a component sprayable from above, comprising a component sensitive to bleach. 10. An intumescent component, preferably having a weight average particle size of 700 to 1400 microns,
The detergent composition according to any one of the preceding claims, comprising a particulate intumescent component, preferably between 750 microns and 1100 microns.