JP2002529583A - Speckle particles and compositions containing speckle particles - Google Patents

Abstract

  (57) [Summary] The present invention provides cleaning composition speckle particles having a specific sparkle index and a transparency index and comprising a solid material, preferably a specific crystalline material, colored with a dye, pigment and / or brightener. The present invention also relates to cleaning compositions comprising the speckle particles of the present invention, especially laundry and dishwashing compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention provides improved speckle particles and compositions comprising the speckle particles,
In particular, it relates to cleaning compositions.

[0002]

[Background Art]

In recent years, detergent manufacturers have used small amounts of dyed particles or speckles in their products. Detergent users have associated products with dye particles with a cleaning effect, and products containing colored particles have been found to be more acceptable to consumers than products without such colored particles. In addition, speckle can mask product bleaching and / or mask this color difference to allow for the incorporation of small amounts of non-colored components in the product into the product. .

[0003] Speckles typically spray an aqueous solution of a particular dye onto a hygroscopic material, add this material to other ingredients, or spray directly on the final detergent base particles,
It is obtained by drying the dyeing material or particles. The problem with this method is that the hygroscopic material absorbs large amounts of water and solidifies the product. this is,
Especially when large quantities of aqueous dye solutions need to be used, e.g. when very dilute dye solutions have to be used, when strongly dyed particles are needed or when the dye is absorbed by the material or particles to be dyed. It is a problem.

Another problem associated with detergents containing large amounts of dye per particle is that the presence of water can cause the dye to “bleed”. This can occur when making the detergent by spraying a large amount of aqueous dye solution, when the detergent contains a large amount of hygroscopic material, or, of course, when the detergent is placed in a cleaning or cleaning liquid. This "bleed" leads to discoloration of the product and the packing material. Furthermore, under certain conditions, dye or dye particles adhering to the fabric can "bleed" into the fabric, causing a color change in the washed fabric.

[0005] Also, in order to avoid the concentration of high concentrations of dyes, which leads to the problems described above,
It has also been found that it is essential that the dye in the product be applied uniformly to the surface of the particles and to the entire product.

[0006] However, despite these problems, it is desirable to have speckle particles present in the product to provide the necessary contrast in the product and / or to mask certain components in the product. .

The present inventors have discovered improved speckle particles. That is, particles that reflect a particular light to give a particular brilliance and have a certain transparency can give good contrast with other components of the product and can mask unwanted colors of other components of the product I learned that. In particular, it has been found that speckle particles containing a crystalline material can provide the necessary contrast and / or masking.
In certain applications, uncolored crystalline materials provide contrast and masking, but the speckle particles are preferably colored.

[0008] Thus, the speckle reflection / transparency can reduce the amount of colorant needed to provide the necessary contrast or masking.

Furthermore, the present inventors have also found that the crystalline material has low porosity and / or low hygroscopicity and thus does not absorb much of the coloring agent, so that the present speckle particles containing the crystalline material are limited in amount. It was also found that only one dye was required. Thus, the speckle particles of the present invention can be more effectively and efficiently colored.

Thus, using the speckle material of the present invention, the maximum amount of dye can optimize the color appearance of the product.

[0011] Advantages further include less colorant in the speckle particles and compositions containing the particles. The risk of colorant bleed is reduced, and the problems associated therewith are reduced.

[0012]

DISCLOSURE OF THE INVENTION

The invention comprises a solid material colored with a colorant having a sparkle index of at least 5
% Of the cleaning composition particles having a transparency index of at least 5%. The particles preferably have a color saturation of at least 10, preferably at least 30, a sparkle index of about 10% and a transparency index of at least 15%.

[0013] The present invention also provides a cleaning comprising a crystalline material, preferably selected from the group consisting of crystalline hydrated salts, crystalline acids, crystalline acid salts, crystalline surfactants, carbohydrates or mixtures thereof. Composition speckle particles are also provided.

The speckle particles are particularly incorporated into solid laundry, dishwashing or hard surface cleaning compositions.

[0015] The present invention also relates to the composition and the method of making the speckle particles and the use thereof.

[0016]

DETAILED DESCRIPTION OF THE INVENTION

Speckle Particles The speckle particles of the present invention have a sparkle index of at least 5%, preferably at least 10%, further at least 15%, and even at least 20%.

The speckle particles have a transparency index of at least 1%, preferably at least 5%
, At least 15%, at least 30%, and even at least 60%.

[0018] The sparkle index and the transparency index can be determined as follows. Installed Universal Analysis Software provided by HunterLab
A spectrophotometer capable of measuring light transmittance and reflectance, such as Hunter Labs UltraScan XE, connected to a suitable personal computer, such as a BM ThinkPad model number 264, is used.

Pour 25 g of speckle particles into a 50 mm long glass cuvette with a path length of 4 mm. Suitable cuvettes are available from Hunter Labs. The spectrophotometer is calibrated using a light trap and white tile according to the accompanying operating manual and the sample is placed in the sample holder. Measure light reflectance and transmittance. The light reflectance measurement is performed so as to include the specular reflection component (Spec in) and to exclude the specular reflection component (Spec ex). The spectrophotometer produces a spectral emission plot. This is found on personal computers.

As used herein, the sparkle index is% reflectance (spec in) −% reflectance (spec ex), both of which are measured at the peak reflectance wavelength determined by a computer. This is seen by the maximum in the spectral reflectance emission curve. This depends on the color of the particles. For example, Monast
For blue particles using ral blue dye, the peak wavelength is 460 nm, and for green particles using Pigmasol green dye, the peak wavelength is 50 nm.
0 nm.

As used herein, the transparency index is the% light transparency at the peak wavelength. this is,
After the transmittance is measured by a spectrophotometer, it is read from a personal computer.

Preferably, the color saturation of the speckle particles is at least 10, preferably at least 30, more preferably at least 50 and even at least 10 in delta saturation.
0.

[0023] Delta color saturation can be determined by standard measurements used in the industry. For example, using standard L, a, b values commonly used in the industry,
With raScan XE and Universal software, the color saturation of the colored material after coloring can be calculated by comparing with the color saturation of the same material before coloring.

The color saturation of the sparkle particles is the delta color saturation obtained by subtracting the color saturation of the same uncolored particles from the color saturation of the colored particles.

The speckle particles of the present invention may be of any color. When present in a cleaning composition, the speckles are preferably of a different color than most of the other components and particles of the composition. As used herein, “color” includes brightness of black and white. Colorant,
The phrase colored, colored, shall be construed as such.

In a preferred embodiment, the speckle particles are preferably colored with a dye, a pigment, a brightener or a mixture thereof described below.

The speckle particles of the present invention have a specific light reflectance and / or light transparency. The speckle particles preferably contain a crystalline hydrated inorganic salt, a crystalline organic acid salt, a crystalline organic salt, a crystalline surfactant, a saccharide, or a mixture thereof.

Preferably, the crystalline material of the speckle particles has at least a transparency and / or reflectance equal to the crude trisodium citrate dihydrate available from ADM.

Highly preferred crystalline organic salts include carboxylate salts. Also preferred are crystalline polymer polycarboxylic acids and salts thereof, preferably polyacrylic and / or maleic acid polymers and salts thereof.

Particularly preferred are those in which the crystalline material comprises trisodium citrate dihydrate, most preferably colored with a dye.

Preferred hydrated crystalline materials in the present invention include hydrated sulfates, hydrated carbonates, hydrated phosphates, hydrated magnesium salts, hydrated carboxylic acids and / or their salts. It is an inorganic salt. Highly preferred are sodium sulfate decahydrate or heptahydrate; sodium carbonate monohydrate; heptahydrate or decahydrate; applicable hydration numbers, especially 1, 2, 3, 6 Or trihydrate sodium tripolyphosphate, orthophosphate, metaphosphate and / or pyrophosphate; magnesium sulfate mono- or heptahydrate, sodium citrate dihydrate or pentahydrate; glucose, maltose , Galactose, fructose or mixtures thereof, especially sugars.

A crystalline material such as a crystalline silicate including a crystalline layered silicate,
Other ingredients commonly used in detergent compositions are also useful.

The speckle particles comprise at least 20% by weight of the particles of the crystalline hydrated material, preferably at least 50%, and even at least 75%, wherein the particles are substantially free of amorphous material. preferable.

The speckle particles may contain other components. In one embodiment, the speckle particles preferably include a binder to bind the crystalline hydration material and / or the colorant.

The speckle particles are preferably made by aggregating a binder with a crystalline hydration material and / or a colorant.

[0036] Any binder material can be used. Preferred binders are
It includes water, a mixture of water and other components, for example, a surfactant paste. Also useful are liquid or viscous surfactants, polyalkylene glycols, preferably polyethylene glycols, waxes and oils.

In one preferred embodiment, the weight average particle size of the speckle particles is 40
0 microns to 2000 microns, preferably 500 microns to 1400 microns, 600 microns to 1180 microns, and even 710 microns to 1000 microns.

When the weight average particle size is between 500 and 1400, at least 70%, at least 80%, at least 90%, and even substantially all particles have a particle size of 6
Preferably it is between 00 microns and 1180 microns. Weight average particle size of 6
At 00 to 1180, at least 70%, at least 80%, at least 9
Preferably, the particle size of 0%, and even substantially all, of the particles is between 710 microns and 1000 microns.

That is, it was found that when the average particle size of the speckle particles was within this range, a necessary result could be obtained using a small amount of speckle particles. When speckle particles having a specific particle size are used, dyeing of the particles can be more effectively controlled, and a small amount of dye can be effectively used per particle, and simultaneously uniformly dyed particles can be obtained. .

[0040] Speckle particles of this particle size are preferably obtained by combining the smaller particles with a binder, for example by agglomeration, as described herein. For example, this material can be obtained from a material having a larger particle size by grinding. Alternatively, speckle particles of this particle size may be obtained by alternatively or additionally by sieving the particles and selecting a material of the required particle size.

Other methods of controlling the particle size of the crystalline material are known to those skilled in the art and can be used to obtain particles of the required size.

The speckle particles may be colored by any method known in the art. Preferably, the colorant is mixed with the crystalline material, preferably in the presence of a binder. The speckle particles are sprayed with a colorant, preferably a dye and / or a brightener, onto a mixing vessel or drum containing the speckle particles, and optionally the colored speckle particles are It may be colored, preferably by drying in a fluidized bed.

Dye The speckle particles of the present invention are preferably dyed particles. The dye used for dyeing the particles used herein is a dye or an aqueous solution of a dye using a carrier material such as, for example, a nonionic surfactant or other organic binder material, a nonaqueous solution or a mixture of the dye. The use of a non-aqueous solution is advantageous because no subsequent drying step is required when the solution is applied to speckle particles.

The dye is an aqueous solution at a concentration that results in a suitable dyeing of the particles, preferably, as described above, a concentration at which the dye solution contains up to 2% by weight, more preferably up to 0.5% by weight, speckle particles. It is preferred that Optionally, the dye also contains other components, such as an organic binder material.

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), and ultramarine blue (trade name). ), E133-Food Blue 2
(Brilland Blue FCF), E140-Natural Green 3 (chlorophyll and chlorphyrin), E141 and Pigment Green 7 (Cu phthalocyanine chloride). Preferred dyes are Monstral blue BV paste (trade name) and / or Pigmasol green (trade name).

The speckle particles preferably comprise such dyes in low concentrations, preferably up to only 2%, preferably up to 1%, and even up to 0.7%, the dye comprising 0.5% by weight of the speckle particles. %, Preferably at a concentration of less than 0.2%, even more preferably 0.1% by weight.

Brightener The speckle particles are colored by a brightener, preferably some hydrophilic optical brightener.

The speckle particles comprise such brighteners at a concentration of preferably up to 20%, more preferably up to 10% and even up to 5% by weight of the speckle particles.

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-
Selected from 2-hydroxyethyl-N-methylamino, morpholino, chloro and amino, where M is a salt-forming cation such as sodium or potassium.

In the above formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, M
Is a cation such as 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 particular brightener type is available from Ciba Geigy Corporation as Tinopal-UNP
It is marketed under the trade name A-GX. Tinopal-CBS-X and T
Inopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the present detergent compositions.

In the above formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl-N
-2-methylamino, when M is a cation such as 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 particular brightener species 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 such as sodium, the brightener is 4,4′-bis [(4-anilino-6-morpholino-
s-Triazin-2-yl) amino] 2,2′-stilbenedisulfonic acid, disodium salt. This particular brightener species is commercially available from Ciba-Geigy Corporation under the trade names Tinopal-DMS-X and Tinopal AMS-GX.

Pigment The speckle particles may also include a pigment as a colorant. Any pigment suitable for the cleaning composition can be used in the present invention.

Composition The speckle particles are preferably present in a cleaning composition, preferably a granular cleaning composition. The exact concentration of speckle particles to be present in the composition depends, inter alia, on the color of the degree of light reflectance or transparency of the speckle particles, the color of the speckle particles and other components of the composition, the speckle particles and other components of the composition. Depends on the particle size of the components and the method of application of the composition.

The composition may contain speckle particles at any concentration, but is preferably from 0.05% to 50%, more preferably from 0.1% to 30% by weight of the composition, More preferably, it is 0.3% by weight to 10% by weight.

The cleaning composition of the present invention is preferably a solid laundry, dishwashing or hard surface cleaning composition, preferably a granule, extrudate, flake or tablet.

The cleaning composition may further comprise conventional ingredients commonly used in cleaning compositions, rather than colored speckle particles. Preferred components will be described later.

The speckle particles of the present invention may be a composition containing a component having no color of a desired product,
It is particularly useful for compositions containing a hygroscopic component that absorbs moisture and bleeds the dyes present.

The compositions of the present invention preferably include ingredients such as particles comprising surfactants, enzymes, bleach activators, cellulose derivatives or mixtures thereof that tend to have an undesirable color.

The surfactant containing the particles is preferably an aggregate with an anionic and / or non-ionic surfactant, preferably a LAS and / or ethoxylated alcohol surfactant.

Also preferred are particles containing a peroxyacid bleach precursor such as TAED, NAC-OBS and other OBS-variants or mixtures thereof.

When the present composition containing speckle particles contains other components in particulate form, these other particles or a portion thereof also reduce particle separation and increase dye locally. It is preferred to have a weight average particle size as defined below, so that the concentration can be reduced so that the dye can be distributed evenly throughout the product. This will also reduce the likelihood of discoloration of products, packaging materials and fabrics during the cleaning or cleaning process.

In one embodiment, the composition has an average particle size of between 600 microns and 1400 microns, preferably between 700 microns and 1100 microns, and even between 750 and 1000 microns, preferably at least 60%, more preferably at least 80%.
% Granules. In the composition, the fine particle component having a particle size of less than 300 microns, less than 450 microns, and less than 600 microns is less than 20% by weight;
Further less than 10% by weight, less than 5% by weight and / or more than 1600 microns,
Preferably, the particulate component having a particle size greater than 1400 microns, and even greater than 1200 microns, is less than 20% by weight, less than 10% by weight, and less than 5% by weight.

The compositions can be made by methods known in the art, including agglomeration and / or spray drying, wherein the particular ingredients are mixed or sprayed as described herein. The composition is made by agglomeration or spray drying,
And mixing all or part of the granules containing the speckle particles of the present invention, adding a binder, agglomerating the mixture with the binder to form an aggregated detergent granule, or having a required particle size. It is preferable that the particles are sieved to obtain particles of various sizes.

The composition comprises at least 350 g / l, more preferably at least 50 g / l
It is preferably a solid detergent having a density of 0 g / l, more preferably 580 g / l.

The detergent composition preferably comprises one or more anionic surfactants and an aluminosilicate builder, in particular less than 50%, more preferably less than 30%, of the total amount of anionic surfactant and aluminosilicate. Preferably, a small mixture of less than 50%, even less than 30%, of the silicate and an anionic surfactant is in an intimate mixture. Further, it is preferred that the anionic surfactant and the aluminosilicate builder are not substantially in an intimate mixture. in this way,
The composition is preferably composed of at least two types of discrete particles containing either an anionic surfactant or an aluminosilicate. "Intimate mixture", according to the present invention, means that two or more components are substantially uniformly distributed in the components or particles. That is, it has been found that the solubility and / or formulation of the composition is improved by this.

It is also preferred that the composition contains only low concentrations of aluminosilicate builder, for example less than 10%, and even less than 5% of the composition. The composition preferably comprises a very soluble builder, such as sodium citrate or citric acid, carbonate and / or crystalline layered silicate.

The composition may also contain from 0.5% by weight as a builder system or part of a builder system.
80% by weight of the crystalline layered silicate, 10% by weight to 70% by weight of an agglomerate containing a surfactant, preferably an anionic surfactant, and 1% of an agglomerate containing no water.
More preferably, it is less than 0% by weight, the crystalline layered silicate is 30% to 60% by weight, and the anionic surfactant is 20% to 50% by weight.

Foaming Component The detergent composition is preferably an acid capable of reacting to form a gas when contacted with water, especially carbon dioxide gas formed by the reaction of an organic carboxylic acid with a carbonate source. It is highly preferred to include a foaming component comprising a source and an alkali source. In the present invention, the foaming components may be present as an intimate mixture with one another, preferably in the form of granules, or as separate particles.

The foaming component is preferably a fine particle component having an average particle size of 700 to 1400 microns, preferably 750 to 1100 microns, including an acid source and an alkali source.

It is preferable that the foaming component does not substantially mix water with the foaming component or a part thereof so that water does not exist except for the water content of the raw material itself. Usually, the concentration of water in an intimate mixture with the foaming component is such that the total weight of the granules is less than 5% by weight, preferably 3% by weight.
Less than 1.5% by weight, preferably obtained by dry powder compression or pressure agglomeration.

[0072] These preferred dry expanded particles produce carbon dioxide very quickly,
The dispersibility and decomposition rate of the present granule composition are promoted. The granule compositions of the present invention, including the dry foam granules described herein, can disperse and disintegrate the granule composition in water in a short period of time and with a low total concentration of foam particles / material, allowing the detergent components to It is intended to more effectively reach the cleaning object.

Acids suitable for use in the present invention include solid organic, mineral or inorganic acids, salts or derivatives thereof, or mixtures thereof. The acid can be 1-, 2- or 3-
Preferably, it is a basic acid. Such acids include mono- or polycarboxylic acids,
Preferably citric acid, adipic acid, glutaric acid, 3-ketoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid are exemplified. Such acids are preferably used in acidic form, and also preferably in anhydrous form or as a mixture thereof. Derivatives also include esters of acids.

[0074] Effervescent ingredients or sources include carbonate sources, including carbonates, bicarbonates and percarbonates, especially bicarbonates and / or carbonates. Suitable carbonates for use in the present invention include carbonates such as potassium, lithium and sodium and hydrogen carbonates, with sodium carbonate and potassium carbonate being preferred. Bicarbonates suitable for use in the present invention include alkali metal salts of bicarbonates such as lithium, sodium and potassium, with sodium bicarbonate and potassium bicarbonate being preferred. Bicarbonate is preferred over carbonate because bicarbonate is more effective by weight, ie, an equal weight of bicarbonate has a greater “storage capacity” for CO ₂ than carbonate. However, the choice of carbonates, bicarbonates or mixtures thereof in the dry foam granules depends on the desired pH in the aqueous medium in which the dry foam granules are dissolved. For example, if a relatively high pH (eg, above pH 9.5) is desired for the aqueous medium, it is preferable to use only carbonate or a combination of carbonate and bicarbonate. At this time, the concentration of carbonate is higher than the concentration of bicarbonate, and the weight ratio of carbonate to bicarbonate is 0.1 to 10, more preferably 1 to 5, and most preferably 1 to 2. .

[0075] Such effervescent granules may also include a binder that includes a surfactant, such as anionic and nonionic surfactants.

The foaming component is present in the composition according to the invention in a concentration of 0.5% to 60% by weight, preferably 2% to 50% by weight, more preferably 5% to 45% by weight, The acid component is present at a concentration of 0.3% to 40%, more preferably 1.0% to 35%, 2% to 25%, and even 15% by weight of the composition. .

Surfactants Compositions according to the present invention may be anionic, nonionic, cationic, amphoteric (amphol)
It preferably comprises one or more surfactants selected from the group consisting of ytic, amphoteric) and amphoteric surfactants and mixtures thereof.

For the types and species of anionic, nonionic, amphoteric and zwitterionic surfactants, see US Pat. No. 3,929,678 issued Dec. 30, 1975 (L
(Ahlin and Heuring). It is also exemplified in "Surfactants and Detergents" (Schwartz, Perry and Berch, Volumes I and II). Suitable cationic surfactants are described in U.S. Pat. No. 4,259,217 issued Mar. 31, 1981 (Mur.
phy) is listed.

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

Anionic surfactant The composition according to the invention preferably further comprises an anionic surfactant. Essentially any anionic surfactant useful for detergent purposes can be included in the detergent composition. Salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and tri-ethanolamine salts). Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred are surfactant systems comprising sulfonate and sulfate surfactants, preferably the linear or branched alkyl benzene sulfonates and alkyl ethoxy sulfates described herein are those described herein. It is preferred to use in combination with a cationic surfactant.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monosulfones of sulfosuccinates ester(
In particular, mention may be made of saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters), and N-acyl sarcosinates. Also suitable are resin acids and hydrogenated resin acids, such as rosin and hydrogenated rosin, wherein the resin acids and hydrogenated resin acids are present in or derived from tallow.

Anionic Sulfate Surfactants Suitable anionic sulfate surfactants for use in the present invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl 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 polyglucosides (herein non (Described as ionic non-sulfate compounds).

[0084] alkyl sulfate surfactants, linear and branched it is preferably selected from alkyl sulfates primary _C 10 _{-C 18,} more preferably _C 11 _{-C 1 5} branched chain alkyl sulfates and _{C 12} ~ is a linear alkyl sulfates of C _14.

The alkyl ethoxy sulphate surfactant is preferably selected from the group consisting of C ₁₀ -C ₁₈ alkyl sulphates ethoxylated with 0.5 to 20 mol of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is 0.5 to 7 moles per molecule, preferably _C 11 _{-C 18} ethoxylated with 1-5 moles of ethylene oxide, more preferably _{C 1} 1 _{-C 15} It is an alkyl sulfate.

A particularly preferred embodiment of the present invention is to use a mixture of the preferred alkyl sulphate and / or sulphonate with an alkyl ethoxy sulphate surfactant. Such a mixture is disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactants Suitable anionic sulfonate surfactants for use in the present invention include C ₅ -C ₂₀ linear alkyl benzene sulfonates, alkyl ester sulfonates, and C ₆ -C ₂₂ primary or secondary alkane sulfonates, olefin sulfonates of C ₆ -C _{2 4,} sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, and fatty oleyl glycerol sulfonates, and mixtures thereof.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps (“alkyl carboxyls”), especially Specific secondary soaps mentioned in the description are mentioned.

Suitable alkylethoxycarboxylates include those of the formula RO (CH ₂ CH ₂ O
^{_{) X CH 2 COO - M +}} ( wherein, R is an alkyl group of _C 6 _{~C 18,} x is 0-10
The ethoxylate distribution is such that the amount of material is less than 20% when x is 0 on a weight basis, and M is a cation. ). Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula RO- (CHR ₁ -CHR ₂ -O) -R _{3 where} R is a C ₆ -C ₁₈ alkyl group and x is 1 to 25
, R ₁ and R ₂ are selected from the group consisting of hydrogen, methyl acid radical, succinic radical, hydroxysuccinic radical and mixtures thereof, R ₃ is hydrogen, a substituted or unsubstituted hydrocarbon of 1 to 8 carbon atoms And mixtures thereof.

Suitable soap surfactants include secondary soap surfactants containing a carboxyl unit attached to a secondary carbon. Second preferred for use in the present invention
Grade soap surfactants are 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptane. It is a water-soluble group selected from the group consisting of water-soluble salts of acids.

[0091] Certain soaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactants Other suitable anionic surfactants are of the formula R-CON (R¹) CH₂COO
M (where R is C₅~ C₁₇A chain or branched alkyl or alkenyl group of ¹ Is C₁~ C₄An alkyl group, and M is an alkali metal ion)
It is sarcosinate. A preferred example is myristyl in the form of a sodium salt.
And oleyl methyl sarcosinate.

Alkoxylated Nonionic Surfactants Essentially any alkoxylated nonionic surfactant is suitable in the present invention. Ethoxylated and propoxylated nonionic surfactants are preferred.

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

Nonionic alkoxylated alcohol surfactants Condensation products of aliphatic alcohols with alkylene oxides, especially ethylene oxide and / or 1 to 25 moles of propylene oxide, are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol is either linear or branched, primary or secondary, and usually contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having alkyl groups containing 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic Polyhydroxyfatty Acid Amide Surfactants Polyhydroxyfatty acid amides suitable for use in the present invention have the structural formula R ² CON
R ¹ Z. Wherein R ₁ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or mixtures thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl. alkyl, most preferably alkyl _{C 1} (e.g., methyl), _{R 2} is _C 5 _{-C 3 1} hydrocarbyl, preferably straight-chain alkyl or alkenyl _C 5 _{-C 19,} more preferably straight chain _C 9 -C ₁₇ alkyl or alkenyl, most preferably linear C ₁₁ -C ₁₇ alkyl or alkenyl, or mixtures thereof, Z
Is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction. More preferably, Z is glycityl.

Nonionic fatty acid amide surfactants Suitable fatty acid amide surfactants are those represented by the formula R ⁶ CON (R ⁷ ) ₂ . Wherein R ⁶ is an alkyl group containing 7-21, preferably 9-17 carbon atoms, each R ⁷ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and _{- (C 2 H 4 O)} x H ( wherein, x is in the range of 1 to 3)
Selected from the group consisting of:

Nonionic Alkyl Polysaccharide Surfactants Alkyl polysaccharides suitable for use in the present invention are disclosed in US Pat. No. 4,565,647 (Llenado) issued Jan. 21, 1986. Was
It contains a hydrophobic group containing 6 to 30 carbon atoms and a polysaccharide containing 1.3 to 10 saccharide units, for example, a polyglycoside or a hydrophilic group.

Preferred alkyl polyglycosides are of the formula R ² O (C _n H _2n O) _t (glycosyl) _x , wherein R ² is alkyl, alkylphenyl, hydroxyalkyl,
Selected from the group consisting of hydroxyalkylphenyls and mixtures thereof, wherein the alkyl group contains 10-18 carbon atoms, n is 2 or 3, t is 0-10, x
Is from 1.3 to 8. Glycosyl is preferably derived from glycol.

Amphoteric Surfactants Suitable amphoteric surfactants for use in the present invention include amine oxide surfactants and alkyl amphoteric carboxylic acids.

Suitable amine oxides include compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ , wherein R ³ is an alkyl, hydroxyalkyl containing 8 to 26 carbon atoms. , Acylamidopropyl and alkylphenyl groups or mixtures thereof, wherein R ⁴ is an alkylene or hydroxyalkylene containing 2-3 carbon atoms or a mixture thereof, and x is 0-5, preferably 0-5 3 and each R ⁵ is a polyethylene oxide group containing 1-3 alkyl or hydroxyalkyl groups or 1-3 ethylene oxide groups. Preferred are acyl amides alkyl dimethyl amine oxide alkyl dimethyl amine oxides and _{C 10 to 18} of the _C 10 _{-C 18.}

Suitable alkyl amphoteric carboxylic acids are available from Miranol (New Jersey, USA).
Miranol ™ C2M concentrate (Dayton).

Zwitter Surfactants Zwitter surfactants can also be incorporated into the detergent compositions according to the present invention. The surfactant is generally a derivative of a secondary and tertiary amine, a derivative of a heterocyclic secondary and tertiary amine, or a quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound. It is described as a derivative. Betaine and sultaine surfactants are exemplified as zwitterionic surfactants for use in the present invention.

Suitable betaines are compounds of the formula R (R ′) ₂ N ⁺ R ² COO ⁻ , wherein
R is a C ₆ -C ₁₈ hydrocarbyl group, each R ¹ is a C ₁ -C ₃ alkyl, and R ² is a C ₁ -C ₅ hydrocarbyl group. Preferred betaines are _C12-18 dimethyl-ammoniohexanoate and _{C10-18 acylamidopropane} (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention.

Cationic Surfactants Cationic surfactants suitable for use in the present detergents include quaternary ammonium surfactants.
Surfactants. Preferred quaternary ammonium surfactants are mono C ₆ ~ C₁₆, Preferably C₆~ C₁₀N-alkyl or alkenyl ammonium
Surfactants wherein the remaining N-position is methyl, hydroxyethyl or hydro
It is substituted by a xypropyl group. Also, mono-alkoxylation
And bis-alkoxylated amine surfactants are also preferred.

Another suitable class of cationic surfactants that can be used in the detergent compositions or components of the present invention are cationic ester surfactants. Cationic ester surfactants are compounds that have surfactant properties, preferably containing at least one ester (i.e., -COO-) linkage and at least one cationically charged group, which are preferably water dispersible. .

Suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

In one preferred embodiment, the ester linkage and the cationically charged group have at least 3
Interface, preferably a chain comprising 3 atoms, preferably 3-8 atoms, more preferably 3-5 atoms, most preferably 3 atoms (ie a chain length of 3 atoms). Are separated from each other in the activator molecule. The atoms forming the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms and mixtures thereof. However, a nitrogen or oxygen atom in the chain bonds only to a carbon atom in the chain. Thus, for example, -OO- (i.e., peroxide), -NN- and-.
Spacer group having a N-O-bond is removed, 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 spacer group has only carbon atoms, and most preferably the chain is a hydrocarbyl chain.

Cationic mono-alkoxylated amine surfactants Very preferred according to the invention are preferably cationic mono-alkoxylated amine surfactants of the general formula I
It is an alkoxylated amine surfactant.

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

Preferably, if the ApR ⁴ group in Formula I is a hydroxyalkyl group having 1 or less and 6 carbon atoms or less, the —OH group may be separated from the quaternary ammonium nitrogen by 3 or less carbon atoms. Separated. Particularly preferred ApR ⁴ _{groups, -CH 2 CH 2 OH -,} - CH 2 CH 2 CH 2 OH -, - CH 2 CH (CH 3) OH and -C
H (CH ₃ ) CH ₂ OH, particularly preferred is —CH ₂ CH ₂ OH. Preferred R ¹ groups are linear alkyl groups. Preference is given to linear R ¹ radicals having 8 to 14 carbon atoms.

Another highly preferred cationic mono-alkoxylated amine surfactant for use in the present invention is of the formula:

Embedded image Wherein R ¹ is a C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C _18.
Alkyl of C _14, preferably C ₁₀ alkyl and C _12, X is an anion which is suitable providing charge balance, preferably chloride or bromide.

Compounds of the type described above include ethoxy (CH₂CH₂O) Unit (EO) is
Toxy, isopropoxy [CH (CH₃) CH₂O] and [CH₂CH (CH ₃ O] unit (i-Pr) or n-propoxy unit (Pr) or EO and / or
Or those substituted with a mixture of Pr and / or i-Pr units.
You.

The concentration 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%.
. It is from 2% to 7% by weight, most preferably from 0.3% to 3.0% by weight.

Cationic Bis-alkoxylated amine surfactant The cationic bis-alkoxylated amine surfactant is preferably of the following structural formula II:

Embedded image Wherein R ¹ is an alkyl or alkenyl moiety containing about 8 to about 18 carbon atoms, preferably about 10 to about 16 carbon atoms, and most preferably about 10 to about 14 carbon atoms; R ² is an alkyl group containing 1 to 3 carbon atoms, preferably methyl, R ³ and R ⁴ are independently different and are selected from hydrogen (preferred), methyl and ethyl, and X ⁻ Anions such as chloride, bromide, methyl sulfate, sulfate, etc., sufficient to confer properties. A and A ′ are independently different and are C ₁ -C ₄ alkoxy, especially ethoxy (—CH ₂ CH ₂ O—),
Each selected from propoxy, butoxy and mixtures thereof, wherein p is from 1 to about 30;
, Preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, and most preferably p and q are both 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use in the present invention are of the formula:

Embedded imageWhere R¹Is C₁₀~ C₁₈Of hydrocarbyl and mixtures thereof, preferably
C₁₀, C₁₂, C₁₄And mixtures thereof. X gives charge balance
Any suitable anion, preferably chloride. The above cationic bis-alco
With respect to the general structure of the xylated amine, preferred compounds include R¹Is (palm)
C₁₂~ C₁₄Is a fatty acid of the alkyl fraction of²Is methyl, ApR ³ And A'qR⁴Is monoethoxy.

[0116] Other cationic bis-alkoxylated amine surfactants useful in the present invention include compounds of the formula:

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, independently p is 1 to about 3, q is 1 to about 3, and R ² is C ₁ -C _3. Alkyl, preferably methyl, X is an anion, especially chloride or bromide.

Other compounds of the type described above include ethoxy (CH ₂ CH ₂ O) units (EO
) Is, butoxy (Bu) isopropoxy _{[CH (CH 3) CH 2} O] and [C
Also include those substituted with a mixture of H _{2 CH} (CH 3 O] units (i-Pr) or n- propoxy units (Pr) or EO and / or Pr and / or i-Pr units.

Perhydration bleach A preferred additional component of the composition is a perhydration bleach such as metal perborate, metal percarbonate, especially the sodium salt. The perborate can be mono- or tetra-hydrated. Sodium percarbonate is 2Na ₂ CO ₃ . Represented by the formula 3H ₂ O ₂ ,
It is commercially available as a crystalline solid.

The superhydration bleach may be coated, for example, with sulfates, carbonates, silicates or mixtures thereof.

[0120] Potassium, sodium peroxymonopersulfate is any other inorganic perhydrate salt used in the present detergent compositions.

Bleach Activator The composition comprises a bleach activator, preferably an organic peracid bleach precursor. The composition comprises at least two peracid bleach precursors, as defined herein, preferably at least one hydrophobic peracid bleach precursor and at least one hydrophilic peracid bleach precursor. It is preferred to include.

The bleach activators may also include a preformed peracid bleach.

The production of the organic peracid is made by the in-situ reaction of the precursor and the hydrogen peroxide source.

Peracid bleach precursor The peracid bleach precursor is a compound that reacts with hydrogen peroxide in a perhydrolysis reaction to generate peracid. Peracid bleach precursors are usually represented as follows:

Embedded image In the formula, L is a residue, and X may be essentially any functional group as long as the structure of the peracid generated in the perhydrolysis is as follows.

Embedded image

In the present invention, the hydrophobic peracid bleach precursor is represented by the above formula (where X is at least 6
Peroxyacid) having a peroxy acid of the formula (X).
Is a group containing 1 to 5 carbon atoms).

The peracid bleach precursor compound may comprise from 0.5% to 20%, more preferably from 1% to 15%, most preferably from 1.5% to 10% by weight of the detergent composition. Preferably, it is incorporated at a concentration of

Suitable peracid bleach precursor compounds contain one or more N- or O-acyl groups, and the precursors can be selected from a wide variety. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazole and oximes. For examples of useful materials within this class, see GB-A-First
No. 586,789. Suitable esters are GB-A-83
No. 6988, No. 864798, No. 1147787, No. 2
No. 143231 and EP-A-0170386.

Residues Residues (hereinafter L groups) must have sufficient reactivity to produce a perhydrolysis reaction within an optimal time frame (eg, a wash cycle). However,
If the reactivity of L is too strong, the activator is difficult to stabilize for use in bleaching compositions.

Preferred L groups are selected from the group consisting of: and the mixtures thereof.

Embedded image Wherein R ¹ is an alkyl, aryl or alkaryl group containing ¹ to 14 carbon atoms, R ³ is an alkyl chain containing 1 to 8 carbon atoms, and R ⁴ is H or R ³ and Y is H or a soluble group. R ¹ , R ³ and R ⁴ may be substituted by essentially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

A preferred soluble group is —SO₃ ⁻M⁺, -CO₂ ⁻M⁺, -SO₄ ⁻M⁺, −
N⁺(R³)₄X⁻And O <-N (R³)₃And most preferably -SO ₃ ⁻ M⁺And -CO₂ ⁻M⁺It is. Where R³Contains 1 to 4 carbon atoms
Al is an alkyl chain, M is a cation that renders the bleach activator soluble, and X is a bleach activator.
It is an anion that gives solubility to water. Preferably, M is an alkali metal, ammonium
Or substituted ammonium cations, with sodium and potassium being the most
Preferably, X is a halide, hydroxide, methyl sulfate or acetate anion.
You.

Alkyl Percarboxylic Acid Bleach Precursor The alkyl percarboxylic acid bleach precursor forms a percarboxylic acid by perhydrolysis. Preferred precursors of this type give peracetic acid by perhydrolysis.

Preferred alkyl percarboxylic acid precursor compounds of the imide type include N, N, N ¹ N ¹ tetraacetylated alkylenediamines in which the alkylene group contains from 1 to 6 carbon atoms, and especially alkylene diamines. Mention may be made of compounds wherein the group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED)
Is particularly preferred as a hydrophilic peracid bleach precursor.

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

Amide-Substituted Alkyl Peracid Precursors Amide-substituted alkyl peracid precursor compounds are suitable in the present invention, and include those represented by the following general formula.

Embedded imageWhere R¹Is an aryl or alkaryl group having about 1 to about 14 carbon atoms
And R²Are alkylene, arylene and arylene containing from about 1 to 14 carbon atoms.
And an alkylene group;⁵Is H or an atom containing 1 to 10 carbon atoms.
Alkyl, aryl or alkaryl groups, where L is essentially any residue.
You may. R¹Preferably contains from about 6 to 12 carbon atoms. R²Is preferred
Or about 4 to 8 carbon atoms. R¹Is a chain or branched alkyl, branched,
It may be a substituted aryl or alkylaryl containing a substitution or both.
It originates from either natural sources or natural sources including, for example, tallow fat. As well
The structural deformation of R²Is also allowed. R²Includes alkyl and aryl;
R²Can also be halogen, nitrogen, sulfur and other typical substituents or organic compounds.
Things may be included. R⁵Is preferably H or methyl. R¹And R ⁵ Must not contain more than 18 carbon atoms in total. This kind of amide substitution drift
Whitening agent activator compounds are described in EP-A-0170386.
ing. R¹And R⁵Must combine with nitrogen and carbon atoms to form a ring structure
preferable.

Preferred examples of this type of bleach precursor include amide-substituted peracid precursor compounds selected from (6-octanamido-caproyl) oxybenzenesulfonate and (6-decanamido-caproyl) oxybenzene-sulfonate. And
Highly preferred are described in EP-A-0170386 (
6-nonanamidocaproyl) oxybenzenesulfonate and mixtures thereof.

Perbenzoic acid precursor The perbenzoic acid precursor compound gives perbenzoic acid by perhydrolysis. Suitable O
-Acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, sorbitol, glycol and benzoylation products of whole sugars with benzoylating agents, imide species such as N-benzoylsuccinimide , Tetrabenzoylethylenediamine and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include:
N-benzoyl imidazole and N-benzoyl benzimidazole are mentioned. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Preformed Organic Peracid The present detergent compositions comprise, in addition to or instead of an organic peracid bleach precursor compound, a preformed organic peracid, generally from 1% by weight of the composition. It may be contained at a concentration of 15% by weight, more preferably 1% by weight to 10% by weight.

A preferred type of the organic peracid compound is an amide-substituted compound represented by the following 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 and alkarylene group having 1 to 14 carbon atoms, and R ⁵ is H, or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. This type of amide-substituted organic peracid compound is described in EP-A-0170386.

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

Heavy Sequestering Agent The compositions of the present invention preferably include a heavy metal sequestering agent, a chelating agent or a chelating agent as an optional ingredient. The heavy metal ion sequestering agent herein refers to a component that acts to sequester (chelate) heavy metal ions. These components also have the ability to chelate calcium and magnesium, but preferentially bind heavy metal ions such as iron, manganese and copper.

Heavy sequestering agents usually comprise from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7% by weight of the composition or component.
. It is present at a concentration of 5% by weight, most preferably 0.3% to 2% by weight.

[0142] Suitable heavy metal ion sequestering agents for use in the present invention include organic alkylates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxydisphosphonates and nitrotrimethylene phosphonates.

Preferred among the above types are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate) hexamethylenediaminetetra (methylenephosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonate. Acids and 1,1 hydroxyethanedimethylenephosphonic acid.

Other heavy metal ion sequestering agents suitable for use in the present invention include nitrilotriacetic acid and ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid, and the like. Polyaminocarboxylic acids or salts thereof.

Other heavy metal ion sequestering agents suitable for use in the present invention are EP-A-
Iminodiacetate derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid described in US Pat. No. 317,542 and EP-A-399,133. EP-A-516,102, iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N
-Carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestering agents are also suitable. EP-A- [beta] -alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid- described in JP-A-509,382.
N-monoacetic acid and iminodisuccinic acid sequestering agents are also suitable.

[0146] EP-A-476,257 describes suitable amino-based sequestering agents. EP-A-510,331 describes suitable sequestering agents derived from collagen, keratin or casein. EP-
A-528,859 describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N'-disuccinic acid (GADS
), Ethylenediamine-N, N′-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N′-disuccinic acid (HPDDS) are also suitable.

Particularly preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N, N
'-Disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or an alkali metal, alkaline earth metal, ammonium or substituted ammonium salt, or a mixture thereof.

In particular, amino or chelating agents having an amino group can be bleach sensitive and are suitable for the compositions of the present invention.

Enzymes Other highly preferred components useful in the present compositions are enzymes that are added by one or more.

Preferred additional enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Can be For suitable enzymes see US Pat. No. 3,519,5.
No. 70 and 3,533,139.

Preferred commercial protease enzymes include Novo Industry A / S (
Denmark) from Alcalase, Savinase, Primase, Du
Gis, sold under the trade names razym and Esperase
Maxatase, Maxacal and Maxap from t-Brocades
em, those sold by Genencor International, and those sold by Solvay Enzyme under the trade names Opticlean and Optimase. The protease enzyme may be incorporated into the composition according to the present invention at a concentration that results in 0.0001% to 4% by weight of the composition of active enzyme.

Preferred amylase includes, for example, α-amylase obtained from a special strain of B. licheniformis. See GB Nos. 1 and 2 for details.
No. 69,839 (Novo). Preferred commercially available amylases include, for example, those sold under the trade name Rapidase by Gist-Brocades and Termam by Novo Industries A / S.
yl, Duramyl and BAN. Highly preferred amylase enzymes are those described in PCT / US9703635 and WO95 / 26397 and WO96 / 23873.

The amylase enzyme is present in the composition according to the invention in an amount of from 0.0001% to 2% by weight of the composition.
It may be incorporated at a concentration that results in wt% active enzyme.

The lipolysis-promoting enzyme is present in an amount of 0.0001% to 2%, preferably 0% by weight of the composition.
. 001% to 1%, most preferably 0.001% to 0.5% by weight of active lipolysis-promoting enzyme may be incorporated at a concentration that results.

Lipases can be derived from fungi or bacteria, for example, Humicola s
p. , Thermomyces sp. Or Pseudomonas pse
udoalcaligenes or Pseudomas fluoresce
ns. And Pseudomonas sp. Can be obtained from a lipase-producing strain. Also useful are chemically or genetically altered mutants of these strains. Preferred lipases are granted European Patent No. EP-B-021
No. 8272, Pseudomonas pseudoalca
lineages.

Another preferred lipase is obtained by cloning the gene from Humicola lanuginosa and expressing the Aspergillus oryza gene as host, which is described in European Patent Application EP-A.
No. 0258 068, Novo Industry A / S (
It is commercially available from Bagsvaerd, Denmark under the trade name Lipolase. U.S. Pat. No. 4,810,414 issued Mar. 7, 1989 (
Huge-Jensen et al.) Also describes this lipase.

Optical Brighteners The present compositions may also comprise from about 0.005% by weight of the specific types of hydrophilic optical brighteners described above.
It is preferred to contain 5% by weight.

Photobleaches Photobleaches are a preferred component of the present compositions. Preferred photobleaches include compounds having a porphine or porphyrin structure.

Although porphine and porphyrin are used synonymously in the literature, porphine is usually the simplest porphyrin without substituents, and porphyrin is a subclass of porphine. When reference is made to porphine in the present application, porphyrin is also included.

In the porphine structure, metal elements or cations, preferably Ca, Mg, P,
Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or G
a, more preferably Al, most preferably Zn.

The photobleaching compound or component is selected from alkyl groups such as methyl, ethyl, propyl, t-butyl groups and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties. Is preferably substituted by the substituent to be formed.

[0162] The photobleaching compound or component can have a soluble group as a substituent. Alternatively or additionally, the photobleach may comprise a polymer component capable of dissolving the photobleaching compound, for example, PVP, PVNP, PVI or a copolymer thereof or mixtures thereof.

Very preferred photobleaching compounds are compounds having a phthalocyanine structure,
It preferably has the above-mentioned metal element or cation.

Metal phthalocyanines and derivatives thereof have the structure shown in FIG. 1 and / or FIG. 2, and the positions of the atoms in the phthalocyanine structure are usually numbered.

The phthalocyanines can be substituted, for example, 1-4, 6, 8-11, 1
A phthalocyanine structure in which one or more of 3,15-18,20,22-25,27 atom positions are substituted can be provided.

Water-soluble builder compounds The compositions according to the invention preferably comprise a water-soluble builder compound and generally comprise from 1% to 80%, preferably from 10% to 6% by weight of the composition in the detergent composition.
It is present at a concentration of 0% by weight, most preferably 15% to 40% by weight.

The detergent compositions of the present invention preferably include a phosphate-containing builder material. Preferably 0.5% to 60%, more preferably 5% to 50%, more preferably 8%
It is present at a concentration of ４０40%.

Preferably, the phosphate-containing builder material comprises tetrasodium pyrophosphate, more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds are water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts,
(Polycarboxylic acids have at least two carbon atoms separated from each other by no more than two carbon atoms.
Having two carboxyl radicals), borates and mixtures thereof.

The carboxylate or polycarboxylate builders can be of the monomer or oligomer type. However, monomeric polycarboxylates are usually preferred for cost and performance.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, ether carboxylate and sulfinyl carboxylate. Water-soluble salts. Examples of polycarboxylates containing three carboxy groups or acids thereof include water-soluble citrates, aconitrates and citraconates, carboxymethyloxysuccinates described in GB 1,379,24, UK patents Succinate derivatives such as lactoxy succinate described in 1,389,732 and amino succinate described in Dutch application 72050873, British Patent 1,387,447 Oxypolycarboxylate materials, such as the 2-oxa-1,1,3-propanetricarboxylate described herein. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably from 0.1% to 15% by weight of the composition.
% By weight, more preferably from 0.5% to 8% by weight.

As polycarboxylates containing four carboxy groups, British Patent No. 1
Oxydisuccinates disclosed in U.S. Pat.
-Ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propanetetracarboxylate.
Polycarboxylates containing sulfo substituents include GB 1,398
421,421 and 1,398,422, U.S. Patent 3,936.
, The sulfosuccinate derivatives disclosed in U.S. Pat.
And the sulfonated pyrolytic citrate described in JP 39,000.
Preferred polycarboxylates are hydroxycarboxylates, especially citrates, containing up to three carboxy groups per molecule.

Mixtures of the monomeric or oligomeric polycarboxylate chelators with the parent acid or salts thereof, such as citric acid or citrate / citric acid mixtures, are also considered useful builder components.

[0174] Borate builders, and builders containing borate-forming materials capable of producing borate under detergent storage or washing conditions, are water-soluble builders useful in the present invention.

Suitable examples of water-soluble phosphate builders include alkali metal tripolyphosphate, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphoric acid, sodium having a degree of polymerization of about 6-21. Polymeta / phosphoric acid, and phthalic acid salts.

Partially soluble or insoluble builder compounds The compositions according to the invention may contain partially soluble or insoluble builder compounds, in detergent compositions from 0.5% to 60% by weight of the composition, Preferably 5
It is present at a concentration of from 50% to 50%, most preferably from 8% to 40% by weight.

Examples of the builder mainly insoluble in water include sodium aluminosilicate.
As mentioned above, in one embodiment of the present invention, it is preferred that only a small amount of aluminosilicate builder be present.

Suitable aluminosilicate zeolites have the unit formula Na _z [(AlO ₂ ) _z (S
iO ₂ ) _y ]. an _x H ₂ O, molar ratio from 1.0 to 0.5 of wherein, z and y are at least 6, z pairs y, x is at least 5, preferably from 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in a hydrated form,
It is preferred that the crystals contain from 0% to 28%, more preferably from 18% to 22%, water in bound form.

The aluminosilicate zeolite is a naturally occurring material, but is preferably
Induced by synthesis. Synthetic crystal aluminosilicate ion exchange materials
Olite A, Zeolite B, Zeolite P, Zeolite X and Zeolite HS
And mixtures thereof. Zeolite A has the formula Na₁₂[(AlO ₂ )₁₂(SiO₂)₁₂]. xH₂O (where x is 20-30, especially 27
). Zeolite X has the formula Na₈₆[(AlO₂)₈₆(SiO₂)_{1 06} ]. 276H₂It is represented by O.

Another preferred aluminosilicate zeolite is a zeolite MAP builder. The zeolite MAP can be present at a level of 1% to 80%, more preferably 15% to 40% by weight of the composition.

Zeolite MAP is described in EP 384070A (Unilever). As the alkali metal amino-silicate of zeolite P, the ratio of silicon to aluminum is 1.33 or less, preferably in the range of 0.9 to 1.33, more preferably in the range of 0.9 to 1.2. Is defined.

Of particular interest are zeolite MAPs having a silicon to aluminum ratio of 1.15 or less, especially 1.07 or less.

In a preferred embodiment, the zeolite MAP detergent builder comprises 1.0 to 10.0
Microns, more preferably 2.0 to 7.0 micrometers, and most preferably has a particle size, expressed as _{the d 50} value of 2.5 to 5.0 micrometers.

The d ₅₀ value indicates that 50% by weight of the particles have a smaller diameter than that number. The particle size can be determined, in particular, by using a scanning electron microscope and ordinary analysis techniques such as an electron microscope and a laser particle sizer. Other methods of obtaining the d _{5 0} values are disclosed in EP No. 384070A.

Organic Polymer Compound The organic polymer compound is a preferable additional component of the present composition, and is preferably present as a component of the fine particle component to cause an action of binding the fine particle component. By organic polymeric compound is meant essentially all polymeric organic compounds commonly used as dispersants, anti-redeposition agents, soil suspending agents in detergent compositions and are quaternary according to the present invention. High molecular weight organic polymer compounds such as clay flocculants, including ethoxylated (poly) amine clay soil removal / redeposition inhibitors.

The organic polymer compound is generally present in the detergent composition of the present invention in an amount of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.1% to 15%, by weight of the composition.
It is incorporated at a concentration of 5% to 10% by weight.

Examples of the organic polymer compound include a water-soluble organic homo- or co-polymer polycarboxylic acid or a salt thereof, and the polycarboxylic acid has at least two carboxy radicals separated from each other by two or less carbon atoms. Contains. The latter type of polymer is disclosed in GB-A- 1,596,756. Examples of such salts are polyacrylates with a MWt of 1000 to 5000 and copolymers with maleic anhydride, having a molecular weight of 2000 to 100,000, especially 40,000.
000-80,000.

Polyamino compounds are useful in the present invention and are described in EP-A-305282.
Specification, EP-A-305283 and EP-A-351629
And those derived from aspartic acid as disclosed in US Pat.

Terpolymers having a monomer unit selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially having an average molecular weight of 5,000 to 10,000, are also suitable in the present invention.

Other organic polymer compounds suitable for incorporation in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

A further useful polymer compound is polyethylene glycol, especially having a molecular weight of 10
00 to 10,000, more preferably 2000 to 8000, most preferably about 40
00.

Highly preferred polymer components in the present invention are US Pat. No. 4,968,45.
No. 1 (Scheibel et al.), US Pat. No. 5,415,807 (
Gosselink et al.) And in particular U.S. Patent Application Serial No. 60/051517, cotton and non-cotton soil release polymers.

Other organic compounds that are preferred clay dispersants / anti-redeposition agents for use in the present invention are ethoxylated cationic monoamines and diamines of the formula

Embedded image Wherein X is a nonionic group selected from the group consisting of H, C ₁ -C ₄ alkyl, hydroxyalkyl ester or ether groups and mixtures thereof;
20, preferably 0 to 4 (eg, ethylene, propylene, hexamethylene);
b is 1 or 0, for cationic monoamines (b = 0), n is at least 16, in the general range 20-35, for cationic diamines (b =
1), n is at least about 12, with a typical range from about 12 to about 42.

Other dispersants / anti-redeposition agents used in the present invention are EP-B-01196.
5, U.S. Pat. No. 4,659,802 and U.S. Pat.
No. 4,846.

Defoaming System The detergent composition of the present invention, when formulated for a machine cleaning composition, comprises a 0.1% composition.
It may contain a foam control system at a concentration of from 01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight.

Suitable foam control systems for use in the present invention may include essentially all known antifoam compounds, including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds.

As used herein, an antifoam compound refers to a compound or a mixture of compounds that acts to suppress foam generated by a solution of the detergent composition, especially when the solution is stirred.

Particularly preferred antifoam compounds for use in the present invention are the silicone antifoam compounds defined herein as antifoam compounds comprising a silicone component. Such silicone antifoam compounds also generally include a silica component. As used herein,
And the term "silicone" as generally referred to in the art includes various relatively high molecular weight polymers containing various types of siloxane units and hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable defoaming compounds include monocarboxylic fatty acids and their soluble salts. These materials are disclosed in U.S. Pat. No. 2,9,27 Sep. 1960.
No. 54,347 (Wayne St. John). The monocarboxylic fatty acids and salts thereof used as foam inhibitors have a hydrocarbyl chain of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts,
Ammonium and alkanol ammonium salts.

Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, cyanuric chloride and primary containing 1 to 24 carbon atoms. or secondary amine 2 moles to 3 moles tri -～ hexa is formed from the product of - alkyl melamine or di -～ aliphatic C ₁₈ -C ₄₀ ketones such as tetra alkyldiamine chlorotriazine (
Examples include (sterone) N-alkylated aminotriazines, propylene oxide, bisstearic acid amides and monostearyl di-alkali metal (eg, sodium, potassium, lithium) phosphates and phosphate esters.

Preferred foam control systems include (a) an antifoam compound, preferably a silicone antifoam compound, most preferably (i) 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound. % Of polydimethylsiloxane and (ii) silica in a concentration of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound, wherein said silica / silicone 5% to 50% by weight, preferably 10% to 40% by weight of the defoaming compound
(B) a dispersant compound, most preferably a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, from 0.5% by weight to A silicone glycol lake copolymer having a polyoxyalkylene content of 72 to 78% at a concentration of 10% by weight, preferably 1% to 10% by weight, a particularly preferred silicone glycol lake copolymer of this type is DCO 544 from Dow Corning. a silicone glycol rake copolymer commercially available under the name, (c) an inert carrier fluid compound, most _preferably comprising ethoxylated alcohols of C 16 _{-C 18,} degree of ethoxylation from 5 to 50, preferably 8 to 15 And 5
% Of inert carrier fluid compound at a concentration of from about 10% to about 80%, preferably from about 10% to about 70% by weight.

A highly preferred particulate foam control system is described in EP-A-0210731, which comprises a silicone antifoam compound and an organic carrier material having a melting point of 50 ° C. to 85 ° C. The carrier materials are glycerol monoester and 1
A fatty acid having a carbon chain containing 2 to 20 carbon atoms. EP-
A-0210721 discloses other preferred particulate foam control systems wherein the organic carrier material is a fatty acid or alcohol containing 12 to 20 carbon atoms with a melting point of 45 ° C to 80 ° C or a mixture thereof. I have.

Other highly preferred foam control systems include polydimethylsiloxanes or polydimethylsiloxanes, silicone mixtures such as aluminosilicates, polycarboxylic acid polymers such as copolymers of laic and acrylic acid.

Polymer Migration Inhibitors The present compositions may also contain from 0.01% to 10%, preferably from 0.05% to 10% by weight.
It may contain 0.5% by weight of a polymer transfer inhibitor.

Preferably, the polymeric migration inhibitor is selected from N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof. These polymers can also be crosslinked polymers.

Polymer Soil Release Agent A polymeric soil release agent (referred to herein as “SRA”) can optionally be used in the detergent compositions of the present invention. When used, the SRA is usually 0.1% of the present detergent composition.
01 to 10.0% by weight, generally 0.1% to 5% by weight, preferably 0.2%
-3.0% by weight.

A preferred SRA is a hydrophilic portion, such as polyester or nylon, that renders the hydrophobic surface hydrophilic, and adheres to the hydrophobic fibers and remains there until the wash and rinse cycle is completed. And a hydrophobic part that functions as an anchor for the hydrophilic part. This makes it possible to more easily clean stains generated after the SRA process in a subsequent cleaning procedure.

Preferred SRAs include oligomer terephthalate esters, which are generally prepared by at least one transesterification / oligomerization process using a metal catalyst such as a titanium (IV) alkoxide. .
Such esters are made with additional monomers that can be incorporated into the ester structure at one, two, three, four or more positions, without significant cross-linking of the overall structure.

A suitable SRA is described, for example, in US Pat. No. 4,968,4, Nov. 6, 1990.
No. 51 (JJ Scheibel and EP Gosselink)
The sulfonation product of a substantially linear ester oligomer composed of an oligomer ester backbone of terephthaloyl and oxyalkyleneoxy repeating units and an allyl-derived sulfonation end moiety covalently bonded to the backbone, as described in US Pat. including. Such ester oligomers ethoxylate (a) allyl alcohol and (b) convert the product of (a) to dimethyl terephthalate ("DMT").
And 1,2-propylene glycol ("PG") by a two-stage transesterification / oligomerization procedure and (c) prepared by reacting the product of (b) with sodium metabisulfite in water. Can be. Other SRAs include U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 (Gosse).
link et al.) nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters such as poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG").
Such as those produced by transesterification / oligomerization of
Other examples of SRA include U.S. Pat. No. 4,721, Jan. 26, 1988.
No. 580 (Gosselink), ethylene glycol ("EG"),
Partially and fully anionic end-capped oligomeric esters such as PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; US Pat. No. 4,702,857, Oct. 27, 1987. (Goss
elink) nonionic capped block polyester oligomer compounds,
For example, DMT, methyl (Me) capped PEG and EG and / or P
G or a combination of DMT, EG and / or PG, Me-capped P
Produced from EG and Na-dimethyl-5-sulfoisophthalate; 1
U.S. Pat. No. 4,877,896, Oct. 31, 989 (Maldona)
dos, Gosselink et al.), especially the sulfoaroyl end-capped terephthalate esters, the latter being a typical SRA useful for both laundry and fabric conditioning products; Mention may be made of ester compositions made from sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising a PEG, for example PEG3400.

SRA also includes ethylene terephthalate or propylene terephthalate;
A simple copolyethylene oxide or propylene oxide terephthalate
Marlock (US Pat. No. 3,959,230, May 25, 1976)
(Hay) and U.S. Pat. No. 3,893,929, Jul. 8, 1975.
(See Basadur); available as METHOCEL from Dow
Cellulose derivatives such as pure hydroxyether cellulose polymers; C₁~ C ₄ Alkyl cellulose and C4 hydroxyalkyl cellulose (1976)
U.S. Pat. No. 4,000,093, Dec. 28, 2014 (Nicol et al.));
And the average degree of substitution (methyl) per unit of anhydrous glucose is about 1.6 to about 2.3.
And the viscosity of the solution measured with a 2% aqueous solution at 20 ° C. is about 80 to about 120 centipoise.
Of methylcellulose ether. Such materials are available from Shin-Etsu Chemical Co., Ltd.
METOLOSE SM100 and METH trade names of chilled cellulose ethers
Available as OLOSE SM200.

Further classes of SRAs include (I) nonionic terephthalates using diisocyanate coupling agents to crosslink the polymer ester structure (US Pat. No. 4,201,824 (Violland et al.) And US Pat. Patent No. 4,24
0,918 (Lagasse et al.)), (II) adding a trimellitic anhydride to a known SRA to convert the terminal hydroxyl group to a trimellitate ester to provide a carboxylate end group. SRA possessed. With the proper choice of catalyst, trimellitic anhydride will not open the anhydride bond,
An ester of the isolated carboxylic acid of trimellitic anhydride forms a bond at the end of the polymer. Nonionic or anionic SRAs may be used as starting materials if they have an esterifiable hydroxy end group. U.S. Pat. No. 4,525
, 524 (Tung et al.). Another class is (III)
There is a urethane-bonded anionic terephthalate SRA. US Patent 4,20
See 1,824 (Violland et al.).

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

[0213] A highly preferred composition comprises from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, in combination with a carbonate, a small amount (less than about 20% by weight) of a neutralizing agent, a buffer, a phase adjuster, a hydrotrope, an enzyme stabilizer, a polyacid, a foam adjuster,
Opacifiers, antioxidants, bactericides may be present.

Form of Composition The composition of the present invention can be prepared by various methods including dry mixing, agglomeration, compression or spray drying, or a combination thereof of various compounds contained in detergent components. Can be.

The compositions can be in various physical forms, including liquids, but are preferably in solid form, such as tablets, flakes, tablets, and bars, and are preferably in granular form.

The compositions according to the present invention can also be used in combination with bleach additive compositions containing, for example, chlorine bleaches.

Example 1 The following speckle particles are preferred speckle particles of the present invention.

The crude sodium citrate dihydrate ex ADM is mixed with the Monastral Blue BV paste solution in a mixing drum by spraying the dye paste solution onto a drum containing sodium citrate particles. When the colored particles are dried, speckle particles containing 1000 ppm of the dye are obtained.

Measurement: Sodium citrate dihydrate crystals with Monastral blue dye
The following results were obtained when measured by the method described in this specification. Sparkle index = 10.4% Transparency value = 22% Delta saturation = 120 Sodium citrate dihydrate crystals with Pigmasol green dye
The following results were obtained when measured by the method described in this specification. Sparkle index = 10.1% Transparency value = 22% Delta color saturation = 63

Abbreviations Used in Granular Detergent Composition Examples In the detergent composition, the meanings of the abbreviations of the components are as follows. LAS: sodium linear C11-13 alkyl benzene sulfonate TAS: sodium tallow alkyl sulfate CxyAS: sodium C1x-C1y alkyl sulfate C46SAS: sodium C14-C16 secondary (2,3) alkyl sulfate CxyEzS: condensed with z moles of ethylene oxide C1x-C1y sodium alkyl sulfate CxyEz: C1x-C1y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS: R2. N + (CH3) 2 (C2H4OH), R2 = C12-C14 QAS1: R2. N + (CH3) 2 (C2H4OH), R2 = C8-C11 APA: Amidopropyldimethylamine of C8-C10 Soap: Chain alkyl sodium carboxylate derived from a mixture of tallow and coconut fatty acid 80/20 STS: Sodium toluenesulfonate CFAA: (coconut) alkyl N-methylglucamide of C12-C14 TFAA: alkyl N-methylglucamide of C16-C18 TPKFA: Top-hole cut fatty acid of C12-C14 STPP: Sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: hydrated sodium aluminosilicate of the formula Na12 (AlO2SiO2) 12.27H2O with a primary particle size of 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6: formula δ-Na2 Crystalline layered silicate of i2O5 Citric acid: anhydrous citric acid Borate: sodium borate carbonate: anhydrous sodium carbonate having a particle size of 200 μm to 900 μm Bicarbonate: anhydrous sodium bicarbonate silicate having a particle size distribution of 400 μm to 1200 μm : Amorphous sodium silicate (SiO 2: Na 2 O = 2.0: 1) sulfate: anhydrous sodium sulfate magnesium sulfate: anhydrous magnesium sulfate citrate: tricitrate with an activity of 86.4% having a particle size distribution of 425 μm to 850 μm Sodium dihydrate MA / AA: 1: 4 maleic / acrylic acid copolymer with average molecular weight of about 70,000 MA / AA (1): 4: 6 maleic / acrylic acid copolymer with average molecular weight of about 10,000 AA: average molecular weight 4,500 sodium polyacrylate polymer CMC: Nato Lithium carboxymethyl cellulose Cellulose ether: Methyl cellulose ether with a polymerization degree of 650 available from Shin-Etsu Chemical Protease: NOVO Industry A / S under the trade name Savinase
3.3% by weight of proteolytic enzyme, sold by Protease I: Genecor Int. Sold by the company, WO 95
4. Proteolytic enzyme alcalase of 4% by weight of active enzyme described in the specification of US Pat. No. 5,105,91: Active enzyme sold by NOVO Industries A / S
3% by weight of proteolytic enzyme Cellulase: Active enzyme sold by NOVO Industries A / S under the trade name Carezyme 0.23% by weight of cellulase degrading enzyme Amylase: Sold by NOVO Industry A / S under the trade name of Termamyl 120T Active enzyme 1.6% by weight amylase-degrading enzyme Lipase: 2.0% by weight of active enzyme, lipase-degrading enzyme lipase (1) sold by NOVO Industries A / S under the trade name Lipolase (1): Lipolase Ultra Active enzyme sold by NOVO Industry A / S under the trade name 2.0% by weight of lipase-degrading enzyme Endase: Active enzyme sold by NOVO Industry A / S
5% by weight of endoglucanase enzyme PB4: particles containing sodium perborate tetrahydrate of the general formula NaBO2.3H2O, having a weight average particle size of 950 microns and 85% of particles having a particle size of 850
Microns to 950 microns PB1: General formula NaBO2. Particles containing anhydrous sodium perborate bleach of H 2 O 2 having a weight average particle size of 800 microns and 85% of particles having a particle size of 75
0 micron to 950 micron percarbonate: particles containing sodium percarbonate of the general formula 2Na2CO3.3H2O2, having a weight average particle size of 850 microns and 85% of particles having a particle size of 750 to 950 microns NOBS: sodium salt form NAC-OBS: particles containing (6-nonamidocaproyl) oxybenzenesulfonate, having a weight average particle size of 825 microns to 875 microns. TAEDI: particles containing tetraacetylethylenediamine, weight average particle size of 700 to 1000 microns TAEDII: tetraacetylethylenediamine, particle size of 150 to 600 microns DTPA: di Tylenetriaminepentaacetic acid DTPMP: diethylenetriaminepenta (methylenephosphonate) commercially available from Monsanto under the trade name Dequest 2060 Photoactive bleach: bleach (1) Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Photoactive bleach Agent: Bleach (2) Sulfonated aluminophthalocyanine encapsulated in dextrin-soluble polymer Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Brightener 2: 4,4'-bis (4 -Anilino-6-morpholino-1,3,5-triazin-2-yl) aminostilbene-2,2'-disulfonate disodium EDDS: ethylenediamine-N, N'-disuccinic acid in the form of its sodium salt,
S, S) isomer HEDP: 1,1-hydroxyethanediphosphonic acid PEGx: polyethylene glycol having a molecular weight of x (usually 4,000) PEO: polyethylene oxide having an average molecular weight of 50,000 TEMPE: tetraethylenepentamine ethoxylate PVI: Polyvinylimidazole having an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer having an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer having an average molecular weight of 50,000 PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole having an average molecular weight of 20,000 QEA: Bis ((C2H5O) (C2H4O) n) (CH3) -N + -C6H1
2-N +-(CH3) bis ((C2H5O)-(C2H4O)) n, n = 20-
30 SRP1: Anionic end-capped polyester SRP2: Diethoxylated poly (1,2 propylene terephthalate) short block polymer PEI: Polyethyleneimine having an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen of 7 Silicone defoaming Agent: Polydimethylsiloxane suds suppressor to which siloxane oxyalkylene copolymer is added as dispersant in a ratio of suds suppressor to dispersant 10: 1 to 100: 1 Opacifier: BASF Actiengezelshaft under the trade name Lytron 621 Commercially available aqueous monostyrene latex mixture Wax: paraffin wax Speckle: prepared in Example 1 In the following examples, all concentrations are given in weight percent of the composition.

[0221]

[Table 1]

[0222]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/20 C11D 3/20 3/22 3/22 3/37 3/37 11/00 11/00 17 / 06 17/06 (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, CR , CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, K Z, 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) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) ) Inventors Stephen, Patterson Washington, UK, Oxcross, Berwick, 36 (72) Inventors Judit, Esther, Jansen, UK -Castle, Appon, Tyne, Harton, Shaftsbury, Grove, 27F term (reference) EB25 EB28 EB30 EB34 EB36 EB38 EB41 EB42 EC01 EC02 EC03 EE05 EE10 FA09 FA12 FA14 FA41

Claims (15)

[Claims] 1. A cleaning composition speckle particle comprising a solid material colored by a colorant, wherein the particle has a sparkle index of at least 5% and a transparency index of at least 5%. Particle. 2. The cleaning composition speckle particles according to claim 1, having a color saturation of at least 10, preferably of at least 30, a sparkle index of at least 15% and a transparency index of at least 15%. 3. A colored crystalline material, preferably selected from the group consisting of crystalline hydrate salts, crystalline acids, crystalline acid salts, crystalline surfactants, carbohydrates or mixtures thereof. The cleaning composition speckle particles according to claim 1 or 2, wherein 4. The speckle particles according to claim 1, which are colored with a dye, a pigment, and / or a brightener. 5. The crystalline material is a hydrated sulfate, hydrated carbonate, hydrated phosphate, hydrated magnesium salt, crystalline carboxylic acid or a salt thereof, crystalline silicate, crystalline polymer polycarboxylic acid. The speckle particles according to any one of claims 1 to 4, comprising a salt thereof, a crystalline surfactant, a saccharide, preferably a saccharide, or a mixture thereof. 6. The method of claim 1, wherein the crystalline material comprises sodium citrate dihydrate.
The speckle particles according to any one of the above. 7. The speckle particles according to claim 1, further comprising a binder. 8. The weight average particle size is between 300 microns and 2000 microns, preferably 50 microns.
Speckle particles according to any of the preceding claims, wherein the particles are between 0 microns and 1400 microns, more preferably between 600 microns and 1180 microns. 9. A step of spraying a colorant into a mixing container containing the solid material, preferably a crystalline material; a step of mixing the colorant with the speckle particles; Drying the colored cleaning composition speckle particles. 10. The method of claim 9, wherein the speckle particles comprise a crystalline material and a binder, wherein the speckle particles are preferably in the form of an aggregate. 11. A cleaning composition comprising speckle particles according to claim 1, wherein the cleaning composition has a concentration of 0.05% to 30% by weight. 12.) a step of coloring the solid material with a colorant to obtain colored speckle particles, preferably by spraying a colorant onto a mixing drum containing the speckle particles, and b) optionally Drying the colored speckle particles obtained in step b), and c) mixing the colored speckle particles of step a) or b) with other components of the cleaning composition. The composition according to claim 11, which comprises colored speckle particles and other components obtained by a production method comprising: 13. A solid laundry or dishwashing detergent composition, preferably a granule composition, an extrusion composition or a tablet composition, preferably comprising a surfactant, an enzyme, a bleach activator, a cellulose derivative or a mixture thereof. 12. A particle comprising:
Or the composition according to 12. 14. Use of speckles in a cleaning composition according to any one of claims 1 to 8, which gives a contrast appearance to the other components of the composition. 15. Use of speckles in a cleaning composition according to any one of claims 1 to 8, which masks undesired colors of other detergent components.