SK83693A3 - Peroxyacid bleach precursor compositions - Google Patents

Abstract

Solid peroxyacid bleach precursor compositions are provided in which the external surfaces of a particulate peroxyacid precursor material is treated with from 2 % to 20 % by weight of a solid organic acid compound of Mpt > 30 DEG C and an aqueous solubility of at least 5g/100g water at 20 DEG C. The bleach precursor material, when so treated, perhydrolyses after 3 minutes in a standard test at 20 DEG C, to at least 90 % of the extent of the untreated bleach precursor material under the same conditions. Preferred organic acid compounds are monomeric aliphatic hydroxycarboxylic and polycarboxylic acids such as citric, lactic and glycolic acids. Detergent compositions containing the treated peroxyacid bleach precursor particulates are also disclosed.

Description

Technical field

The present invention is directed to solid peracid-based bleach precursors, and in particular particulate soaking compositions containing inorganic persistent bleaching agents together with peracid-based bleach precursors containing an N- or O-acyl group (as well as bleach activators). ).

These compositions have been widely used in recent years as high-performance fabric cleaning products, especially in automatic washing machines. Growth in the use of bleaching

Λ activators reflect a decrease in wash temperatures, which is accompanied by an increase in the proportion of substances that are colored.

One problem that is becoming more significant as a result of these tendencies is the deterioration of the colors of the substances and materials that occurs by localized high concentrations of bleaching agents. A high concentration of bleach is formed around any of the bleaching agent particles of several l

reasons. Bleaching agents themselves may have a considerably low solubility, their solubility may be reduced by the presence of other materials, such as viscous surfactant phases, or a mixing regime in the immediate vicinity of the bleach particles may not be sufficient to do so.

to disperse the dissolved bleach.

When the bleach activator is a component of the composition.

the potential problem is increasing. In addition to the potential of localized high peroxide ion concentrations resulting from the dissolution of the inorganic peroxide normally included in detergent detergents, hydrolysis of the bleach activator to form percarboxylic anions leads to significant localized concentrations of percarboxylate bleach.

The development of so-called concentrated products and their dosing by means of devices placed in the machine drum together with the fabric filling only leads to aggravation of these problems. Accordingly, there is a need for soaking compositions which contain a bleach activator in a form that minimizes and preferably eliminates deterioration of the colors of materials and materials during its dissolution and hydrolysis to peroxylates in the wash water.

BACKGROUND OF THE INVENTION

The literature contains many cases of bleach activators coated or agglomerated so as to increase their storage stability in soaking compositions and / or to affect their dissolution behavior.

European patent application no. 0070474 discloses granulated bleach activators made by spray drying an aqueous pumpable dispersion comprising an N-acyl or O-acyl compound together with at least one water-soluble cellulose ether, starch or starch derivative in an activator to coating weight ratio of from 98: 2 to 90: 10 .

British patent application no. No. 1507312 describes the coating of bleach activators with a mixture of fatty acid salts of 8 to 22 carbon atoms with the corresponding fatty acid. 1381121 uses a molten coating, inter alia, a mixture of C14-C18 fatty acids to protect solid bleach activators. British Patent Application No. 1,414,116 describes a similar process in which a mixture of C 12 -C 16 fatty acids and C 10 -C 20 aliphatic alcohols is used. European patent application no. No. 0375241 discloses stabilized bleach activator prints in which C5 -C18 alkyl percarboxylic acid precursors are mixed with a binder selected from anionic and nonionic surfactants, film-forming fatty acid polymers, or a mixture of such binders.

European Patent Application No. 0356700 to increase problems. Accordingly, there is a need for soaking compositions which contain a bleach activator in a form that minimizes and preferably eliminates deterioration of the colors of materials and materials during its dissolution and hydrolysis to peroxylates in the wash water.

I

BACKGROUND OF THE INVENTION

The literature contains many instances of bleach activators coated or agglomerated to be

increased their stability at storage in means on the soaking and / or making It was affected their behavior at dissolution. European partner registration no. 0070474 describes

granulated bleach activators made by spray drying an aqueous pumpable dispersion comprising an N-acyl or O-acyl compound together with at least one water-soluble cellulose ether, starch or starch derivative in an activator to coating weight ratio of from 98: 2 to 90: 10.

British patent application no. No. 1507312 describes the coating of bleach activators with a mixture of fatty acid salts of 8 to 22 carbon atoms with the corresponding fatty acid. British Patent Application No. 1381121 uses a molten coating inter alia with a mixture of fatty acids of 14 to 18 carbon atoms to protect solid bleach activators. British Patent Application No. 1,414,116 describes a similar process in which a mixture of C 12 -C 16 fatty acids and C 10 -C 20 aliphatic alcohols is used. European patent application no. 0375241 discloses stabilized bleach activator prints in which C5 -C18 alkyl percarboxylic acid precursors are mixed with a binder selected from anionic and nonionic surfactants, film-forming fatty acid polymers, or a mixture of such binders.

European Patent Application No. 0356700 to increase with tab

The ease of dispersion / solubility is described in carboxylic acid or hydroxycarboxylic acid water by carbon atoms. Carboxylic acid.

an acid such as citric acid is followed by the activator and then the granules are wound

Citric acid gives an increased multi-linking acid with a 3 to a preferred example of dryness mixed with a bleaching polymer forming a film.

the dissolution rate of the bleach activator granules.

European patent application no. 0382464 is concerned with a process for coating or encapsulating solid particles capsules containing bleaching compounds and bleach activators to form a melt coating material in which the particles form a dispersible phase. This melt is destabilized.

it is crushed into pieces, the phases are embedded in a continuous variety of coating materials. For example, polyacrylic acid is said to be a useful compound of the material, depending on the pH.

wherein the particles of the dispersed (coating) phase. Certain materials such as cellulose acetate phthalate and others are described. Release of the upholstery

Thus, the overall emphasis in the literature has been to protect the bleach activator from the host environment during storage. Relatively little attention was paid to the dissolution properties of the coating or agglomerated material. If poorly soluble materials such as fatty acids have been designed for coating and / or agglomeration, the result was that the rate of hydrolysis of the bleach activator to peroxy forms (i.e., perhydrolysis) was lower than if such protection did not exist. Any use of faster soluble materials, such as citric acid, has led to a more rapid dissolution of the bleach activator in relation to the agglomerated component. In both cases, since peroxylate hydrolysis begins as the soaking product begins to dissolve to form an alkaline hydrogen peroxide solution concentrations of peroxyacid bleach remain unresolved.

One solution to these problems would be to delay the onset of hydrolysis to the peroxylocs in order to circumvent the color deterioration problems associated with the dissolution behavior of the other components of the soaking product. However, it is important that the hydrolysis of the bleach precursor to the peroxy components and the subsequent dispersion of the percarboxylate bleach should be as rapid as possible as soon as it starts, due to the short washing time in modern automatic washing machines.

The current satisfactory solution to these two problems has not been described in the literature to date.

It is known that the rate of perhydrolysis of a percarboxylic acid-based bleaching agent in an aqueous oxidizing medium decreases progressively as the pH of the environment decreases, particularly if the pH drops below the pK® of the respective precursor leaving group. However, the fatty acids referred to as coating agents in the scientific literature are not useful as agents that cause low pH in an aqueous wash liquid because they are insoluble. In addition, it has been found that fatty acids which have been used as coating and / or agglomerating agents for peracid-based bleach precursors reduce the rate of hydrolysis of the bleach precursors to the peroxy compounds and thereby reduce the efficiency of the final percarboxylic acid-based bleach.

Surprisingly, the applicant has now found that these acidic materials having certain specific properties can be used to treat the surface of peroxyacid-based particulate bleach precursors, delaying the onset of hydrolysis to the peroxy compounds during product dissolution under forced mixing conditions of the loaded machine drum without hydrolysis to persistent compounds has been adversely prevented when it occurs.

SUMMARY OF THE INVENTION

According to the present invention, a solid bleaching agent is obtained

a precursor composition based thereon;

comprising a particulate peroxyacid bleach precursor material, wherein the precursor comprises one or more N- or O-acyl groups and has a melting point greater than 30 ° C, the outer surfaces of said peracid-based pure bleach precursor material are treated with an organic compound % of an acid so that said compound adheres to the outer surfaces, said compound being present in an amount of from about 2% to 20% by weight of the treated particle.

the organic acid compound has a water solubility of at least g / 100 g water at 20 ° C and a melting point greater than 30 ° C, wherein the treated particulate bleach precursor material yields at least 90% peracid after 20 minutes in a 20 ° C beaker perhydrolysis test compared to the respective particulate bleach precursor material in the unworked state under the same conditions.

Preferably, the organic acid compound used is a monomeric or oligomeric carboxylate having a water solubility of at least 20 g / 100 g water at 20 ° C. The most preferred such compound is a monomeric aliphatic carboxylic acid with a very high solubility and a melting point greater than 40 ° C.

For the purposes of the present invention, it is important that the outer surfaces of the peroxygen bleach precursor particle, whether in the form of individual particles or agglomerates, be treated so that the organic acid compound adheres to the surfaces. By this treatment, the compound can be obtained in the form of a continuous or discontinuous coating or as masses of the acid compound dispersed on the surface of the particles or as individual particles that are randomly available on the surface. It is a requirement that the treated surface material be readily available upon contact with the aqueous environment so that it rapidly dissolves to form an acidic pH environment around the outside of the bleach precursor particle. Therefore, incorporation of an organic acid compound as an agglomerating agent dispersed within a peracid-based bleach precursor particle is not preferred according to the present invention. This is because, under the conditions of dissolution of the concentrated granular laundry detergent, especially when dosed into the drum of the washing machine by means of a dosing device, an agglomerated but not coated peroxyacid bleach precursor hydrolyzes a substantial portion to the percarbonate and generates high concentrations bleaches leading to local damage to the substance.

The peroxyacid-based solid bleach precursors of the present invention contain precursors having one or more N-O-acyl groups, which precursors may be selected from a variety of classes of substances. Suitable classes of substances include anhydrides, esters, imides, and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in British patent application no. 1586789. The most preferred classes are esters, such as those described in English patent applications no. 836,988, 1,147,871, and 2,143,231, and imides such as those described in U.S. Patent Application Ser. 855735 and no. 1,246,338th

Specific O-acylated precursor compounds include 2,3,3-trimethylhexanoyloxybenzenesulfonates, benzyloxybenzenesulfonates, and pentaacetyl glucose.

Particularly preferred precursor compounds are

N, N, N ¹ , N ¹ -tetraacetylated compounds having the general formula

ABOUT

II

CH ₃ -C CH ₃ -C

G o

about

II

N- _(CH2) x

wherein x denotes a number zero or a number from 1 to 6.

Examples include tetraacatylmethylenediamine (TAMD) in which x denotes the number 1, tetraacetylethylenediamine (TAED) in which x denotes the number 2, and tetracetylhexylenediamine (TAHD) in which x denotes the number 6. These and analogous compounds are described in the British patent application no. 907,356th

The most preferred peracid-based bleach precursor is TAED.

The peracid-based solid bleach precursors useful in the present invention have a melting point greater than 30 ° C, preferably greater than 40 ° C. Such precursors will normally be in powder form or in crystalline form, wherein at least 90% by weight of the powder has a particle size of greater than 150 microns.

The surface of the powder can be treated directly, but more typically it is agglomerated prior to surface treatment to form particulate material, at least 85% having a particle size of between 400 and 1700 microns. Suitable agglomerating agents include C12-18 fatty acids, C12-18 aliphatic alcohols condensed with 10-80 moles of ethylene oxide per mole of alcohol, cellulose derivatives such as methyl, carboxymethyl and hydroxyethylcellulose, polyethylene glycols having a molecular weight of 4 000 to 10,000 and polymeric materials such as polyvinylpyrrolidone.

The agglomerated particulate precursor material itself does not provide the advantages of the invention, but is the preferred form of the precursor to which the organic acid compound is applied during surface treatment.

The organic acid compound must meet several criteria. First, it must be solid at room temperature and have a melting point of at least about 30 ° C, preferably at least about 40 ° C.

Preferred organic acid compounds have a melting point above

50 ° C.

Second, the organic acid compound must be very soluble in water at room temperature. The term "very soluble" according to the present invention indicates that at least 5 < 5 acids are dissolved in 100 grams of distilled water at 20 ° C. Preferably, the organic acid compound has a solubility of at least about 20 g / 100 g water at 20 ° C, most preferably the organic acid compound is dissolved in an amount equal to the amount of water in which it dissolves at 20 ° C.

Thirdly, the organic acid compound should have no more than little effect, preferably substantially no effect, on the perhydrolysis rate of the peracid-based bleach precursor under conditions of good mixing. For purposes of this invention, good mixing conditions are defined as those detailed in the above beaker perhydrolysis test. A material having greater than little effect on the precursor perhydrolysis rate is defined for the purposes of the present invention as a material which, after three minutes in a 20 ° C beaker perhydrolysis test, allows at least 90% peracid to be prepared under the same conditions. of unbleached bleaching material. The rates of hydrolysis to the persecuted material of the treated and untreated material are preferably the same.

Organic acid compounds useful as processing agents of the present invention include aliphatic or aromatic monomeric or oligomeric carboxylates, preferably monomeric aliphatic carboxylic acids. Examples of such aliphatic acid compounds include glycolic, glutamic, citraconic, succinic, 1-lactic and citric acid. These acids are applied in amounts of from 2 to 20% by weight of the treated particle, more preferably from 2 to 15% by weight and most preferably from 3 to 10% of the treated particle. A particularly preferred surface treating agent is glycolic acid in an amount of about 5 weight percent of the treated particle.

Treatment of the surface of the bleach precursor particle ΐΰ with an organic acid compound can be accomplished in several ways. This procedure is not critical to the present invention.

The organic acid compound can be sprayed as a molten material or as a solution or dispersion in a solvent (carrier liquid, which is then subsequently removed by evaporation).

The organic acid compound can also be applied as a powder coating, for example by electrostatic methods, although these methods are less preferred because the adhesion of the powder coating material is more difficult to achieve and can be more expensive.

Melt coating is a preferred method for organic acid compounds with a melting point below 80 ° C, such as glycolic acid or 1-lactic acid. However, this coating method is less preferred for acids with a higher melting point (e.g., greater than 100 ° C), such as citric acid. For compounds having a melting point above 80 ° C, spraying in the form of a solution or dispersion is preferred. Organic solvents such as ethyl alcohol and isopropyl alcohol can be used to form solutions or dispersions, although their use requires a step in which the solvent is regenerated to make them economical to use. However, the use of organic solvents also causes safety problems such as flammability and worker safety. Thus, aqueous solutions or dispersions are preferred.

Aqueous solutions are particularly advantageous if the organic acid compound has high water solubility (e.g. citric acid) and the solution has a sufficiently low viscosity to be used. Preferably, a concentration of at least 25 weight percent of the organic acid compound in the solvent is used to reduce the drying / evaporation of the charge after surface treatment. The processing apparatus may be any apparatus that is normally used for this purpose, such as inclined rotary ladles, rotary drums and a fluidized bed.

ii

The solid peracid bleach precursor compositions of the present invention may take a variety of physical forms. Thus, surface-treated peracid bleach precursor particles can be incorporated into other solid compositions such as tablets, extrudates and agglomerates. These particles may also be suspended in non-aqueous liquid compositions in which the surface of the material treated with the organic acid is insoluble and inert. A preferred application of the persistent bleach-based solid bleach precursor compositions of the present invention is the particulate granular soaking compositions, in particular the so-called concentrated soaking compositions, which are metered into the washing machine by means of a device located in the laundry drum. Concentrated granulated soaking compositions placed in the wash water in the dispenser are more sensitive to dissolution problems compared to the compositions added by the dispenser dispenser, since at the beginning of the entire wash cycle, mixing in the immediate vicinity of the product is inhibited by the presence of a fabric load. While this has the advantage of allowing high intermediate concentrations of the components and surfactant to occur, the formation of high intermediate concentrations of peracids can, as mentioned above, cause damage to the substance and colors. The coated peracid-based bleach precursor particles of the present invention, when added to concentrated soaking products applied to the wash water by the delivery device, alleviate, if at all, the problem.

The soaking compositions comprising the peracid-based bleached precursor particles with a treated surface will normally contain from 0.5% to 10% precursor, more typically from 1% to Q%, and most preferably from 2% to 6% of the precursor based on the weight of the composition. .

Such soaking compositions will, however, comprise a source of the alkaline hydrogen peroxide necessary to form peracid particles in the wash solution. Preferably they will

12 also contain other conventional ingredients for the soaking compositions. Preferred soaking compositions will include one or more surfactants, organic or inorganic components, soil suspending agents, anti-deposition agents, suds suppressors (enzymes), enzymes, fluorescent whitening agents, photoactivating whitening agents, perfumes and the like. dye.

The soaking compositions comprising the surface treated peracid precursor particles of the present invention will contain inorganic peroxygen bleaches, normally in the form of an aqueous salt, as a source of alkaline hydrogen peroxide in the laundry liquid. These peroxide agents are normally present at from 3% to 22% by weight, more preferably from 5% to 20% by weight, and most preferably from 8% to 18% by weight of the composition.

The peroxide reagent may be an inorganic salt such as a perborate, percarbonate, persulfate, and perborate salt, preferably an alkali metal perborate or percarbonate. Although the color deterioration of the substance of the compositions of the invention is low, regardless of whether a perborate or percarbonate salt is used, the improvement over uncoated precursor particles is more noticeable with the percarbonate bleach, since this bleach causes greater color deterioration in the absence of any coating. on a whitening precursor.

Another compound that is a preferred peroxide agent is sodium percarbonate having the formula 2 Na 2 CO 3. 3H2 O2. This material is commercially available as a crystalline solid. Among the commercially available materials involved in the production process are small amounts of heavy metal scavengers such as EDTA, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP) or aminophosphonate. For the purpose of using the soaking compositions of the present invention, the percarbonate may be included without further protection from the soaking compositions. However, they use coated forms of this material as preferred formulations. While a variety of coatings may be used, the most economical is sodium silicate SiCl 2: NaO in a ratio of 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to obtain an 2% to 10% (normally from 3% to 5 solid silicate by weight of percarbonate. Magnesium silicate may also be included in the coatings.

The particle size of the crystalline percarbonate ranges from 350 microns to 450 microns with a mean value of about 400 microns. After coating, the crystals range in size from 400 to 600 microns.

Although the presence of heavy metals in the sodium carbonate used to produce the percarbonate can be controlled by adding traps to the reaction mixture, the percarbonate still requires protection from the heavy metals present as impurities in other product components. Soaking compositions which use a percarbonate as a peroxide salt should not contain more than 25 ppm, preferably less than 20 ppm of iron, copper and magnesium ions to avoid unacceptable adverse effects on the percarbonate stability. Soaking compositions in which the alkali metal percarbonate bleach has increased stability are described by the Applicant in the accompanying patent application no. 9021761.3 (representative document CM343).

A variety of surfactants can be used in the soaking compositions. A typical list of anionic, nonionic, ampholytic, and zwitterionic classes and types of these agents is set forth in U.S. Pat. No. 3,929,678 to Laughlin and Heuring of December 30, 1975. A list of suitable cationic surfactants is disclosed in U.S. Pat. No. 4,259,217 to Murphy of March 31, 1981.

Mixtures of anionic surfactants are suitable, in particular mixtures of sulphate, sulphate and / or carboxylate surfactants. Mixtures of sulfonate and sulfate surfactants are normally used such that the weight ratio of sulfonate to sulfate is from 5 to 1: 2, preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1.

Preferred sulfonates include alkylbenzenesulfonates of 9 to 15, in particular 11 to 13 carbon atoms in the alkyl group, and alpha-sulfonated methyl esters of fatty acids in which the fatty acid is derived from a fatty moiety of 12 to 18 carbon atoms, preferably of 16 to 18 carbon atoms. carbon atoms. In any case, the cation is an alkali metal, preferably sodium. Preferred sulfate surfactants are those wherein the sulphonate sulfate mixtures form alkyl sulfates having 12 to 22, preferably 16 to 18, carbon atoms. Another useful surfactant system comprises a mixture of two alkyl sulfate materials having different mean chain lengths. One such system comprises a mixture of 14 to 15 carbon atoms of alkyl sulfate and 16 to 18 carbon atoms of alkyl sulfate in a weight ratio of 3 to 1: 1. Alkyl sulfates may be combined with alkyl of 10 to 20 carbon atoms, preferably 10 to 10 carbon atoms. The cation is, in all cases, again an alkali metal, preferably sodium.

Other anionic surfactants suitable for use herein are alkali metal sarcosinates having the general formula:

R-CON (R) _CH2 COOM, wherein R denotes a linear or branched alkyl or alkenyl having up to 17 carbon atoms,

R 'denotes an alkyl group of up to 4 carbon atoms and M denotes an alkali metal ion. Preferred examples are laurcyl, cocoyl (C12 -C), myristyl or oleyl-methyl sarcosinates in the form of their sodium salts.

Another class of nonionic surfactants useful in the present invention comprises the condensation products of ethylene oxide with a hydrophobic moiety provided that the surfactants have a hydrophilic to lipophilic moiety (HLB) ratio in the range of from 8 to 17, preferably from 9.5 to 9.5 13.5, more preferably 10 to 12.5. The hydrophilic (lipophilic) moiety may be aliphatic or aromatic in nature. The length of the polyoxyethylene group that is condensed with any particular hydrophobic group can readily be adjusted to give a water-soluble compound with the desired degree of ratio between hydrophilic and hydrophobic elements.

Particularly preferred nonionic surfactants of this type are primary alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per mole of alcohol, especially primary alcohols having 14 to 15 carbon atoms containing 6 to 8 moles of ethylene oxide per mole of alcohol and primary alcohols having 12 to 14 carbon atoms containing 3 to 5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds having the general formula:

B0 (C ₁₁ H ₂ n) 12 _x , in which

Σ denotes a group derived from glucose, R denotes a saturated hydrophobic alkyl group of up to 18 carbon atoms t denotes a number from 0 to 10, n denotes a number 2 or

3a x denotes a number from 1.3 to 4. These compounds contain less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in soaking compositions are described in European patents B0070074, 0070077, 0075996 and 0094118.

Another class of surfactants are semipolar surfactants such as aminooxides. Suitable amine oxides are selected from mono N-alkyl or alkenyl 1-amine oxides having 8 to 20 carbon atoms, preferably 10 to 14 carbon atoms, and propylene-1,3-diaminedioxides in which the other N positions are substituted with methyl, hydroxyethyl or hydroxypropyl group.

Cationic surfactants may be used in the soaking compositions of the invention. Suitable quaternary ammonium surfactants are selected from monoalkyl or alkenyl-ammonium surfactants having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, in which the other N positions are substituted by a methyl, hydroxyethyl or hydroxypropyl group.

The soaking compositions comprise from about 5% to about 20% surfactant, typically from about 7% to about 20%, more preferably from about 10% to about 15%, of the surfactant based on the weight of the composition.

Preferred are combinations of surfactants, especially mixtures of anionic-nonionic and also anionic-nonionic-cationic surfactant. Extremely preferred combinations are described in British patent application no. 2040987 and European patent application no. While surfactants may be included in the compositions as mixtures, it is preferable to control the addition point of each surfactant in order to optimize the physical properties of the composition and to avoid processing problems. Preferred methods and order of addition of surfactants are described herein below.

Another highly preferred component of the soaking compositions incorporating the coated peracid-based precursor particles of the present invention is a soaking component system comprising one or more nonosiolate soaking components. These include, but are not limited to, carbonates, bicarbonates, silicates, aluminosilicates, alkali metal monomeric polycarboxylates, mono or copolymeric polycarboxylic acids, or salts thereof, in which the polycarboxylic acid contains at least two carboxyl groups separated from each other two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates) -and mixtures of any of the foregoing components, this component system is present in an amount of from 25 to 60% by weight of the composition, preferably from 30 to 60% by weight.

Preferred component systems do not contain boron compounds, and any polymeric materials are preferably biodearable.

Suitable silicates are those for which the ratio of silica to sodium oxide is in the range of 1.6 to 3.4, are preferred. so-called amorphous silicates having this ratio preferably from 2.0 to 2.8. These materials can be added at various points in the manufacturing process, such as in a slurry of the components that are spray dried, or in the form of an aqueous solution that acts as an agglomerating agent for other solids, or, if the silicates themselves are in particulate solid materials to other particulate components of the composition. For compositions having a percentage of spray-dried components low, i. 30%, it is preferable to include this amorphous silicate as a spray-dried component.

From the group of silicates, crystalline layered sodium silicates having the general formula:

NaMSi-zOsx + iyHzO, in which M denotes a sodium or hydrogen atom, x denotes a number from 1.9 to 4 and y denotes a number from 0 to 20. Crystalline layered sodium silicates of this type are described in European patent application no. Processes for their preparation are described in German Patent Application Ser. For the purposes of this invention, x denotes 2,3 or 4, preferably 2, in the above general formula. M more preferably denotes sodium and y is 0. Preferred examples of this formula include the forms NazSizOs. materials are available from Hoechst AG, SP.N as NaSKS-11 and NASKS-6. The most preferred material is NazSizOs (NaSKS-6).

Crystalline layered silicates are present here or as dry mixed solids or as solid components of agglomerates with other components.

Of the group of hl-silicone ion exchanger materials that may be used, sodium aluminosilicate zeolites with a unit having the general formula are preferred:

Na _z [(AlO2) _z (S1O2) y]. xHz 0, wherein y denotes at least 6, the molar ratio of from 1.0 to 0.5 and x denotes at least 5, preferably 7.5 to 176, more preferably 10 to 264. The aluminosilicate materials are in hydrated form, preferably they are crystalline and contain from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aforementioned aluminosilicate ion exchange materials are further characterized in that they have a particle size diameter of from 0.1 to 10 microns, preferably from 0.2 to 2 microns. The term particle size diameter herein refers to the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques, such as a scanning electron microscope or a laser granulometer. The aluminosilicate ion exchange materials are further characterized by their capacity for exchanging calcium, which is at least 200 mg equivalents of calcium carbonate per gram aluminosilicate, calculated on the anhydrous materials, and which is typically in the range of 300 mg equivalents per g to 352 mg equivalents / g. The aluminosilicate ion exchange materials are further characterized by a calcium ion exchange rate of at least 130 mg equivalents calcium carbonate per liter (g / l) aluminosilicate (based on anhydrous substances) and which is typically in the range of 130 to 390 mg equivalents calcium carbonate per liter for minute, based on the hardness of the calcium ions.

Optimal aluminosilicates for the purposes of the components exhibit a calcium ion exchange rate of at least 260 mg equivalents of calcium carbonate per liter per minute.

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.

1'5

These may be naturally occurring materials, but are preferably derived from synthetic materials. A method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. Preferred synthetic crystalline HL initosilicate ion exchange materials useful in the present invention are available under the designation

Have a great time i o x x o

Zeolite

And,

Zeolite B,

X, Zeolite HS uses the name of the arrangement (they are commercial zeolite) and their crystalline names;

mixture.

In Czech, an extremely aluminosilicate material is used with zeolite A having the general formula

Nai from [(A1 Os) i 2 (Si O2) 1 2 1 xH ₂ 0, where x denotes a number from 20 to

30, in particular 27. Zeolite X having the formula

Our [(Al 2 O) θ e (S ₂ O ₂ ) io e] 276H ₂ O is also a suitable material.

as well as HS zeolite having the formula

Na «[(AlCh> 6 (SiO ₂ ) ₆ ]. 7.5Hz 0.

Suitable water-soluble monomeric or oligomeric carboxylate components can be selected from a variety of compounds. However, such compounds preferably have a first carboxylic acid logarithmic constant (pKi) of less than 9, preferably between 2 and 8.5, more preferably between 4 and 7.5.

The logarithmic acid constant is defined with respect to equilibrium

H ⁺ + A <==========> h ⁺ A, where A denotes the fully ionized carboxylate anion of the salt of the component.

Thus, the equilibrium constant is (H ⁺ A) (H *) (A) pKi = log 10K.

For purposes of this specification, acidity constants are defined at

25 ° C and at zero ionic strength. If possible, values from the literature are used (see Stability Constants of Metal-Ion

Complexes Special Publication No. 25, The Chemical Society,

London); if in doubt, they are determined by potentiometric titration using a glass electrode.

Preferred carboxylates can also be defined by the calcium ion stability constant (pKca ++), which is defined similarly to ρΚχ by the equations pKc and. + + ogi o K _c a + +, where (Ca ^{++ +} A)

Kc a. ^{+ +}

In particular, polycarboxylates have from about 3 to about (Ca ⁺⁺ ) pKc and.

Again (A) of a range of about 2, values up to about 7, constants are used.

stability of the literature, if possible. The constant is defined at 25 ° C and at zero ionic strength by the glass electrode measurement method as described in Complexation in Analytical

C gaming room

Anders

Ri ngboma (1963).

The carboxylate or carboxylate bed may be monomeric or oligomeric when monomeric polycarboxylates are generally preferred for cost and performance.

Monomeric and oligromeric building blocks of acyclic and 1-cyclic heterocyclic and aromatic (a)

Rx (b)

Y I c Ί

Y 1 x c 1 z n

or (c) wherein R 1 denotes

or a C 1 -C 30 alkenyl group optionally substituted by a hydroxyl group, a carboxy group.

a sulfo group or a phosphonium group or attached to a polyoxyethyleneoxy moiety containing up to 20 ethylene oxide groups,

R2 denotes a hydrogen atom, a (C1-C4) alkyl group, a (C1-C4) alkenyl group, a (C1-C4) hydroxyalkyl group.

an alkaryl group, a sulfo group or an ososion group,

X denotes a single bond, an oxygen atom, a sulfur atom, an SO group, an SO2 group or an NR1 group,

Y represents a hydrogen atom, a carboxy group, a hydroxyl group, a carboxymethyloxy group or an alkyl or alkenyl group having from 1 to 30 carbon atoms optionally substituted by a hydroxyl group or a carboxy group.

Z denotes a hydrogen atom or a carboxy group, m denotes a number from 1 to 10, n denotes a number from 3 to

6.

P and q denote numbers from 0 to 6, the sum of p + q denotes numbers from 1 to 6, or different meanings when repeated in said molecular formula, and at least one of the Y or Z groups in the molecule contains a carboxyl group.

Suitable carboxylates containing a single carboxyl group include lactic acid, glycolic acid and ether derivatives thereof, as described in Belgian patents Nos. 831 368, 821 369 and 821 370.

Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Patent Specification No. 5,938,549. 2,446,686 and 2,446,687; and U.S. Pat.

935,257 and the salt-inyl carboxylates disclosed in Belgian patent no. 840 623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates and conitrates and citraconates, as well as derivatives of antarboxylic acid, such as the carboxymethyloxysuccinates described in the British patent

no. 1 379

241, the lacto-succinates described in British patent

no. 1 389

732 and the aminosuccinates disclosed in the Dutch patent application

no. 7

205,873, oxypolycarboxylate materials.

such as the 2-oxa-1,1,3-propane tricarboxylates described in the British patent

no. 1,387,447.

Carboxypins, polycarboxylates, include U.S. Pat. 1 261 829

3-propanetetracarboxylates which oxydisuccinates contain four described in UK

1,1,2,2-ethanetetracarboxylates, 1,1,3, and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described herein

no. No. 1,398,422 and U.S. Pat. 3 pyrolyzed citrates disclosed in British patent British patent

936,448; 1 439 000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2, 2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyalcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the derivatives of melitic acid, pyromellitic acid, and phthalic acid, described in British Patent No. 5,960,549. 1,425,343.

Original monomeric or oligomeric acids

Of the above polycarboxylates, hydroxycarboxylates containing up to three carboxyl groups per molecule, in particular citrates, are preferred.

polycarboxylate chelating agents, or mixtures thereof with salts, for example citric acid or citrate / citric acid, can also be considered as builders of the soaking compositions of the present invention.

Other water-soluble organic salts are homoa co-polymeric polycarboxylic acids or salts thereof, in which the polycarboxylic acid contains at least two carboxyl groups separated by no more than two carbon atoms. Polymers of the latter type are described in British patent application no. Examples of these salts are polyacrylates having a molecular weight of 2,000 to 5,000 and their copolymers with maleic anhydride, such as copolymers with a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used in amounts of from 0.5 to 10% by weight, more preferably from 0.75 to 8%, most preferably from 1 to 6% by weight of the composition.

Organic phosphonates and aminoalkylene polyols (alkylene phosphonates) include alkali metal ethane-1-hydroxy-diphosphonates, alkali metal nitrilo-trimethylene phosphonates, alkali metal ethylene diamine-tetramethylene phosphonates and diethylenetriaminepentamethylene phosphonates, where the preferred alkali metal materials are less preferred, minimizing phosphorus compounds in the compositions.

For the purpose of the soaking compositions comprising the surface treated bleach precursor particles of the invention, the non-phosphate builder component will contain from 25% to 60% by weight of the composition, more preferably from 30% to 60% by weight. In preferred compositions, the sodium aluminosilicate, such as zeolite A, is included in an amount of from 20% to 60% by weight of the total component, monomeric or oligomeric carboxylate from 10% to 30% by weight of the total component, and crystalline layered silicate. 10% to 65% by weight of the total amount of the component. In these compositions, the component will preferably contain a combination of inorganic and organic auxiliary components such as sodium carbonate and maleic anhydride / acrylic acid copolymers in amounts up to about 35% by weight of the total amount of the component.

Suitable soil release agents and soil suspending agents include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or salts thereof. Polymers of this type include copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride representing at least 20 mole percent of the copolymer. These materials are normally used in amounts of from 0.5 to 10% by weight, preferably from 0.75 to 8%, most preferably from 1 to 6% by weight of the composition.

Other useful polymeric materials are polyethylene glycols, especially polyethylene glycols having a molecular weight of 1,000 to 10,000, in particular 2,000 to 8,000, most preferably about 4,000. These polymeric materials are used in amounts of from 0.20% to 5%, more preferably from 0% to 5%. 25% to 2.5% by weight. These polymers and the aforementioned homo- or co-polymeric polycarboxylate salts are priced to improve whiteness retention, textile ash deposition, clay purification, protein or oxidizable contamination in the presence of transition metal contaminants.

Preferred optical brighteners are anionic in nature. For example, they are 4.4¹bis (2-dietanolarnino-4-anilino-s-triaζίη-6-ylamino) stilbene-2: 2¹disodium disulphonate, 4.4¹-bis- (2-morpholin-4-anilino-2-triazol-6-ylamino) stilbene-2: 2¹ -disul f o sodium disodium, 4,4¹bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2: 2¹disodium disulfonate, 4.4^{1 1}Sodium bis (2,4-dianilinosin-triazin-6-ylamino) stilbene-2-sulfonate, 4,4^r-bis- (2-amino-4- (N-methyl-N-2-hydroxyethylamino) -2-triazin-6-ylamino) stilbene-2,2¹disodium disulfonate, 4.4¹-bis- (4-phenyl-2,1,3-triazol-2-yl) stilene-2,2¹disodium disodium, 4,4¹-bis- (2-anilino-4- (1-methyl-2-hydroxyethylamino) -sym-triazol-6-ylamino) stilbene-2,2¹disodium disulfonate and 2-stilbyl-4^{1 1} - (NAIT¹ 2¹ : 4,5) -1,2,3-triazole-2¹¹ sodium sulfonate.

The soil release agents useful in the compositions of this invention are typically terephthalic acid copolymers or terpolymers with ethylene-glycol and / or propylene glycol units in a variety of configurations. Examples of such polymers are described in U.S. Pat. Nos. 4,115,885 and 4,711,730; 0272033rd particular preferred polymer of the patent application č.0272033 is a polymer of formula (PEG) ₄₃₎ o, (POH) o. 25 [T-PO) _2, 8 (T-PEG) o ₄ 4] T.

wherein PEG denotes - (OC ₃ H ₄ ) O-,

PO denotes the group (OCaHeO) and

T denotes the group ₍₄ pC0CôH C0).

European patent applications (CH ₃ materials, such as with a molecular weight of 5,000 to 5,000)

000, also form useful labile dyes between fabrics bed of the soaking agent are exemplified by silicones and oxide mixtures Silicones can generally represent materials while silica

Some polymeric polyvinylpyrrolidones, typically 20,000, preferably 10,000, to transfer prevention agents during the wash process.

in*

Other potential suds suppressors. Silica with silicones. alkylated polysiloxane is usually used in finely divided forms. Examples are silica aerogels and hydrophobic silica xerogels of various types. These materials may be included herein as particles in which the suds suppressor is preferably releasably included in a water-soluble or water-dispersible, substantially non-surfactant, non-permeable wetting carrier. The suds suppressor may also be dissolved or dispersed in a liquid carrier and applied to one or more other ingredients.

As mentioned above, useful silicone suds controlling agents may comprise a mixture of an alkylated siloxane of the above type and a solid silica. Such mixtures are prepared by fixing the silicone to the surface of the solid silica. Preferred foam control silicone agents are hydrophobic silanated (most preferably trimethylsilane) silica having a particle size in the range of from 10 nanometers to 20 nanometers and a specific surface area of over 50 m ² / g, immediately mixed with a dimethylsilicone liquid having a molecular weight in the range of about 500 to about 200,000 at a silicone to silane silica weight ratio of from about 1: 1 to about 1: 2.

Preferred silicone agents.

described by Bartollot et al.

US patent regulates foaming,

933 672. Next

no. 3 a particularly useful suds suppressor is the self-emulsifying 1 icon suds suppressor which is described in the German patent application DTOS 2 646 126 published April 28

For example, such a compound is DCO544, commercially available from Dow Corning. It is a siloxane / glycol copolymer.

The suds suppressors as described above are normally used in amounts of from 0.001% to 0.5% by weight of the composition, preferably from 0.01% to 0.1% by weight.

A preferred method of incorporating them in the composition is by applying spray suds suppressors in liquid form to one or more of the major components of the composition, or else by preparing suds suppressors as separate particles, which can then be mixed with other solid components of the composition. The inclusion of suds modifiers as discrete particles also allows them to contain other suds controlling materials such as 20-24 carbon atoms fatty acids, microcrystalline waxes and copolymers of high molecular weight ethylene oxide and propylene oxide that could otherwise adversely affect the dispersibility of the matrix. . Methods for preparing such suds modifying particles are described in U.S. Pat. No. 3,933,672 to Bartollt et al. .

Another optional ingredient useful in the present invention is one or more enzymes.

Preferred enzymatic materials include commercially available amylases, neutral and alkaline proteases, lipases, esterases, and cellulases conventionally included in soaking compositions. Suitable enzymes are discussed in U.S. Pat. 3,519,570 and 3,533,139.

Fabric softening agents (fabric softeners) may also be included in the soaking compositions of the present invention. These agents may be of the inorganic or organic type. Examples of inorganic fabric softeners are smectite described in British patent application no. Organic fabric fabric softeners include the water-insoluble tertiary amines described in British Patent Application Ser. 1 514 276 and European patent B-0011340.

Their combinations with mono-quaternary ammonium salts of 12 to 14 carbon atoms are described in European patent no. B-OO26527 and 528. Other useful organic fabric softeners are two long chain amides as described in European patent B-0242919. Other organic components of fabric softener systems include high molecular weight polyethylene oxide materials as described in European Patent Application Nos. 0299575 and 0313146.

The amount of smectite is usually in the range of from 5% to 15%, more preferably from 8% to 12% by weight. The material is usually added as a dry blended component to the remainder of the composition. Organic fabric softening agents, such as water-insoluble tertiary amine or amide (two long chain) materials, are included in the composition in an amount of 0.5 to 5 weight percent, normally from 1 to 3 weight percent, while high molecular weight polyethylene oxide materials and the water-soluble cationic materials are added in amounts of from 0.1 to 2%, normally from 0.15 to 1.5% by weight. As long as. Part of the composition is sprayed, then these materials can be added to the aqueous slurry fed to the spray tower, although in some cases it may be appropriate to add them as dry mixed particles or spray them as molten liquid onto other solid components of the composition.

The peracid-based surface treated bleach precursor particles of the present invention are particularly useful in concentrated granular soaking compositions which are characterized by a relatively high density compared to conventional soaking detergents. These high density compositions have a bulk density of at least 650 g / liter, more typically at least 700 g / liter, and more preferably greater than 800 g / liter.

The bulk density is measured using a simple funnel and a cup device that forms a conical funnel firmly attached to the bottom-flap pedestal allowing the contents of the funnel to be emptied into an axially positioned cylindrical cup that is underneath the funnel. The funnel is 130 mm and 40 ml at the top and bottom. The funnel is fixed so that its lower end is 140 mm above the top in the surface of the pedestal. The cup has a total height of 90 mm, an inner height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

During measurement, the funnel is filled with powder by pouring the powder into the funnel by hand, opening the flap and allowing the powder to pour into the crucible. The filled crucible is removed from the base and the excess powder is removed from the crucible using a device having a straight edge, e.g. by rubbing the upper end of the knife. The filled crucible is weighed and the powder weight obtained is doubled. This gives the bulk density, in grams per liter. The measurement is repeated as necessary.

Concentrated soaking compositions are also normally included in at least one multi-component component, i. they do not contain compositions made by merely mixing the individual ingredients. Compositions in which the individual ingredients are dry-mixed are usually dusty, slowly dissolve, tend to sinter, and acquire a poor flow properties during storage.

Taking into account the above limitations on bulk density and composition of the composition, the compositions of the invention can be manufactured in a variety of ways including dry blending, spray drying, agglomeration and granulation. Preferably, the methods comprise combinations of these methods. A preferred method of making the compositions comprises a combination of spray drying, agglomeration in a high speed mixer, and dry blending.

Preferred soaking compositions according to the invention comprise at least two particulate multi-component components. The first component comprises at least 15%, usually from 25 to 50, even more preferably not more than 35% by weight of the composition. The second component comprises from 1% to 50, preferably 10 to 40% by weight of the composition.

The first component comprises particles comprising an anionic surfactant in an amount of from 0.75 to 40% by weight of the powder and one or more inorganic and / or organic salts in an amount of from 99.25 to 60% by weight of the powder. The particle may be in any suitable form, such as granules, flakes, lumps, noodles, and the like. however, preferably they have a granular shape. The granules themselves may be agglomerates made by ladle or drum agglomeration or directly in-line mixers, but are usually spray-dried particles produced by atomizing the aqueous slurry of the components in a stream of hot air that removes most of the water. The spray dried granules are then subjected to a thickening step, e.g. in high speed cutting / mixers and / or compacting mills to increase density before agglomeration.

By way of illustration, the first component described herein is a spray-dried powder.

It has been found that agents for an alkyl sulfate of average 16 that suitable anionic surfactant component of up to 2 alkylcarboxylate of average 16-22 surfactant types are slowly dissolving which alkyl group of carbon atoms (s) in which the alkyl group of active carbon contains and contains non-linear atoms. The alkyl groups of both agents preferably originate from natural sources such as tallow fat and spermaceti oil.

The amount of anionic surfactant in the powder by spray drying constituting the first component is from 0.75 to 40% by weight, more usually from 2.5 to 25%, preferably from 3 to 20%, and most preferably from 5 to 15% by weight. Water-soluble surfactants such as linear alkylbenzene sulfonates or alkyl sulfates of 14 to 15 carbon atoms may be present in the M powder, or they may also be applied by spraying onto a spray-dried powder.

Another major component of the spray-dried powder is one or more inorganic or organic salts which give the granules a crystalline structure. The inorganic and / or organic salts may be water-soluble or water-insoluble. The latter type comprises a major part of the water-insoluble building components, where these components form part of the building component. Suitable water-soluble salts include alkali metal carbonates and bicarbonates. Alkali metal silicates other than crystalline layered silicates may also be present in the spray-dried granules, provided that the aluminosilicate does not form part of the spray-dried component.

However, it is preferred that the concentrated soaking compositions are free of water-soluble sulfate, especially sodium sulfate, in an amount greater than 2.5% by weight of the composition. Preferably no sodium sulfate is added as a separate component. Its content in the composition as a by-product, e.g. sulphate surfactants should be minimized.

If the zeolite aluminosilicate constitutes or is part of the builder component, it is preferred that it is not added directly to the other spray-dried components but to be included in the multi-component (s) component (s). If the inclusion of zeolite is carried out in a spray-dried granule, no silicate should be included in the spray-dried granule. In these cases, the inclusion can be accomplished in several ways, e.g. preparing a separate silicate containing the spray dried particles, including the silicate in an agglomerate of the other ingredients, or more preferably adding the silicate as a dry dry blended ingredient.

The first component may also include up to 15% by weight of other ingredients, such as brighteners, anti-fouling agents, photoactivating bleaches (such as tetrasulfonated zinc phthalocyanine), and agents that. cause heavy metal uptake. If the first component is a spray-dried powder, the component is normally dried to a moisture content of from 7 to 11 weight percent, more preferably from S to weight percent of the spray-dried powder. The moisture content of powders produced by other processes such as agglomeration may be lower; it may be from 1 to 10% by weight.

The particle size of the first component is customary. Typically, not more than 5 weight percent should be no more than 1.4 mm in size, and not more than 10 weight percent should be less than 0.15 mm in maximum dimension. Preferably at least 60%, most preferably at least 80% by weight of the powder has a size between 0.7 and 0.25 mm. For spray-dried powders, the bulk density of the particles from the tower in which the spray-drying occurs is usually in the range of 540 g / liter to

600 g / liter.

This density is then increased in further processing steps, such as size reduction in a high-speed chain / mixer followed by compaction.

Use other methods than spray drying alone to obtain high density particles.

The second component of the preferred composition of the invention is another multicomponent particle containing a water-soluble surfactant.

The agent may be an anionic, nonionic, cationic or semipolar agent or a mixture of any of these agents. Suitable surfactants are listed above. Preferred surfactants, however, are C14-C15 alkyl sulfates, C11-C15 linear alkylbenzene sulfonates and fatty (C14-C18) fatty acid methyl ester sulfonates.

The second component may take any suitable physical form, i. there may be such as flakes, lumps, noodles, gums, granules and others which may be agglomerates that are spray dried or not spray dried. While the second component could theoretically contain its water-soluble surfactant, at least one organic or inorganic salt is practically included to facilitate processing. Thus, a certain degree of crystallinity and thus acceptable flow properties of the particles are obtained. One or more organic or inorganic salts may be present in the first component.

The particle size of the second component should be such that separation of this component from the particles of the first component is evident when mixed together. Therefore, it should not be more than 5% by weight above 1.4 mm, but not less than 0.15 mm at the maximum

Bulk density of the second preparation of this component. conveniently

more dimension. than 10% by should be ingredients is a f unkciou way through the second component it is

mechanically mixed agglomerate.

which may be prepared by adding individual dry ingredients or by adding these ingredients with an agglomerating agent to the ladle agglomerate.

a paddle mixer Σ or more preferably an in-line mixer.

such as Equipment manufactured by Schugi (The Netherlands)

BV, 29

Chroomstraat 8211 AS, Lelystad, The Netherlands and Gebruder

Lodige

Maschinenbau GmbH,

D-4790

Paderborn 1,

Elsenstrasse 7-9,

Postíach 2050, Germany.

This gives a second component having a bulk density in the range of 650 g / liter to 1190 g / liter.

more preferably from 750 g / l to 850 g / l.

The amount of alkali metal carbonate in the second component is preferably from 3 to 15% by weight of the composition, more preferably from 5 to 12% by weight. As a result, the amount of carbonate in the second component will be from 20 to 40% by weight.

A highly preferred component of the second bed is also the hydrated water-insoluble aluminosilicate ion exchange material of the synthetic zeolite type described above. This material is present in an amount of from 10 to 35% by weight of the second composition. In this manner, the water-insoluble aluminosilicate material is included in the composition in an amount of from about 10% to about 10% by weight of the composition, more preferably from about 2% to about 10% by weight.

In one method of preparing the second component, the surfactant salt is formulated in situ in an in-line mixer.

The liquid acid form of the surfactant is added to the blend of sodium hydrous sodium aluminosilicate hydrous sodium carbonate with a continuous high speed mixer, such as

Lodige KM mixer.

and neutralized to a surfactant salt while maintaining the particulate nature of the mixture. The final agglomerated mixture forms a second component which is then added to the other components of the product.

In one variant of this process, the surfactant paste is first neutralized to the salt and added as a viscous mixture of the other ingredients. In this variant, the mixer serves only to agglomerate the components to form a second component.

According to a particularly preferred process for the manufacture of soaking compositions comprising the coated peracid-based bleach precursor particles of the invention, a portion of the spray-dried product containing the first granular bed is removed and subjected to a small amount of surfactant spray before.

again mixed with the remaining material.

The second granular component is prepared by the preferred process described above.

Then, the belt conveyor with the first and second components together with the coated bleaching particulate material.

perhydrate bleach, other dry-mixed beds, such as a carboxylate chelating agent.

a soil release polymer, silicate of the conventional or crystalline layered type.

is transferred to a horizontally rotating drum, in and with an enzyme, by which the product is sprayed with Paris and a silicone suds suppressor. For a particularly preferred composition, an additional drum mixing step is used during which a small amount (about 2% by weight) of the finely divided crystalline material is added to increase the density of the composition and to improve its granular flow properties.

It has been found that preferred concentrated soaking products that contain alkali metal percarbonate as the peroxide salt need to regulate several aspects of the product, such as heavy metal ions and relative humidity.

Compositions of this type which contain sodium percarbonate and which have enhanced stability are described in British patent application

no. 9021761.3 z

October 6, 1990 (document no.

CM343).

The compositions of the invention may also benefit from the systems supplied, which cause transient localized high product concentrations in the drum of the washing machine at the beginning of the wash cycle. This avoids the problems associated with product loss in the duct or at the bottom of the machine.

Delivery to the drum is readily accomplished by placing the composition in a sachet or container from which it can be rapidly released at the start of the wash cycle in response to mixing, raising the temperature or immersion in the washing water in the drum. Alternatively, the washing machine may also be adapted to allow direct addition of the composition to the drum, for example by a dispensing device in the access window.

Products containing a soaking agent in a sachet or container are typically designed to keep the entire container dry so as to prevent leakage of the contents when dry, but to normally be immersed when the container is exposed to the wash environment into an aqueous solution, releasing the contents of the container.

Usually, the container will be flexible, such as a bag or pouch. The bag may have a fibrous structure coated with a water-impermeable protective material so as to maintain its content, as described, for example, in European Patent Publication no. It can also be made of a synthetic, water-insoluble polymeric material with a sealed edge or a closure that ruptures in an aqueous environment, as described in European Patent Application Laid-Open No. 0011500, 0011501, 0011502 and 0011968. A suitable form of water-sensitive closure comprises a water-soluble adhesive that is embedded in one corner of the bag and closes the corner of the bag formed of a water-impermeable polymer film, such as polyethylene or polypropylene. In the case of a bag or container variant, laminated products may be used whose intermediate flexible layer is impregnated and / or coated with the composition and one or more outer layers are applied thereto such that the product resembles a fabric. The layers may be sealed together to remain bonded during use, or may be separated upon contact with water to facilitate release of the coated or impregnated material.

Another laminate layer comprises one layer convex or deformed to give a row of pocket-like containers in which measured amounts of the components to be soaked are stored. The second layer overlaps the first layer and all is sealed into these pocket-like containers in which the two layers are in contact. The components may be stored in particulate, paste or molten form. Laminated layers should prevent the contents of the pouch containers from leaking before placing them in water. The layers may remain joined after contact with water;

the only requirement is that the structure permits rapid release of the contents of the pocket of the sachets into the solution.

The number of pocket-shaped containers per unit area is the subject of choice. It normally moves between

500 and 25

000 per square meter.

Suitable materials that can be used for flexible laminate layers in this aspect of the invention include.

inter alia, sponges, paper and woven and nonwoven fabrics.

However, a preferred method of carrying out the process of the invention is to introduce the composition into the liquid environment surrounding the fabrics that are in the drum by a reusable dispensing device with liquid-permeable walls that are impermeable to the solid composition.

A device of this type is described in European patent application no. 0343069 and 0343070. The second application discloses a device comprising a flexible pouch in the form of a pocket having a carrier ring defining an opening. This aperture is adapted to allow access to a sufficient quantity of bag product for a single wash cycle during washing. A portion of the laundry detergent will flow through the orifice into the pouch, dissolve the product, and the solution will then pass through the orifice to the wash environment. The support ring is equipped with a masking device to prevent the wet, undissolved product from escaping. This arrangement typically includes radial walls from a central protrusion of the spoke configuration or a similar structure with walls in a helical form.

The invention is illustrated by the following non-limiting examples. Percentages in the examples refer to weight percentages unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

In soaking compositions, the abbreviations of the components have the following meanings:

C12LAS refers to sodium alkylbenzenesulfonate with a linear alkyl group of 12 carbon atoms,

TAS refers to tallow alcohol alcohol sodium,

C14 / 15AS refers to sodium alkyl sulphate of 14 to 15 carbon atoms,

TAEn refers to tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol,

45E7 denotes a predominantly linear primary alcohol of 14 to 15 carbon atoms condensed with an average of 7 moles of ethylene oxide,

.5ηΑΕεβ.5 denotes a primary alcohol having 12 to 13 carbon atoms condensed with 6,5 moles of ethylene oxide,

PRG refers to polyethylene glycol (usually followed by molecular mass),

TAED refers to tetraacetylethylenediamine.

silicate refers to amorphous sodium silicate (usually followed by the ratio of silica to sodium oxide),

NASKS-6 refers to crystalline layered silicate.

having the formula NazSisOs, carbonate refers to anhydrous sodium carbonate.

CMC refers to sodium carboxymethylcellulose, zeolite (resp.

Zeolite

A) refers to hydrated sodium aluminosilicate.

that has the formula

_I2 (AIO2SÍO2) 12th 27H ₂ O, having a primary particle size ranging from up to micrometers, molecular weight 4000, citrate refers to trisodium salt dihydrate photoactivated bleach refers to tetrasulfonated citric zinc talcyapolyacrylate refers to acrylic acid homopolymer with acrylic acid

ηϊη.

MA / AA refers to a copolymer male í nove j acids with akrylevou acid, in ratio 1 4 p average molecular about 80 000. MVEMA refers to a copolymer anhydride of malei novej

with vinyl methyl ether, which is assumed to have an average molecular weight of 240,000. This material is prehydrolyzed with sodium hydroxide prior to addition, • perborate refers to sodium perborate tetrahydrate having the nominal formula NaBO2.3H2O.H2O2, * perborate monohydrate refers to bleach of anhydrous sodium perborate , which has the empirical formula of NaBCb. H 2 O 2, percarbonate refers to sodium percarbonate having the nominal formula 2N z CO 2. 3Hz O2, the enzyme refers to the mixed proteolytic and amylolytic enzyme sold by Novo Industries AS; Sodium 2'-disulphonate,

DETPMP refers to diethylenetriaminepenta (methylenephosphonic acid) sold by Monsanto under the trade name Dequest 2060 and a suds suppressor mixture denotes 25% paraffin wax with a melting point of 50 ° C, 17% hydrophobic silica ¹ and 58% paraffin oil.

For the purposes of the present invention, the non-limiting dissolution conditions are defined in the same manner as for the Beaker Perhydrolysis Test performed on a Sotax Dissolution Tester Model AT6 supplied by Sotex AG CH-4008, Basel, Switzerland. This device contains a series of polycarbonate beakers, each of which has a capacity of 1 liter of water, in a thermostatically controlled water bath. Each beaker has a lever stirrer, the speed of which can be regulated.

The two beakers in the Sotax Tester are used for perhydrolysis as follows:

1. Set the water bath to the desired temperature (20 ° C).

2. Add 1 liter of distilled water to each Sotax beaker and allow the contents to equilibrate to the desired temperature.

3. Prepare a sample of exactly 2.10 g of the wettable reagent and precursor sample.

4. Prepare a series of titration beakers by adding: 25 ml of a 3: 2 glacial acid / distilled water solution together with 2 ice cubes.

5. Set the mixing speed of the Sotax to 150 rpm.

6. In Sotax Beaker 1, the first sample is added and the time counts (t = 0 minutes). Add 5 ml of potassium iodide to the first titration beaker.

7. Take 10 ml aliquots of Sotex Beaker no. 1a is transferred to the first titration beaker at t ^: = 1 minute.

8. In the Sotex beaker no. 2, a second sample is placed at t = 1 minute and 5 ml of potassium iodide are added to the second titration beaker.

9. Titrate the first portion with 0.005 M sodium thiosulphate until the solution is first bleached (Color slowly regenerates as the solution heats up and the peroxide reacts with the iodide).

10. Take 10 ml aliquots of Sotex Beaker no. 2 at time t = 2 minutes, transfer to a second titration beaker and repeat step 9.

11. Additional fractions (t = min) shall be taken at the following times:

beaker no. 1 (t): beaker no. 2 (t): 3 4 5 6 10 11 15 16 20 21

Beaker shares no. 1 at 1 minute and beaker no. 2 at 2 minutes represent repetition. The results are the average of the two data. This yields numbers from which the% perhydrolysis can be calculated.

Example 1

The fine powder TAED (90% particle size is less than 150 microns) is agglomerated with TAE25. This gives particles of which 85% have a mass of between 400 microns and 1700 microns. This material is divided into five fractions designated A to F, fraction A denotes an untreated fraction and the remaining fractions are treated as follows: surface treatment material:

B with 5% octanoic acid

C with 5% polyacrylic acid (2000 molecular weight)

D with 5% glycolic acid with 5% citric acid.

The processing is carried out by spraying the material by hand in a small coating drum. The octanoic acid is melted at 60 ° C, the remaining materials are applied as aqueous solutions at room temperature (20 ° C).

The citric acid solution had a concentration of 50% by weight, a glycolic acid solution of 66% and a polyacrylic acid solution of 50% by weight.

The material of each fraction was then included in a model soaking composition having the following composition (in parts by weight):

C ₁₂ LAS 9.0 TAS 2.8 Dobanol 45E7 3.8 Zeolite A 23.5 or trát 7.5 MA / A 3.75

carbonate 17.0 silicate 4.2 (oxide ratio Silica and sodium oxide is 2 : 1) DETPMP 0.4 CMC 0.5 percarbonate 18.7 TAED 5.85 Differently 3.00 These five funds is then submitted Beaker Perhydrolysis test how to above. Extracts of peracids

are given in Table I. The results are given for time 1, 3, 5,

10, 15 and 20 minutes and are expressed as a percentage of the theoretically available peracid weight.

Table I product with TEAD minutes from start of perhydrolysis: ____ fraction: 135 10 15 20

A 37.3 74.2 86.0 93.9 97.8 97.2 B 23.2 60.1 75.9 90.8 97.4 96.5 • C 29.0 67.2 77.2 88.2 90.8 90.0 D 37.6 73.7 85.1 94, 9 97.5 98.6 4 E 36.8 74.5 87.2 92.5 96.8 97.6

From the table, it can be seen that the formulations containing fractions D and E provide substantially the same peracid yield as the formulation containing fraction A (both after 3 minutes and throughout the perhydrolysis reaction). That is, perhydrolysis under non-dissolution conditions was not substantially affected by machining. In contrast, however, compositions containing fractions B and C showed a lower yield of peracid, especially at the beginning of perhydrolysis.

Compositions comprising TEAD fractions A and D of the example

Example 2

1 were tested for washing machines in a Miele washing machine (Model W754) set for a short wash cycle at 40 ° C. Each apparatus was filled with four cotton tarpaulins (3.3 kg). To the fabrics in the drum, 100 g of the composition was added with the Arielator (RTM) dosing device. Each washer is filled with 12 liters of water having a hardness of 150 ppm (expressed as calcium carbonate) with a Ca: Mg ratio of 3: 1.

Two scrubbers, which were adjusted to open the loading window during the cycle, were used to carry out the same procedure as the beaker perhydrolysis test. The results are shown in Table II and are expressed in the same quantities as in Table I.

Table II

product with TEAD fraction: minutes from the start of perhydrolysis. 1 3 5 10 15 20 A 31.5 56, 1 82.1 92, 1 89.4 89.4 D 9.1 50.6 68.0 99.5 98.5 96.7

From the table, it can be seen that under conditions where the dissolution conditions in the loaded scrubber are limited, the product containing fraction D (TEAD with glycolic acid treated surface) perhydrolyses more slowly than the product containing fraction A (untreated material) during the initial washing stages. This shows that TEOL surface treatment with glycolic acid inhibits perhydrolysis during a period when there is a high localized concentration of product in the wash cycle, where high acid solubility in water is believed to produce a low pH around the TAED particles. However, at subsequent stages of washing, the peracid yield of the treated TAED is superior to that of the untreated material, indicating that delayed release of TAED results in its more efficient conversion to peroxy.

Example 3

A washing machine test was carried out comparing three compositions containing fractions B, C and D of the surface treated precursor of Example 1. These fractions were added to a modified form of the soaking composition of Example 1 in which sodium percarbonate was replaced with an equal weight of monohydrate sodium perborate.

In the washing machine comparison, the same method as that used in Example 2 was used, the washing temperature being 20 ° C. This is the typical temperature that exists in the washing machine during the initial cold load of European washing. The results are shown in Table III.

Table III

product with TEAD fraction: minutes from the start of the perennial call: 1 3 5 10 15 20 B 4.6 33.6 54.7 74, 8 78.0 80.3 C 4.6 32.6 54, 3 80.7 84.8 88.0 D 3.65 54, 8 70.8 83.0 88.5 85.0

The results in this table show that the peracid-based bleaching precursor surface treated according to the invention provides better peracid yields under real washing conditions compared to a non-inventive surface treatment of the precursor.

Example 4

The compositions are compared in a washing machine similar to the example

3. Precursor fractions A, B, C and E are used, and the fabric fill contains colored pieces of fabric sensitive to bleach. These pieces were made from 100% purple wool sheepskin fabric 49 (Design No. W3970) supplied by Borval Fabrics, Albert Street,

Huddersfield, West Yorkshire, England. Each treatment was repeated 24 times. The pieces were then visually evaluated for color damage by the panel of experts using the following evaluation system.

Three colored pieces with different color damage were used as standards for expressing the four-point color damage scale. 1 indicates really no damage and 4 indicates very damaged ”. These three standards are used in defining midpoints between different descriptions of color damage, see Figure 3. :

actually no damage slight damage damaged very damaged.

The services of two panel experts were used. The results obtained were averaged.

This method of comparing color damage caused by the use of compositions containing precursor fractions A, B, C and E gave the following results:

means with precursor fraction pieces that also have a degree: overall stupetí 1 2 3 4 A 50 29.2 8.33 12.5 1.83 B 52.2 26.1 21.7 0 1.70 C 47.8 30.4 17.4 4.4 1.78 E 66.6 16.6 10.5 6.2 1.56

From these results, it can be seen that the composition comprising fraction E of the invention provides a significantly less color deterioration of the fabric than the untreated or non-treated surface precursor.

Example 5

The comparison of Example 4 in the washing machine is repeated, using compositions containing TEAD fractions A and D of Example 1 as well as another TEAD fraction F containing fraction A which is agglomerated with 10% by weight of glycolic acid (based on total weight agglomerate). These compositions are subjected to a degradation test of colored pieces of matter as described in Example 4.

The following results are obtained:

% of coils. which also has a degree: overall degree 1 2 3 4 A 16 20 25 38 2.83 D 29 38 29 4 2.08 F 9 35 35 22 2.70

It can be seen that fraction D, which contains the precursor particle surface treated with the% glycolic acid of the present invention, has a significantly lower overall degree of damage than the untreated fraction A.

In contrast, the use of 10%, i.

twice the amount of glycolic acid as the agglomerating agent leads to a small decrease in the degree of damage due to the raw material. This confirms the importance of surface treatment of the bleach precursor particles in order to reduce fabric damage as a result of the beneficial effects of the present invention.

Claims (19)

A peroxyacid-based solid bleach precursor composition comprising a particulate peracid-based bleach precursor material, wherein the precursor comprises one or more N- or a melting point greater than 30 ° C, a particulate bleaching composition. O-acyl groups and having a point outer surfaces of said peracid-based precursor material are treated with an organic acid compound so that said compound adheres to the outer surfaces, said compound being present in an amount of 2 to 20% by weight of the treated particle, the organic acid compound having a water solubility of at least 5 g / 100 g water at 20 ° C and a melting point greater than 30 ° C, wherein the treated particulate bleach precursor material provides at least 90% peroxygenation in the beaker perhydrolysis assay at 20 ° C after three minutes compared to the particulate bleach precursor material under the same conditions. The peroxyacid-based solid bleach precursor composition of claim 1, wherein the organic acid compound has a water solubility of at least about 20 g / 100 g water at 20 ° C. Peracid-based solid bleach precursor composition according to any one of claims 1 and 2, characterized in that a monomeric or oligomeric carboxylate is used as the organic acid compound. 4th A peroxyacid based bleach precursor composition according to any one of the claims 1- to 10, characterized in that a monomeric aliphatic carboxylic acid having a melting point greater than 40 ° C is used as the organic acid compound. A peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 4, characterized in that the organic acid compound used is a compound selected from glycolic acid, 1-lactic acid and citronic acid. The peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 5, wherein the amount of material to be treated is from 2 to 15% by weight of the composition. The peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 6, wherein the amount of material to be treated is from 3 to 10% by weight of the composition. Solid based bleach precursor composition based on. The peracid according to any one of claims 5 to 7, wherein the treated particulate bleach precursor material provides substantially the same amount of peracid after 3 minutes in a beaker perhydrolysis test at 20 ° C as obtained under the same conditions with the particulate bleach precursor material in untreated form. The peracid-based solid bleach precursor composition according to any one of claims 1 to 8, wherein the peracid-based bleach precursor comprises at least one N-diacyl group. peracids according to any one of the claims 1 to 9. as a bleaching precursor based on peracid 10th Solid bleach precursor composition based on tetraacylated alkylenediamine. The peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 10, wherein the peracid-based bleach precursor is a tetraacetyl alkylenediamine. The peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 11, wherein the particulate precursor material comprises agglomerated precursor particles, wherein the agglomerated particles are treated with an organic acid compound. The peroxyacid-based solid bleach precursor composition of claim 12, wherein the agglomerating agent is selected from ethoxylated fatty alcohols, polyethylene glycols, and cellulose derivatives. A peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 13, characterized in that the peracid-based particulate bleach precursor material is treated with the molten organic acid compound to obtain a coating of the outer surfaces of the particulate bleach precursor material. . A peroxyacid-based solid bleach precursor composition according to any one of claims 1 to 13, characterized in that the outer surfaces of the particulate bleach precursor material are based on. the peracid base is treated with a solution or dispersion of the organic acid compound. A peroxyacid-based solid bleach precursor composition according to any one of claims 14 and 15 as finely divided, characterized by. The organic acid is applied to the powder. A peroxyacid-based solid bleaching composition according to any one of claims 1 to 16, wherein the bleaching composition comprises an inorganic peroxygen bleach. A granular bleaching composition according to any one of claims 1 to 17, characterized in that it is a peroxygen bleach. uses sodium perborate or sodium percarbonate, which is present as a dry granulated material. 19th Granulated white · The detergent according to any of the above 20th of claims 17 and 18, characterized in that <3. The composition further comprises anionic nonionic, cationic or amiolytic agents of any type The granulated v / y agent is a bleaching peroxyacid other surfactant or mixture thereof. in that the surfactant present as a constituent of the precursor composition based and inorganic, wherein the solid based on said article of content is particles of no more than 5% by weight is less than 250 micrometers. 21. Concentrated granulated soaking agent. it has a bulk density of at least 650 g / liter and that it contains the granulated bleaching agent according to any of the preceding points.