PT78253B

PT78253B - Process for preparing a bleaching and laundering composition free of water-soluble silicates

Info

Publication number: PT78253B
Application number: PT78253A
Authority: PT
Inventors: Guy Broze; Leopold Laitem
Original assignee: Colgate Palmolive Co
Priority date: 1983-03-15
Filing date: 1984-03-14
Publication date: 1986-04-30
Also published as: GB8406757D0; DK101184D0; PT78253A; ES8506793A1; NO161444B; CH661055A5; SE8401047L; GB2138039A; DK161895B; NO161444C; BE899162A; CA1227717A; SE460053B; FR2542757B1; DK161895C; IT1184258B; NL8400808A; MX162791A; ES530579A0; ZA841401B

Abstract

A particulate bleaching detergent composition is provided comprising (a) a bleaching agent comprising a peroxyacid compound and/or a water-soluble salt thereof; and (b) at least one surface active agent selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; said bleaching detergent composition being substantially free of (i) water- soluble silicate compounds and (ii) agglomerate particles which essentially comprise said activator, a water-insoluble silicate compound and a nonionic surfactant.

Description

Detailed Description of the Invention

The detergent bleaching compositions object of the invention are essentially free of water soluble silicate compounds and are formed by two major components.

(a) a bleaching agent; and (h) a surfactant.

The bleaching agent useful in such compositions includes a water-soluble peroxyacetic compound and / or a water-soluble salt thereof. Peroxyacid compounds are characterized by the following general formula:

0

«

H00-0-RZ

where R represents an alkylene group containing from 1 to about 20 carbon atoms, or a phenylene group and Z represents one or more groups selected from hydrogen, halogen, alkyl, aryl and anionic groups.

Organic peroxyacids and their salts may contain from about 1 to about 4 preferably 1 or 2 peroxide groups and may be aliphatic or aromatic. Preferred aliphatic peroxyacids include diperoxiazelaic acid, diperoxydodecanedioic acid and diperoxydodecanedioic acid and monoperoxysuccinic acid.

Among the aromatic peroxyacid compounds useful in this process, monoperoxyphthalic acid (MPEA) and in particular its magnesium salt, as well as diperoxytherephthalic acid, are especially preferred.

A detailed description of the production of MFFA and its magnesium salt is given on pages 7 to 10, inclusive of European Patent Publication

No. 0,027,693, issued April 29, 1981, said pages 7-10 being incorporated herein by reference.

The bleaching agent may optionally also include a peroxygen compound in addition to the peroxyacid compound. Useful peroxygen compounds include peroxide releasing compounds. of hydrogen in aqueous media such as alkali metal perborates, for example, sodium perborate and potassium perborate, alkali metal perphosphates and alkali metal percarbonates. Alkali metal perborates are usually preferred because of their commercial availability and relatively low cost. If desired, an organic activator may be used in association with that peroxygen compound. Conventional activators such as those described, for example, in column 4 of U.S. Patent 4,259 * 200 are suitable for use in association with the aforesaid peroxygen compounds, this disclosure being described herein

incorporated by reference, polyacylated amines are generally of particular interest, in particular, tetraacetylethylenediamine (TAED) is a highly preferred activator.

TAED is preferably present in the compositions of the invention in the form of "coated" granules containing TAED and a suitable carrier, such as a mixture of sodium and potassium triphosphate

These TAED coated granules are conveniently prepared by mixing finely divided particles of sodium triphosphate and TAED and then spraying this mixture with an aqueous solution of potassium triphosphate using suitable granulation equipment, such as rotary granulator.

A typical method of preparation for this type of coated TAED is described in U.S. Patent 4,238,302 to Eoret et al. TAED granules have preferably a size distribution

of particles having the following: 0-20% greater than 150 microns 10-100% greater than 100 μm but less than 150 μm or 050% less than 75 μm; and 0-20% less than 50 Âμm.

Another especially preferred particle size distribution is that where the mean particle size of TAED is 160 microns, i.e., 50% of the particles have a size greater than 160 microns. The above-mentioned size compositions refer to TAED present in the coated granules and not to the coated granules themselves. The molar ratio of the peroxygen compound to the activator can vary greatly, depending on the exact choice of the peroxygen compound and the activator.

However, the molar ratios of about 0.5: 1 to about 25: 1 are generally suitable to provide a satisfactory bleaching action.

The detergent bleaching compositions of the invention are characterized in that they are substantially free of (i) water soluble silicate compounds and (ii) agglomerate particles which are essentially composed of a blend of three components. The organic activator for the peroxygen compound; a water insoluble silicate compound such as clay or zeolite; and a nonionic surfactant being such a blend formed by at least 80% by weight, of particles, of agglomerate.

Agglomerate particles which are excluded for use in this blend are those of the type formed in equipment with the granulator and serve to incorporate the bleach activator into a matrix of materials as described in European Patent Publication No. 0.028.432.

In a particular embodiment of the invention, the bleaching compositions are further characterized in that they are essentially free of sequestering agents, exhibiting a stability constant for a complex formation or greater than about 20 in water at 25Â ° C and at an ionic strength of 0.1 mol / liter., the water-insoluble silicate materials which may be advantageously employed in the present bleaching compositions are preferably aluminosilicates, such as zeolites and the clays 4o-type. Crystalline zeolite types which may be used include those described in Zeolite Molecular Series by Donald W. Eteck, and published in 1974 by John Wiley & Sons, with typical zeolites being available

commercially recorded in Table 9.6 of pages 74-7 "749 of the text, this framework being incorporated herein by reference.

Zeolite structures of the type to be especially desirable are extensively described in the art; see, for example, page 133 of the Breck Text mentioned above, as well as U.S. Patent No. 2,882,243. Zeolites are particularly useful as builder salts in detergent compositions with enhanced action. The aforementioned seam-type clays are three-layer clays, characterized by the ability of the layered structure to increase its volume several times, either by swelling or expanding when in the presence of water, forming a gelatinous fixotropic substance. There are two classes of clays of the smectic type, in the first class aluminum oxide is present in the crystalline silicate network in second grade magnesium oxide is present in the crystalline silicate lattice. Substitution of the atoms by iron, magnesium, sodium, potassium, calcium and the like can occur within the crystalline network of the esmetic clays. It is usual to distinguish between clays at the base of their predominant cation.

For example, a sodium clay is one in which the cation is predominantly sodium. With respect to the present detergent bleaching compositions, aluminum silicates, characterized in that sodium is the predominant cation, such as, for example, bentonite clays. Especially preferred among bentonite clays are Wyoming (generally referred to as Western bentonite) or Wyoming). Calcium and magnesium clays are also useful, although less preferred for the purposes of this invention. Preferred instrumental bentonites

are sold under the trademark Mineral Colloid, with industrial bentonites, by the "Benton Clay Company," a subsidiary of "Georgia Kaolin Go." These materials, which are the same as those previously sold under the trademark THIKO-JELs, are selectively extracted bentonites and those which are considered to be the most useful are referred to as "Mineral Colloid" Nos. 101, etc., corresponding to "THIXO-JELs" Nos. 1,2,3 and 4. These materials have pH's (6% water concentration) in the range of 8 to 9.4, a maximum moisture content of about 8% and a specific weight of about 2.6 and in the spray state, about 85% at least (and preferably 100%) pass through a 200 mesh screen of the US Sieve Series

In an even more desirable form, the bentonite is characterized in that its particles (i.e., at least 90% thereof or preferably above 95%) are characterized by passing through a No. 2 mesh sieve. 325 and, in the epitome, all particles pass through this sieve. The inertness of the bentonites in the water is usually in the range of 3 to 15 ml / g and their viscosity at a water concentration of 6% is usually about 8 to 30 centipoises.

In a particularly desirable embodiment of the invention, the carrier particles include finely separated bentonite agglomerates having particle sizes smaller than a No. 200 screen, particulate agglomerates of substantially the size of the sieves Nos. 10-100, of a density on the order of 0.7 to 0.9 g / ml and a moisture content of 8 to 13%. Such agglomerates contain about 1 to 5% of a binder or agglomerating agent which assists in maintaining the integrity of the agglomerates until they are added to the water in which they are intended to be disintegrated and dispersed. A detailed description of the method of preparation of such agglomerates is shown in U.S. Patent Application Serial No. 366,587 filed April 8, 1982, which is hereby incorporated by reference.

Instead of using THIXO-JEL or Mineral COlloid benches, competitive equivalent products such as those sold by the American Colloid Company Industrial Division may also be used in the form of "General Purpose Bentonite Powder"

(Bentonite Powder for beneficial purposes) of 325 mesh where a minimum of 95% is finer than the 325 mesh or 44 microns in diameter (wet particle size) and a minimum of 96% finer than the 200 mesh or 74 mesh microns in diameter (dry particle size). Such hydrated aluminosilicate is composed mainly of montmorillonite (90% minimum) with minor proportions of feldspar, biofite and selenite.

A typical analysis on an anhydrous basis showed 63.0% silica, 21.5% alumina, 3.3% ferric iron (as Ee ₂₀ ) and 0.4% ferrous ( as EEO), 2.7% of magnesium (as MgO), 2.6% sodium and potassium (as Na ₂ 0) 0.7% calcium (as CaO ), 5.6% of crystal water (as _H2 0) and 0.7% of trace elements.

Although "western" bentonites are preferred, it is also possible to use synthetic bentonites, such as those obtainable by treating Italian bentonites or the like, which contain relatively small proportions of exchangeable monovalent metals (sodium and potassium) with materials

alkali metals, such as sodium carbonate, in order to enhance the cation exchange capabilities of these products. It is contemplated that the Na ₂ O content of the bentonite should be about 0.5%, at least preferably at least 1%, and still more desirable at least 2%, so that the clay is satisfactorily odorless , with good softening and dispersion properties in aqueous suspension. Preferred inorganic bentonites of the synthetic types described are sold under the trade names Laviosa and Vinkelmann, for example, Laviosa AGB and Vinkelmann G-13 · i

The compositions of the present invention contain one or more surfactants selected from the group of anionic, non-ionic detergents. cationic, ampholytic and zwitterionic. |

Among the surfactants

I

anionic compounds useful in the present invention are those. surfactant compounds which contain an organic hydrophobic group I which includes in its molecular structure from about 8 to 26 carbon atoms and preferably from about 10 to 18 carbon atoms and at least one water solubilizing group selected from from the group formed by the sulfonate, sulfate, carboxylate, phosphonate and phosphate to form a water-soluble detergent.

Soaps are included in the examples of suitable anionic detergents, such as water-soluble salts (for example sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. Suitable fatty acids may be obtained from oils and waxes of animal or vegetable origin, for example tallow,

fat, coconut oil or mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, for example, coconut sodium soap and tallow potassium soap.

The anionic class of detergents

includes sulphated and sulphonated water-soluble detergents having an alkyl radical containing from about 8 to 26, and preferably from about 12 to 22, carbon atoms (the term "alkyl" includes alkyl of the higher acyl radicals Examples of the sulfonated anionic detergents are the higher alkyl aromatic mononuclear sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain such as, for example the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.

Other suitable anionic detergents are olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfates or mixtures of alkenesulfonates and hydroxyalkylene sulfonates. '

I

The olefin sulfonate detergents!

can be prepared in a conventional way through! of the SO2 reaction with long chain olefins containing from about 8 to 25, and preferably from about 12 to 21 carbon atoms, these olefins having the formula ECH-OHfij, wherein E is a higher alkyl group of about 6 to 23 carbon and is an alkyl group containing | about 1 to 17 carbon atoms or hydrogen,

j

to form a mixture of sulfones and alkenesulfonic acids which is then subjected to treatment, to

converting sulfones to sulfonates further examples of sulfate or sulfonate detergents are paraffin sulfonates containing from about 10 to 20 carbon atoms, and preferably from about 15 to 20 carbon atoms.

The main sulfonate paraffins are made by the reaction of long-chain olefins and bisulfites. The paraffin sulfonates having the sulfonate group distributed along the paraffin chain are disclosed in U.S. Patents 2 · 5 · 3 · 280; 2 · 5θ7 · 088; 3 · 260 · 741; 3 372,188 and in German Federal Patent No. 735, 096, other suitable anionic detergents are the ethoxylated and sulfated higher fatty alcohols of the formula RO (O-OH), wherein R is a fatty alkyl of 10 to 18 carbon atoms, m is 2 to 6 (preferably having a value of about 1/5 to 1/2 the number of carbon atoms in R) and M is a cation for the formation of solubilizing salts such as a metal alkali, ammonium, lower alkylamino or lower alkanolamino, or a higher alkyl benzene sulfonate in which the higher alkyl has 10 to 15 carbon atoms.

The proportion of ethylene oxide in the polyethoxylated higher alkanol sulphate, and preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, three moles being preferred, especially when the higher alkanol contains 11 to 15 carbon atoms.

In order to maintain the desired hydrophile-lipophilic balance, when the carbon chain content of the alkyl chain is in the lower portion of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about of two moles per mole, whereas when the higher alkanol contains from 16 to 18 carbon atoms at the top of the scale the number of the ethylene oxide groups may be increased to 4 or 5θ, in some cases even to 8 or 9. Similarly, the salt-forming cation may be altered so as to obtain the best solubility. It may be any suitably solubilizing metal or radical, although in most cases it is an alkali metal, sodium or ammonium. If alkylamine or alkanol amine groups are used, alkyls and alkanols will usually contain 1 to 4 carbon atoms and the amines and alkanolamines may be mono-, di- and tri-substituted, such as monoethanolamine, diisopropanolamine and trimethylamine.

A polyethoxylated alcohol sulfate detergent, which is preferred, is that marketed by Shell Chemical Company under the designation Neodol 25-35

The most preferred water-soluble anionic detergent compounds are the ammonium salts and the solubilised and substituted ammonia (such as alkali metal mono-, di- and triethanolamine) and potassium) and alkaline earth metal (such as calcium and magnesium), the higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates.

Among the above-described anionics, the most preferred are linear alkyl benzene sulfonates (ALBS), and especially those characterized by the alkyl group being a straight chain alkyl radical of 12 to 13 carbon atoms.

Synthetic nonionic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an aliphatic organic compound or hydrophobic alkyl aromatic with ethylene oxide (hydrophilic in nature).

Virtually any hydrophobic compound containing a carboxy, hydroxy, amido, and amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or its polyhydric product, polyethylene glycol, to form a nonionic detergent, .

The length of the hydrophilic or polyoxyethylene chain can be easily adjusted so as to achieve the desired balance between the hydrophobic and the hydrophilic groups.

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!

The non-ionic detergent used is preferably a poly (lower alkoxy) lower alkanol, characterized in that the alkanol is formed of 10 to 18 carbon atoms and in that the number of moles

i

lower alkylene (of 2 or 3 carbon atoms) and will be between 3 to 12. Among these materials, it is preferred to use | those wherein the higher alkanol is a fatty alkanol

greater than 11 to 15 carbon atoms and which contain from ^5!

to 9 lower alkoxy groups per mole. Preferably, ! the lower alkoxy is ethoxy, but in some cases it may be desirable to mix it with propoxy, the latter being, in the case of these, a secondary component (less than 5%). Examples of such compounds are those the alkanol having 12 to 15 carbon atoms and having about 7 ethylene oxide groups per mole, for example Neodol ® 25-7 ® Neodol 23-65, products made by Shell Chemical Company Inc. The first is a product of condensation of a mixture of higher fatty alcohols with an average of 12 to 15 carbon atoms with about 7 mole of ethylene oxide, and the second is a corresponding mixture where the carbon atom content of the higher fatty alcohol is from 12 to 13 and the average number of groups of ethylene oxides per mole is about 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol ™ 15-S-7 and Tergitol 15-S-9 which are both linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation.

The first is a mixed ethoxylation product of a linear secondary alkanol having 11 to 15 carbon atoms and 7 mol of ethylene oxide and the second is a similar product where there is a reaction of nine mol of ethylene oxide.

Also useful in the present compositions are the higher molecular weight nonionics with Neodol 45-11 which are similar condensation products with ethylene oxide of higher fatty alcohols, the higher fatty alcohol being of 14-15 carbon atoms and number of ethylene oxide groups per mole of about 11. These products are also manufactured by Shell Chemical Oompany, are also useful.

Zwitterionic detergents such as betaines and sulphobetaines according to the following formula

^R 2,

where R is an alkyl group containing from about 8 to 18 carbon atoms, R 2 and R 3 are each an alkyl or hydroxyalkyl group having about 1 to 4 carbon atoms,

R ₄ is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and X is 0 or S: O. The alkyl group may contain one or more intermediate linkages, such as, amide, ether and polyether linkages or non-

functional groups such as hydroxyl or halogen, which do not substantially affect the hydrophobic character of the group.

When X is C the detergent is called betaine; and when X is S: O, the detergent is called sulfole betaine or sultaine.

The cationic surfactants can also be used. They contain compounds

surfactant detergents which include an organic hydrophobic group which represents part of a cation when the compound P is dissolved in water and an anionic group. The

cationic surface active agents of amine and quaternary ammonium surface. ,

! Cationic detergent examples | Suitable synthetic cos include: normal primary amines ^are

more with the formula EDIL, where E is an alkyl group containing from about 12 to 15 atoms; diamines of the formula;

! Wherein R is an alkyl group containing from about

of 12 to 22 carbon atoms, such as γ-2-aminoethyl | stearylamine; and γ-2-aminoethyl-myristylamine; amines i

? linked to amides such as those having the formula (wherein R1 is an alkyl group containing

about 8 to 20 carbon atoms, such as α-2-amino- ¹

1

tetralyl-amide and N-aminoethyl-myristyl amide; I ate

i

quaternary ammonium units, typically characterized! by one of the groups attached to the nitrogen atom is an alkyl group containing about 8 to 22 carbon atoms and three of the groups attached to the nitrogen atom are alkyl groups containing 1 to 3 carbon atoms including alkyl groups having inert substituents , such as phenyl groups

and an anion such as halogen, acetate, metassulfate, etc. is present. The alkyl group may contain intermediate bonds, such as amide, which do not substantially affect the hydrophobic character of the group, for example, the stearyl amide-propyl-quaternary ammonium chloride are typical quaternary ammonium detergents, ethyl dimethyl chloride benzyl dimethyl stearyl ammonium chloride, trimethylstearyl ammonium chloride, trimethyl cetyl ammonium bromide, dimethyl ethyl lauryl ammonium chloride, dimethyl propyl myristyl ammonium chloride, and the corresponding methasulfates and acetates.

Ampholytic detergents are also suitable for the invention. Ampholytic detergents are well known in the art and many working detergents of this class are described by Schwartz, Peny and Berch in the above-mentioned "Surface Active Agents and Detergent." Examples of

suitable amphoteric detergents include alkyl betaiminodipropionates; alkyl aminopropionates and long chain imidazole derivatives having the generic formula:

RC-N-CILCYLOCYLCOOM

. / ^{2 2 2} OH CH ₂ COO

wherein, in each of the above formulas, R is in the acyclic hydrophobic group, containing about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion.

Specific operating amphoteric detergents include the disodium salt of undecylcicloimidinium-ethoxyethionic acid-2-ethionic, de-acyl beta alanine, and the interim salt of 2-trimethylamino-lauric acid. The detergent bleaching compositions of the invention J may optionally contain a detergent builder of the type widely used in detergent formulations.

Useful builders include any of the conventional water soluble inorganic builder salts, such as, for example, water soluble salts, phosphates, pyrophosphates, orthophosphates, polyphosphates, carbonates and the like. The or- include water-soluble phosphonates, polyphosphonates, polyhydroxysulphonates, polyacetates, carboxylates,

polycarboxylates, succinates and the like. j

i

I

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Specific examples of inorganic phosphate builders include tripolyphosphates, pyrophosphates and hexametaphosphates, and sodium and potassium. ! The organic polyphosphonates specifically include, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid . Examples of these and of ^! other phosphoteric builder compounds are described in U.S. Patents 3 · 213 · 030; 3,422,021;

3,422,137 and 3,400,176. Pentasodium tripolyphosphate and

Tetrasodium pyrophosphate are especially preferred inorganic, water soluble inorganic builders.

Specific examples of non-phosphorous inorganic builders include carbonyl- water soluble bicarbonate. The alkali metal carbonates and bicarbonates, for example sodium and potassium, are particularly useful in this process.

Water soluble organic builders are also useful. For example, the ammonium and substituted ammonium alkali metal polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful builders for the compositions and processes. of the invention. Specific examples of polyacetate and polyoarboxylate builders include the sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilohiacetic acid benzene, polycarboxylic (i.e., penta- and tetra-), carboxymethoxysuccinic acid and citric acid .

Water insoluble builders, in particular complex silicates and more particularly complex sodium aluminosilicates such as zeolites, for example zeolite 4A, a type of zeolite molecule, can be used, characterized in that the monovalent cation is sodium and the pore size of pores is about 4Angstrom.

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The preparation of such a type of zeolite is described in U.S. 3,114,603. The zeolites may be amorphous or crystalline and contain water I

of hydration as is known in the art. It is desirable that an inert water soluble filler salt be included in the laundry compositions of this invention. The alkali metal sulfate is a preferred filler salt, such as potassium, sodium or sodium sulfate, the latter being especially preferred.

Various adjuvants may be included in the laundry detergent compositions of this invention. In general, these include perfumes; dyes; For example pigments and paints; bleaches such as sodium perborate, anti-redeposition agents such as alkali metal salts of carboxymethylcellulose; optical brighteners such as anionic, cationic

pORTUC ^ j

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or non-ionic; foam stabilizers such as alkanolamides and the like, all well known in the art of tissue washing for use in detergent compositions.

Flow promoting agents, commonly referred to as flow aids, may also be used to maintain the particulate compositions, such as free flowing granules or standing.

Starch derivatives and special clays are commercially available as additives to increase the flowability of particulate compositions which would otherwise be sticky and paste. Two of these clay additives are currently marketed under the names "Satintone" and "Microsil".

According to the invention, a preferred bleach detergent composition typically comprises (a) about 2 to 50% by weight of a bleach agent containing a peroxyacid compound and / or a water soluble salt thereof; (b) from about 5 to 50% by weight of a surfactant detergent; (c) of

about 1 to about 60% by weight of a builder salt for detergents; and (d) from about 0.1 to about 10% by weight of a sequestering agent, said composition being substantially free of (i) water soluble silicate compounds and (ii) agglomerate particles which essentially contain said activator, a water insoluble silicate compound and a non-ionic surfactant. The remainder of the composition will contain, predominantly, water, fillers, such as sulphate, sodium and minor additives selected from the various adjuvants described above.

Bleaching detergent compositions

particulate composition of this invention are prepared by adding the bleaching agent and the optional sequestering agent to the spray-dried detergent composition having a last formula in order to avoid the use of more water-soluble silicate compounds especially sodium silicate.

It is contemplated in the present invention in the presence of very small amounts of water soluble silicate composites in the final compositions, i.e., below about 0.5%, preferably below about 0.2%, and most desirably still, not more than about 0.1% by weight as may occur with the use of silicate-containing pigments or paints or by contacting the aqueous slurry of the mixer with the residual amounts of the sodium silicate in the form of spray.

Spray drying of a silicate-free detergent formulation may result in a relatively powdery granular product due to the absence of the silicate as a binder by the spray-dried granules. However, alternative binder materials such as starch, carboxymethylcellulose and materials comparable thereto may be used. The resistance of the spray dried granules can also be increased by maximizing the solids content of the silicate-free paste in the mixer and / or by keeping the temperature as low as possible

of the hot air stream into the spray tower.

The bleaching agent may be mixed either directly with the spray dried powder or with the bleaching agent and the optional sequestering agent may be coated separately

or collectively with coating material, so as to avoid premature activation of the bleaching agent. The coating process is carried out according to methods well known in the art. Suitable coating materials include compounds such as magnesium sulfate, polyvinyl alcohol, lauric acid and the salts thereof and the like.

The detergent compositions of

bleaching agents of the invention are added to the washing solution in an amount sufficient to provide from about 3 to about 100 parts of active oxygen per million parts of solution, a concentration of about 5 to about 40 ppm being generally preferred.

The particulate bleaching detergent compositions described above may be produced by methods such as spray drying, dry blending or agglomeration of the individual components.

Example 1

A preferred silicate-free detergent bleach composition is comprised as follows:

Components

Percentage of body weight

linear alkyl-benzene sulfonate

primary alcohol (11 mol OE per mole of alcohol)

Soap (Carboxylic acid sodium salt θΐ2 "θ22 ^

Pentasodium Tripolyphosphate (TPP)

32.0

EDTA

0.5

monoperoxyphthalic acid (MPPA), magnesium salt

Carboxymethylcellulose

0.5

Optical shakers, pigment and perfume

Proteolytic enzymes

Sodium sulfate and water

0.4

0.5

remaining part

The above product is produced by spray drying an aqueous slurry containing 60% by weight of a mixture containing all

the above components except for the enzymes, perfume, and monoperoxyphthalic acid (MPFA).

The resulting particulate spray product presents particles having the mesh size range of 14 mesh to 270 (US Screeners Series)

The spray-dried product is then mixed in a rotating drum with appropriate amounts of MPEA of the same mesh size, enzymes and perfume to form a particulate product having a moisture content of approximately 14% by weight.

The above described product is used to wash dirty fabrics in the manual process as well as in automatic washing machines, with both washing methods being well washed and whitened.

Other satisfactory products may be obtained by altering the concentrations of the following major components in the compositions described above:

Components

Percentage of body weight

alkyl benzene sulfonate 4-12

ethoxylated alcohol 1-6

Soap 1-10

TPP 15-50

Enzymes 0.1-1

EDTA 0.1-2

MPPA 1-20,

For highly concentrated detergent action detergent powder the alkyl benzene sulfonate, TPP and soap components may be voided in the composition described above and the ethoxylated alcohol content may be increased up to a maximum of 20%.

Example 2

The bleaching tests performed according to the following description comparing the bleaching action of a water-soluble bleach-free detergent composition according to the invention and a corresponding composition containing silicate, the latter composition being comparable to another

in almost all respects, with the exception of the presence of the water soluble silicate compound.

The bleaching agent used is a mixture of monoperoxyfenamic acid salt and sodium perborate. The compositions are formulated by subsequent addition to the particulate detergent composition and spray-dried granules of the H-48 bleaching composition (described in the note to Table 1) to form the detergent bleach compositions A and B shown in Table 1.

The numbers given in the Table represent the percentage by weight of each component in the composition.

Table 1

Component

Composition

THE

(free from silicates) ""

B

(containing silica

J & s) _ J

linear alkyl

Sodium ^{aluminum hydride}

6.00%

ethoxylated primary alcohol (11 mole OE per mole of alcohol)

3.50

Table 1 Ccont)

Component

THE

(free of silicates)

Composition

B

(containing silicates)

Soap (sodium salt of carboxylic acid

12 ° ^"C ^ 22 2.50 2.50 Sodium silicate (Na ₂ O: 2 S: O ₂ ) - 9.00 Tripolyphosphate pentasi sodium (TPF) 35.00 35.00

Optical brighter (stilbene)

0.22 0.22 Sodium perborate tetrahydrate 3.00 3.00 48 ¹ ^ H ^ 9.00 9.00 EDTA (disodium salt) 1.00 1.00 Sodium sulfate 35.00 10.60

Water

remaining part remaining

4

(1)

A bleaching composition sold as "Interox Chemical Ltd.," - ^ ondres, England, containing about 65% by weight of magnesium monoperoxyphthalate, 11% by weight of magnesium phthalate and the balance of _H2O.

Testing Process ₍

The concentration of active oxygen in solution is determined as a function of time for separate washing solutions containing compositions A and B, respectively, using the following process ^:

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A liter of water is introduced; tap a two - liter beaker, which is then heated ^first at a constant temperature of 60 ° C in a water bath boiler. Ten grams of the composition being tested: (A or B) is added to the beaker (time? 0), mixing well to form a uniform washing solution. After certain periods of time (5, 7, 13, 20, 30,

40, and 50 minutes), an aliquot of 5 ml is withdrawn from the lavage solution and the concentration of total active oxygen is determined by the following procedure.

Determination of a Total Asset Concentration 0 ₂

The above 50 ml aliquot part is poured into a 300 ml Erlenmeyer flask containing 15 ml of a sulfuric / molybdenate mixture, the latter mixture being prepared in large quantities, dissolving 0.18 grams of ammonium molybdate in 750 ml of deionized water, to which is added 320 ml of H ₂ SO ₄ (about 36N) under stirring.

The solution is then thoroughly mixed in the Erlenmeyer flask, to which is then added 5 ml of a 10% K1 solution in deionized water. The Erlenmeyer flask is sealed with a stopper, stirred and then left to stand in a dark place for about seven minutes. The solution of the flask is then titrated with 0.1 N sodium thiosulfate solution in deionized water. The required volume of thiosulfate in ml is equal to the concentration of total active oxygen in millimole / liter in the wash solution.

The test results of the two compositions tested are presented below, in Table 2.

Table 2 in solution Time (min) Total Active Oxygen Washing (mmol / liter) A Silicate Free B Containing Silicates 5 4.8 2,4 ' 7 4.4 1.2 15 4.2 1.0 20 5.9 0.8 50 5.7 0.6 40 5.4 0.5 50 5.2 0.4

As shown in Table 2, the silicate-free composition A is significantly more stable and is characterized by a much slower loss of active oxygen from the solution than the corresponding silicate-containing composition B.

Claims

12. A process for the preparation of a bleaching detergent composition in the form of particles, characterized in that said composition comprises:

(a) a bleaching agent consisting of a peroxyacid compound and / or a water-soluble salt thereof; and

(b) at least one surfactant selected from

from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; said bleach detergent composition being substantially free of (i) water soluble silicate compounds and (ii) agglomerated particles J consisting essentially of a mixture of said activator, a water insoluble silicate compound and an agent nonionic surfactant. ;

22. A process according to claim 1, wherein a sequestering agent is also included in said composition.

32. A process according to claim 2, wherein said sequestering agent consists of ethylenediaminetetraacetic acid and / or a water-soluble salt thereof.

42, - Process according to the king.

characterized in that said drying agent,

transt consisting of diethylenetriaminepentamethylene,

phosphonic acid and / or a water-soluble salt thereof.

5 ^a · - Process according to king. characterized in that said branching agent consists of monoperoxyphthalic acid and / or a water-soluble salt thereof.

6. ^A process according to claim 5, characterized in that said bleaching agent consists of magnesium monoperoxyphthalate.

7 ^a · - Process according to king. v. 1, characterized in that said bleaching agent also contains a peroxygen compound.

8 ^a · - Process according to king. v. 7, wherein said peroxygen compound is an alkali metal perborate.

9 ^a · - Process according to king. characterized in that a builder salt for detergents is also included in said composition.

10. ^A process according to claim 9, wherein said builder salt is a zeolite.

11. ^A process according to claim 1, wherein said surfactant is an anionic detergent.

12. ^A process according to claim 11, characterized in that said anionic detergent is a linear alkyl benzene sulfonate.

13.-Process according to the king. A composition according to claim 1, characterized in that a bentonite clay is also included in said composition.

14. A process for the preparation of a bleaching detergent composition, characterized in that it is included in said composition.

(a) from about 1 to about 50% by weight of an agent

I

whitening compound, which consists of a peroxy compound. eido and / or a water-soluble salt thereof

(b) from about 5 to about 50% by weight of an agent

surfactant detergent, selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; '

(c) from about 1 to about 60% by weight of a detergent builder salt; !

(d) from about 0.1 to about 10% by weight of an agent

sequestrant; and ,

(e) the remainder consisting of water and optionally: a filler salt; said composition being. substantially whitening bleach

(i) water-soluble silicate compounds and (i) agglomerated particles consisting essentially of a mixture of said activator, a water-insoluble silicate compound and a nonionic surfactant.

15 ^â · Process according to

! Claim 14, characterized in that said

bleaching consists of monoperoxyphthalic acid and / or

in a salt thereof in water.

-42 '

16. ^A process according to claim 15, wherein said bleaching agent consists of magnesium monoperoxyphthalate.

· Process according ^to claim 17,

I

Claim 14, characterized in that said bleaching agent also contains a peroxygen compound.

^To 18 .- The process according to claim 14, earacterizado in that the structuring agent consists of ethylenediaminetetraacetic acid and / or a water soluble salt. !

I

19 Method according ^to the ί

i

Claim 14, characterized in that the structuring salt) is a zeolite.

20. ^The process of claim 14, wherein said bentonite clay is also included in said composition. i

! i

I. i

· 21 ^to - t earacterizado bleaching process comprises contacting the material with

i

spots and / or stains to be bleached with a solution i; aqueous detergent composition of a bleach granular detergent composition

consisting of:

I

; (a) a bleaching agent consisting of a compound i

peroxyacid and / or a water-soluble salt thereof; ee

(b) at least one surface-active agent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents, said bleaching detergent composition being substantially free of (i) water-soluble silicate compounds and (ii) agglomerated particles consisting essentially of a mixture of said activator, a water insoluble silicate compound and a nonionic surfactant.

22. The process of claim 21, wherein the bleaching agent consists of monoperoxyphthalic acid and / or a water-soluble salt thereof.

^A process according to claim 22, characterized in that said bleaching agent consists of magnesium monoperoxyphthalate.

24. The process of claim 21, wherein the bleaching agent also contains a peroxygen compound.

25. The process of claim 21, wherein said surfactant is an anionic detergent. j

I

26. The process of claim 25, wherein said detergent: anionic is a linear alkyl benzene sulfonate.

27. A process according to claim 21, wherein said composition ¹ also contains a sequestering agent. j

28. A process according to claim 1,

Claim 27, characterized in that said agent

sequestering agent consists of ethylenediaminetetraacetic acid and / or a water-soluble salt thereof.

I

29 ² .- A method according to King vindication 27, characterized in that said sequestering agent consist of diethylene triamine trante acid and / or a water soluble salt.

30. A process according to claim 21, wherein said composition further comprises a builder salt for detergents.

^Â · 31 - Process according to King vindication 30, characterized in that said builder salt consists of pentasodium tripolyphosphate.

32 ² · - Process according to king. characterized in that said structuring salt is a zeolite.

^Â · 33 - Process according to the king. wherein said detergent bleaching composition also contains a clay of the sealing type.