JPH0645799B2 - Granular phosphorus-free wash bleaching composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a particulate phosphorus-free bleach activator containing a wash bleaching composition. The present invention particularly relates to particulate compositions containing a peroxygen bleach activator in the form of an organic peroxyacid bleach precursor that can be used in phosphorus-free granular wash bleaching compositions.

Granular cleaning compositions containing organic bleach activators in addition to common cleaning substances having a cleaning action, builders and peroxygen bleaches are known in the art. Commonly used peroxygen bleaches are bleaches that release hydrogen peroxide in aqueous solution, such as alkali metal perborates, persilicates, percarbonates, perphosphates and urea peroxide. Is mentioned. These peroxygen bleaches are referred to as "persalts" in the text below.
Also called. The most commonly used persalts in detergent compositions are alkali metal perborates, especially sodium perborate tetrahydrate or monohydrate.

The organic bleach activators referred to herein are generally organic N-acyl or O-acyl compounds, or carbonic or pyrocarbonic acid esters, which react with hydrogen peroxide in solution (for example generated from persalts), Unlike persalts, eg ambient temperature to 60 ° C
It forms peroxyacids or percarbonates which are bleaching species effective for bleaching at moderately low temperatures.

Such bleach activators are described in detail in the literature, for example Detergent Age, June 1967, pages 18-20, July.
1967, pages 30-33 and August 1967, pages 26, 27 and 67 published by Allan H. Gilbert in a series of articles, as well as British Patents 836988, 855735, 907356, 907358, 97.
0950, 1003310 and 1246339, U.S. Pat.
32882, 3277750, 4128494 and 4412934.

Examples of active agents that can be used in the present invention are listed below, but by no means as a comprehensive example.

(a) N-diacylation and N, such as N, N, N ', N'-tetraacetylmethylenediamine or -ethylenediamine, N, N'-diacetylaniline and N, N'-diacetyl-p-toluidine. N'-tetraacylated amines or, for example, the compounds 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-
1,3-diacylated hydantoins such as dipropionylhydantoin, (b) compounds N-methyl-N-mesylacetamide, N-methyl-N-mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide, And N-alkyl-N-sulfonylcarbonamides such as N-methyl-N-mesyl-p-methoxybenzamide, (c) N such as monoacetylmaleic acid hydrazide
-Acylated cyclic hydrazides, acylated triazoles or urazoles, (d) such as O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine, Op-methyloxybenzoyl, N, N- O, N, N-trisubstituted hydroxylamines such as succinylhydroxylamine, Op-nitrobenzoyl-N, N-succinylhydroxylamine and O, N, N-triacetylhydroxylamine, (e) e.g. N, N'- N, N'-diacylsulfurylamides such as dimethyl-N, N'-diacetylsulfurylamide and N, N'-diethyl-N, N'-dipropionylsulfurylamide, (f) eg triacetylcyanurate and tribenzoyl Triacyl cyanurates such as cyanurate, (g) such as benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride and 4-chlorophthalic anhydride. Carboxylic acid anhydride, (h) such as sugar esters such as glucose pentaacetate, (i) such as 1,3-diformyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-diacetoxy imidazoline,
1,3-Diacyl-4,5-diacyloxyimidazolines such as 1,3-diacetyl-4,5-dipropionyloxyimidazoline, (j) tetraacetylglycoluril and tetrapropionylglycoluril, (k) e.g. 1,4-diacetyl-2,5-diketopiperazine, 1,4-
Diacylated 2,5-diketopiperazine, such as dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine, (l) propylenediurea And acylated products of 2,2-dimethylpropylenediurea, especially tetraacetyl or tetrapropionylpropylenediurea and its dimethyl derivatives, (m) eg p- (ethoxycarbonyloxy) benzoic acid and p- (propoxycarbonyloxy) benzenesulfone Carbonates such as sodium salts of acids, (n) α-acyloxy- (N, N ′) polyacyl malonamides such as α-acetoxy- (N, N ′)-diacetylmalonamide.

Since these bleach activator compounds are generally hydrolyzable substances, they need to be protected from the surrounding medium when incorporated into the cleaning composition. On the other hand, if it is a suitable method of protecting the bleach activator from the environment, it must be able to release or dissolve it in the wash liquor relatively quickly. The release of the activator must occur well before the end of the wash cycle so as to give the activator time to react with the persalt to form the peroxyacid. Preferably this time should be as early as possible in the wash cycle to maximize the bleaching effect.

The most common way of protecting bleach activators is to make them into granules or agglomerates.

Bleach activator granules of various compositions and morphologies have been proposed in the art, most of which are phosphates due to the ideal property of good structure in relation to the rapid dispersion rate of the granules. , Especially sodium triphosphate is used as an essential component of the granulating agent. A typical example of such a bleaching activator granule composition which gives good storage stability and sufficient release contains a mixture of sodium triphosphate and potassium triphosphate as granulating agent, Compositions such as are used in many commercial detergent powder compositions.

It is true that phosphates such as sodium triphosphate have long been used as wash builders.

However, as phosphates and phosphorus-containing compounds are generally considered to be environmental pollutants, there is a growing legislative move to ban phosphorus from cleaning compositions in many countries, and thus It has been sought to provide detergent compositions that are free or substantially free.

Therefore, in the preparation of such a phosphorus-free cleaning bleaching composition containing a bleaching activator, phosphorus-free bleaching activator granules are obtained when used in a cleaning composition under phosphorus-free conditions. There is also a need to find other plausible bleach activator granule compositions that have comparable physical properties and performance characteristics.

A large number of phosphorus-free builders have been proposed to replace conventional ones, and in particular, for example, British Patent No. 1437950 (Unileve
r), 1481516 (Unilever) and 1481685 (Unilever), and mixtures of alkali metal carbonates such as sodium carbonate with water insoluble calcium carbonate species such as calcite. The phosphorus-free bleach activator particulate compositions of the present invention are specifically intended for use in compositions containing such builders.

Phosphorus-free bleach activator granule compositions are known in the art and various proposals have been made for the preparation of such granules and their use in detergent compositions.

In most cases organic compounds or mixtures of organic compounds have been proposed as binders or coatings, for example nonionic compounds, fatty acids, fatty alcohols, waxes and polymeric substances, to which inorganic salts are optionally added. It may or may not be used.

West German Patent DE-OS2657042 discloses a detergent composition containing granular tetraacetylethylenediamine (TAED), which composition comprises the TAED activator and a nonionic interface having a melting point of at least 35 ° C. as a binder. It consists of an activator.

European Patent EP-B-0051987 (Procter & Gamble) discloses a bleaching activator granule composition consisting of a bleaching activator and as binder a nonionic surfactant having a melting point of 40 ° C. or lower.

The biggest drawback of nonionic surfactants is that they tend to wet out and stick, causing caking problems, especially under high summer temperature conditions. The migration of nonionic surfactants in the composition also tends to promote decomposition of bleach sensitive components by reaction with the oxidative bleaching system. The high melting point of nonionic surfactants leads to poor dispersibility, poor release of bleaching activators, settling of granules and loss of washer dead space, known as mechanical loss. It has unfavorable results. The same is true for fatty acids, fatty alcohols and waxes.

European patents EP-0070474 and EP-0037026 (Henkel) describe the preparation of bleach activator granules with a bleach activator content of 90-99% by weight, as a granulating binder, water-soluble cellulose ethers, starch or starch. A method of using starch ether is disclosed. The method described here is only effective when using coarse particle size bleach activators.

European patent application EP-0075818 (BASF) is a) 70-99.5%
Of bleaching activators according to claim 1, and b) 0.5 to 30% of swelling agent, non-hydrated activator granules, wherein the granules compress compounds a) and b) without the addition of water, optionally Are obtained by grinding the compact into smaller particles.

Examples of the swelling agent include starch, powdered cellulose, high molecular weight carbohydrate such as wood pulp, crosslinked polyvinylpyrrolidone (PVP) and starch ether, and further carboxymethyl cellulose.

None of the above proposals are intended to use such bleach activator granules in phosphorus-free detergent compositions, especially detergent compositions containing an alkali metal carbonate and a calcium carbonate seed material as a builder system.

Therefore, it is an object of the present invention to provide a non-water soluble particulate carbonate material and an alkali metal carbonate which are capable of acting as seed crystals for a precipitate formed by the reaction between water soluble carbonate and calcium hardness ions of water. It can be used in a phosphorus-free granular wash bleaching composition containing as a builder a mixture, for example a mixture of sodium carbonate and calcite, which is toxic to water-insoluble carbonate substances, especially calcite and reduces seed activity. It is an object of the present invention to provide a granular phosphorus-free bleaching activator composition which is effective and stable without blemishes.

Another object of the present invention is a stable and usable phosphorus-free granular wash bleaching composition comprising a phosphate-free builder selected from the group consisting of aluminosilicate cation exchange materials, nitrilotriacetic acid compounds and mixtures thereof. An object is to provide an effective phosphorus-free bleach activator composition.

These objects and other objects will be made clear by the description of the present invention described below, and include an inert non-alkali phosphate-free inorganic or organic salt, and a low carboxylate content or containing it. Water-soluble film-forming polymer material having an average molecular weight of 500 to 100,000
lymeric material) as the granulating agent, and by granulating the finely divided granular bleach activator to a size of about 0.2-2.0 mm.

It is known that calcite is sensitive to poisons and significantly toxic to calcite settling. Therefore, the type of polymeric material used in the present invention is extremely important.

Therefore, the granular bleaching activator composition of the present invention contains substantially no phosphorus substance, and (i) finely divided granular bleaching activator, and (ii) inert, non-alkaline, phosphorus-free Acid salts, water-soluble inorganic or organic salts, and (iii) water-soluble film-forming polymeric substances having an average molecular weight of 500 to 100,000 with a low or no content of carboxylic acid salts.

Suitable bleach activators are the N-diacylated or listed in a) above.
N, N'-tetraacylated amines, especially N, N, N ', N'-tetraacetylethylenediamine, carbonic or pyrocarbonic acid esters mentioned under m) above, and U.S. Pat. No. 4,112,934 and British Patent No. 836988. And reactive phenolic esters as described in U.S. Pat. No. 864798.

Inert, non-alkaline, phosphate-free inorganic or organic salts that can be used in the present invention are, for example, sodium sulfate, sodium nitrate, sodium chloride, sodium citrate, calcium sulfate and calcium chloride. The preferred salt is sodium sulfate.

The film-forming polymeric material with low or no carboxylate content that can be used in the present invention is a polymer having a carboxyl group to polymer weight ratio of less than 1: 5 and can be a homopolymer or a copolymer. These polymers consist of monomers such as vinyl acetate, vinyl pyrrolidone, methyl vinyl ether, styrene and styrene sulfonates, alkyl acrylates and the like. Examples of suitable polymeric materials include polyvinylpyrrolidone, polyvinyl alcohol, copolymers of polyvinyl alcohol and polyvinyl acetate, carbohydrates and carbohydrate ethers such as carboxymethyl cellulose, and vinyl acetate polymers modified with dextrin. Polymers having an average molecular weight of less than 500000, especially less than 100,000 are suitable.

Polymeric materials other than those specified in this invention are unsuitable as they tend to significantly poison calcite.

Effectively, the particulate bleach activator composition comprises: (a) 50-90 wt%, preferably 55-85 wt% bleach activator, and (b) 5-45 wt%, preferably 10-35 wt%. % Inorganic or organic salts, and (c) 1-15% by weight, preferably 5-10% by weight, of polymeric material having low or no carboxylate content.

Water may be present in an amount up to about 5%, preferably 4%.

As explained above, the particulate bleach activator composition contains as a builder a mixture of an alkali metal carbonate such as sodium carbonate and a water insoluble carbonate seed material such as calcium carbonate, such as calcite material. It is particularly applicable to phosphorus detergent compositions.

Therefore, according to one embodiment of the present invention, (i) a cleaning active substance, (ii) a water-soluble carbonate substance that is a cleaning builder, and (iii) a water-insoluble granular carbonate substance that is a seed crystal of calcium carbonate, A wash bleaching composition is provided which comprises (iv) a peroxygen bleaching agent and (v) a phosphorus-free granular bleaching activator composition as defined above, substantially free of phosphorus-containing substances.

The cleaning active can be anionic, nonionic, cationic or zwitterionic, or a mixture thereof.

Nonionic surfactants suitable for use in the present invention include water soluble compounds obtained by condensing ethylene oxide with hydrophobic compounds such as alcohols, alkylphenols, polypropoxyglycols or polypropoxyethylenediamine. Also suitable are alkyl amine oxides, alkyl polyglycosides and alkyl methyl sulfoxides. A suitable nonionic surfactant is 1
A polyethoxy alcohol formed as a condensate of -30 mol ethylene oxide with 1 mol branched or straight-chain primary or secondary aliphatic alcohol having from about 8 to about 22 carbon atoms, and more particularly 6-15 moles of ethylene oxide are condensed with 1 mole of a straight or branched chain primary or secondary aliphatic alcohol having about 10 to about 16 carbon atoms. The designated polyethoxy alcohol is trade name "Neod
commercially available as "ol", "Synperonic" and "Tergitol".

Suitable anionic surfactants for use in preparing the wash bleaching composition of the present invention include water-soluble alkali metal alkylbenzene sulfonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, α-olefin sulphonates, α-sulphocarboxys. Rate and its ester, alkyl ceryl ether sulfonate, fatty acid monoglyceride sulfate and sulfonate, alkylphenol polyethoxy ether sulfate, 2-acyloxyalkane-1
-Including sulfonates and β-alkyloxyalkane sulfonates. Soap can also be used as anionic surfactant. Suitable anionic surfactants are alkylbenzene sulfonates having about 9 to about 15 carbon atoms in the linear or branched alkyl chain, more particularly about 11 to about 13 carbon atoms, about 8 in the alkyl chain. ~ About 22 carbon atoms,
More specifically, alkyl sulfates having from about 12 to about 18 carbon atoms, having from about 10 to about 18 carbon atoms in the alkyl chain and averaging from about 1 to about 12 carbon atoms per molecule. C
Alkyl polyethoxy ether sulphates having H ₂ CH ₂ O- groups, from about 8 to about 24 carbon atoms, more specifically about
Linear paraffin sulfonates having 14 to about 18 carbon atoms, about 10 to about 24 carbon atoms, more specifically about 14
.Alpha.-olefin sulfonates having about 16 carbon atoms and soaps having 8 to 24, especially 12 to 18 carbon atoms.

Suitable cationic surfactants for use in the present invention include quaternary ammonium compounds such as cetyl trimethyl ammonium bromide or chloride and distearyl dimethyl ammonium bromide or chloride, and fatty alkyl amines.

Zwitterionic surfactants that can be used in the present invention include aliphatic substituents in which the aliphatic portion may be linear or branched and contain about 8-18 carbon atoms and an anionic water solubilizing group. Water-soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium cation compounds with aliphatic substituents, especially alkyl dimethyl ammonium propane sulfonates and carboxylates (betaines) and alkyl dimethyl ammonio hydroxypropane sulfonates and carboxylates, which Alkyl groups of the type also contain from about 8 to 18 carbon atoms.

Examples of typical types of surfactants useful in the present invention are Schw
“Surface Active Agents” by artz & Perry, Vol.I
(Interscience 1949) and “Surface Active Agents” by Schwartz, Perry & Berch, Vol.II (Interscience 1
958).

Suitable detersive active compounds are fully described in the above mentioned GB 1437950.

Effective amounts of the detersive active compound used in the composition generally range from 5 to 40% by weight of the composition, preferably up to 30% by weight.

The second essential ingredient of the composition is a water soluble carbonate material as a builder. The material is preferably sodium or potassium carbonate or a mixture thereof for cost and efficiency reasons. The carbonate is preferably sufficiently neutralized, but it may be partially neutralized, for example, part of the standard carbonate salt may be sesquicarbonate, but this partial salt tends to have weak alkalinity. Therefore, the efficiency is low. The amount of water-soluble carbonate substance in the detergent composition can be used in a wide range,
This amount is at least 5% by weight, for example 10 to 40% by weight, preferably 10 to 30% by weight, but for special products amounts up to 75% may be used if desired. The amount of water soluble carbonate material is determined based on the anhydride, but the salt may be hydrated prior to or during formulation into the detergent composition. By the way, under the North American customary conditions of low product concentration, higher levels tend to be required within the preferred range, and in Europe it is lower under high product concentration. Level tends to be required.
It is also desirable to limit the carbonate content to a lower level within the above range in order to reduce the risk of internal harm, for example due to accidental swallowing by a child.

In addition to the water-soluble carbonate material, small amounts of other non-existent substances should be used, provided that the total amount of wash builders does not exceed 85% by weight, so that the content of other desirable ingredients remains in the detergent composition. It is also possible to include a phosphorus cleaning builder.

If soap is used as the cleaning active, it may be present in an amount that contributes as an additional builder.

The composition further necessarily comprises a water insoluble particulate carbonate material. This material must be able to act as seed crystals for the precipitate formed by the reaction between the water-soluble carbonate and the calcium hardness ion of water. Thus, this water insoluble particulate material is a seed crystal of calcium carbonate, eg calcium carbonate itself.

The water-insoluble particulate carbonate material should be finely divided and should have a surface area of at least 10 m ² / g, preferably 15 m ² / g.

Particularly suitable materials have a surface area of 30-100 m ² / g. If economically acceptable, insoluble carbonate materials having a surface area of greater than 100 m ² / g may be used.

Surface area is measured by nitrogen absorption using the standard Bruauer, Emmet & Teller (BET) method. A suitable machine for carrying out this method is a Carlo Erba.Sorpty.1750 instrument, operating according to the manufacturer's instructions.

Most preferably, a high surface area material is provided in the absence of poison to maintain seed activity.

Insoluble carbonate materials usually have an average particle size of less than 10 microns as measured by sieving tests.

When the insoluble carbonate substance is calcium carbonate, any crystalline form or a mixture thereof may be used, but since aralelite and vaterite are not commercially available, calcite is preferable, and calcite is the most common washing temperature. It is slightly inferior in solubility to araleite or vaterite. When using aragonite or vaterite, it is generally used by premixing with calcite. In the general description below, the term "calcite" means either calcite itself or other suitable water insoluble calcium carbonate seed material.

The level of calcite selection in the overall composition depends on the specific surface area as described above. The amount of calcite used in the composition should be 5-60%, more preferably 5-30%.

In another embodiment, the wash bleaching composition of the present invention comprises a phosphate-free builder selected from the group consisting of (i) a wash active and (ii) an aluminosilicate cation exchange material, a nitrilotriacetic acid compound and mixtures thereof. And (iii) a peroxygen bleaching agent, and (iv) a phosphorus-free granular bleaching activator as defined above.

The phosphate-free builder is selected from the group below.

i) The following general formula: (Cat _{2 / n} O) _x · Al ₂ O ₃ · (SiO ₂ ) _y · zH ₂ O (wherein Cat is a cation having a valence n exchangeable with calcium (for example, Na ⁺ Or K ⁺ ), x is a number from 0.7 to 1.5, y is a number from 1.3 to 4 and z has a bound water content of 10 to 2
A crystalline and amorphous aluminosilicate cation exchange material having a value selected to be 8% by weight). Suitable aluminosilicates have the following general formula: Na _x (AlO ₂ ) _x · (SiO ₂ ) _y · zH ₂ O (where x and y are integers of at least 6 and x and y
And the ratio is in the range of 1: 1 to 1: 2, and z is a value selected so that the content of bound water is 10 to 28% by weight). Materials, and a particularly preferred material of the zeolite class is type A zeolites.

ii) Notrilotriacetic acid compounds, especially sodium nitrilotriacetic acid (NTA), and iii) mixtures thereof.

The amount of these builders is 5-80% by weight of the composition, preferably 10-60%. A preferred builder is a mixture of zeolite and sodium nitrilotriacetate.

In addition, other phosphorus-free wash builders known in the art and described in numerous patent publications may be added, such as sodium carboxymethyloxydisuccinate, citric acid, mellitic acid, benzene poly Carboxylic acids and polyacetal carboxylates as disclosed in US Pat. No. 4,144,226 may be added.

The amount of peroxygen bleach used in the composition of the present invention is generally 5 to 30% by weight, preferably 7 to 25% by weight.

The amount of phosphorus-free bleach activator granules incorporated into the composition depends on the bleach activator content of the granule composition and is 0.5 to 15% by weight, more preferably 1.5% by weight calculated as pure bleach activator.
Can be ~ 10% by weight.

For the bleach activator used to prepare the granular bleach activator composition, the particle size should be less than 200 μm, more preferably up to 150 μm.

Suitable bleach activators have a majority particle size of 50-150 μm.
Is a bleach activator. Particle size distributions such as those described in US Pat. No. 4,283,302 are particularly suitable.

Detergent compositions containing the particulate phosphorus-free bleach activator composition may contain any conventional ingredients in amounts generally used in textile laundry detergent compositions.

An example of such an optional component is an alkali metal silicate,
It is especially neutral, alkaline, meta- or sodium orthosilicate. Addition of low levels of silicates, for example 2-10% by weight, is generally advantageous in that it reduces corrosion of the metal parts of textile washing machines, which is beneficial for processing.
Higher levels of silicate content up to a practical maximum of 30% by weight, eg 10-20% by weight, significantly improve detergency and slightly reduce the content of water soluble carbonate substances. You can also This effect appears to be particularly beneficial when using the wash liquor in water with significant levels of magnesium hardness. To some extent, the amount of silicate can also be used to control the equilibrium pH of the wash liquor, which is the pH of an aqueous solution of the composition of the recommended concentration.
Is generally 9 to 11, preferably 10 to 11. It should be noted that higher pH (ie pH above 10.5) makes cleaning more effective, but is not desirable for housekeeping safety. Sodium silicate is commonly available as a concentrated aqueous solution or powder, but the amount is calculated based on the anhydride.

Examples of other optional ingredients include foam boosters such as alkanolamides (especially monoethanolamide derived from palm kernel fatty acids and coconut fatty acids), foam control agents, fabric softeners such as sodium sulfate. Inorganic salts, as well as components that are generally present in very small amounts, include fluorescent agents, fragrances, enzymes such as proteases and amylases, bactericides and colorants. It is beneficial to include an anti-ashing agent to reduce the amount of calcium carbonate deposited on the fiber, especially if the composition is free of anionic detersive actives.

Any technique commonly used in the production of textile laundry detergent compositions may be used to produce the detergent composition, including slurry formation and spray drying, particularly for detergent powder production. Process included.

The present invention is further described below by way of non-limiting examples.

Example I The following granular phosphorus-free bleaching activator composition was prepared.

Composition I wt% TAED (bleach activator) 83.8 Sodium sulphate 9.4 Vinyl acetate polymer 3.1 Water 3.7 TAED (average particle size 50-150 μm) A solid feed consisting of a mixture of 90% and sodium sulphate 10%, polymer 15
% And 85% water with an appropriate amount of an aqueous solution sprayed into a Schugi® Flexomix 160 apparatus. The product was aerated and dried to obtain a product of the above composition having the following properties.

An NTA / zeolite based powder containing sodium perborate monohydrate was stored at 37 ° C./70° RH in a wax laminated carton and examined for storage characteristics.

Detergent powder composition weight% _{C 12} sodium alkyl benzene sulfonate 9.0 primary _C 13 _{-C 15} alcohol / 7 ethylene oxide
4.0 Zeolite 30.4 Sodium nitrilotriacetate (NTA) 4.0 Alkaline sodium silicate 5.7 Sodium succinate 4.4 Sodium carbonate 5.0 Sodium carboxymethylcellulose 0.5 Sodium sulfate 15.4 Water 8.0 Defoamer granules 5.0 Sodium perborate monohydrate 5.5 TAED granules 3.5 Control Granule Composition A wt% TAED (bleach activator) 58-62 Sodium triphosphate 18-22 Potassium triphosphate 13-15 Water 5-7 Example II The following granular phosphorus-free bleach activator (TAED) composition Was prepared.

Granular Composition II Wt% TAED 67.8 Sodium Sulfate 22.6 Vinyl Dextrin Polymer 5.6 Water 4.0 A solid feed consisting of a mixture of 75% TAED (average particle size 50-150 μm) and 25% sodium sulphate with a suitable amount of aqueous polymer solution Schugi ( Spray-fed into a Flexomix 160 instrument. The product was dried in a fluid bed to give a product of the above composition with the following properties.

TAED release: Composition II Peracid yield, peak value (mmol /) 1.18 Peracid yield, peak time (min) 15 Storage results Based on calcite / carbonate, containing sodium perborate monohydrate The powder was stored in a non-laminated carton at 37 ° C / 70 ° RH and examined for storage characteristics.

Toxic to calcite In the presence of 10 ppm STP, a test procedure was adopted in which 1.5 g / sodium carbonate and 0.5 g / calcite (Socal U3) were added to a solution containing 20 ° HCa (as CaCl ₂ ). ,
A simulated test of the poison generated in a normal washing liquid was conducted. 0.15
An effect of TAED granules of g / (based on 100%) was observed. The experiment was carried out at 25 ° C. using Na ₂ SO ₄ and the ionic strength of the solvent was 0.1.

The granules formed according to the invention had no effect on the softening of water, whereas the granules containing toxic substances significantly reduced the softening of water.

Washing Machine Performance Comparison of Calcite / Carbonate + Granule II with Commercial Phosphate Powder and Control Granule A [The commercial phosphate powder used is a German Omo based powder. ] Calcite / carbonate powder composition wt% C ₁₂ Sodium alkylbenzenesulfonate 7.7 Nonionic ethoxylate 3.4 Sodium stearate 3.4 Sodium carbonate 30.0 Calcite 20.2 Sodium silicate 6.0 Enzyme 0.5 Sodium perborate monohydrate 5.5 TAED (100% basis) 2.3 Sodium sulphate / SCMC / water up to 100% 2.5 compositions of 2 bleach sensitive test fabrics were used and 2.5 kg of soiled fibers were loaded into a washing machine of capacity 18 and washed. The reflectance of these fabrics was measured before and after washing and the difference (ΔR ₄₆₀ *) was calculated. As for the washing conditions, after prewashing, heating was performed at 15 to 60 ° C. and a washing cycle of 35 minutes was performed. The hardness of water was 40 ° FH (Ca: Mg molar ratio 4: 1). 80g of each composition is used for prewash and 100g for main wash
g was used. The pH of the washing liquid before and after washing was measured. The results of averaging 6 washes are shown below.

Example III The following granular, phosphorus-free bleach activator (TAED) composition was used with similar good results.

Compositions (wt%) II TAED 83.4 Sodium Sulfate 8.6 Vinyl Acetate Homopolymer 8.0 Granules of granular bleach activator were used in a powder composition based on water-carbonate / calcite. No poison to calcite was observed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display part C11D 7:18) (72) Inventor Raymond Jyon Wild, Merseyside El 63, England 5. KYE, Wirral, Hire Bebington, Stanley Avenyu 9

Claims (10)

[Claims] 1. A cleaning bleaching composition substantially free of phosphorus-containing substances, comprising: (i) a cleaning active substance; (ii) a water-soluble carbonate substance which is a cleaning builder; and (iii) calcium carbonate. Seed crystal water-insoluble particulate carbonate material, (iv) peroxygen bleach, and (v) (a) 50-90 wt% bleach activator, (b) 5-45 wt% unbleached. Active, non-alkaline, phosphate-free,
1 to 15% by weight of a water-soluble inorganic or organic salt, and (c) a water-soluble film-forming polymer substance having an average molecular weight of 500 to 100,000 with a low or no content of the carboxylate salt. A cleaning bleaching composition comprising a granular bleaching activator composition. 2. The cleaning bleaching composition according to claim 1, wherein the water-soluble salt is sodium sulfate. 3. Wash bleaching according to claim 1 or 2, characterized in that the polymeric material is a homo- or copolymer having a carboxyl group to polymer weight ratio of less than 1: 5. Composition. 4. The water-insoluble carbonate substance is calcite, claim 1, claim 2, or claim 3.
The cleaning bleaching composition according to the item. 5. From 5 to 40% by weight of said cleaning active substance,
75% by weight of said water soluble carbonate material, 5-60% by weight of calcite, 5-30% by weight of said peroxygen bleach, 0.5-15%
A cleaning bleaching composition according to claim 4, characterized in that it consists of a weight percent of said bleaching activator. 6. A cleaning bleaching composition that is substantially free of phosphorus-containing materials, the group comprising: (i) a cleaning active material; and (ii) an aluminosilicate cation exchange material, a nitrilotriacetic acid compound, and mixtures thereof. A phosphate-free builder selected from (iii) a peroxygen bleach, and (iv) (a) 50-90% by weight bleach activator, (b) 5-45% by weight inert, Non-alkaline, phosphate-free,
1 to 15% by weight of a water-soluble inorganic or organic salt, and (c) a water-soluble film-forming polymer substance having an average molecular weight of 500 to 100,000 with a low or no content of the carboxylate salt. A cleaning bleaching composition comprising a granular bleaching activator composition. 7. The cleaning bleaching composition according to claim 6, wherein the water-soluble salt is sodium sulfate. 8. A wash bleach according to claim 6 or 7, characterized in that the polymeric material is a homo- or copolymer having a carboxyl group to polymer weight ratio of less than 1: 5. Composition. 9. The cleaning bleaching composition according to claim 6, 7, or 8, wherein the phosphate-free builder is a mixture of zeolite and sodium nitrilotriacetate. 10. 5 to 40% by weight of said cleaning active substance, 5
~ 80 wt% of the phosphate-free builder, and 5-30 wt%
7. The peroxygen bleaching agent according to claim 6 and 0.5 to 15% by weight of the bleaching activator.
The cleaning bleaching composition according to item 7, 8 or 9.