WO1996001887A1

WO1996001887A1 - Powdered bleaching and washing agent

Info

Publication number: WO1996001887A1
Application number: PCT/EP1995/002512
Authority: WO
Inventors: Heinz-Manfred Wilsberg; Rolf Puchta
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-07-07
Filing date: 1995-06-28
Publication date: 1996-01-25
Also published as: DE4424005A1

Abstract

A powdered bleaching and washing agent containing alkaline percarbonate, an alkaline salt of a lower alkyl carboxylic acid with up to 4 carboxyl groups and a total of 1 to 5 carbon atoms which may be substituted by hydroxyl groups and a bleaching activator exhibits improved shelf life.

Description

Powdery bleach and detergent

The invention relates to a powdery bleach and detergent for use in household laundry, which as an additive enhances the cleaning action of a conventional detergent or can be added to the wash liquor as the sole detergent-active agent.

Bleaching agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system with a bleach activator which forms an organic peracid under washing conditions have been known for a long time. The most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates. The activators used are generally those compounds which split off carboxylic acids or percarboxylic acids under hydrolysis or perhydrolysis conditions, predominantly those compounds which give peracetic acid in the presence of the oxidizing agents mentioned are used. Since the reaction of the activator with the peroxygen compound, which is only supposed to take place under the aqueous washing conditions, can also take place during the production and in particular the storage of such agents, as a result of which the availability of the peroxygen compound for the actual purpose of use decreases. has been looking for stabilizers for the bleaching systems mentioned for a long time. For example, the coating of the activator or the oxidation component or both with fatty acids has been proposed. The addition of certain stabilizers, for example magnesium silicate, is also known. The problem of inadequate storage stability is particularly difficult to solve for percarbonate-containing bleaching systems, since this perhydrate is extremely susceptible to hydrolysis and is quickly decomposed by normal atmospheric humidity and also disintegrates in bleaching agents which are stored in water-impermeable packaging, with the loss of active oxygen. On the other hand, the problem is that ^'the perhydrates when they are anhydrous, can decompose explosively. In order to stabilize these perhydrates, a certain amount of water is usually present, or stabilizers are added as described above. German patent application DE 31 41 745 describes, for example, an enzyme-containing bleaching agent composition which contains an inorganic peroxide which is effective for bleaching fabrics, and 0.01 to 5% by weight, based on the total mass of the enzymes, hydrolase, transferase, oxyreductase, Lyase, isomerase, ligase, protease, lipase, cellulase or amylase with an optimal action temperature of 10 ° C to 80 ° C at an optimal pH of 4 to 12, and at least 0.1 to 20 wt .-%, based on the total mass of an anhydrous salt from the series of anhydrous sodium nitrate, anhydrous magnesium sulfate, anhydrous calcium chloride and anhydrous zinc sulfate. The water content of the total mass of the composition described is less than 2% by weight.

European patent application EP 0 407 045 describes a stabilized sodium percarbonate composition which, in addition to sodium percarbonate, also 2.5 to 35% by weight of at least one compound from the group consisting of urea, urea derivatives, acetates, amino acids with no more than contains seven carbon atoms or their salts, triazine compounds and guanidine compounds as stabilizers. Compositions are described which consist only of percarbonate or of a mixture of percarbonate and alkali metal carbonates, dicarbonates, sulfates and borates.

However, the commercially available powdered bleaching and washing agents generally also contain builder substances and surfactants. The builder substances and surfactants can be obtained in powder form by spray drying. However, this product obtained from the spray tower still contains small amounts of water. When the spray dried product is mixed with other substances contained therein to make a bleach and detergent composition, e.g. with percarbonate, there is a risk that the water contained in the spray-dried product will decompose the percarbonate and the bleaching effect of the composition will be reduced to a very low value after a short storage period.

The object of the present invention was to provide a storage-stable bleaching and detergent composition which meets the above Does not have disadvantages and which can also contain comparatively large amounts of water.

The present invention relates to a powdery, bleaching and washing agent which contains alkali percarbonate, an alkali salt of a lower alkyl carboxylic acid with up to 4 carboxyl groups and a total of 1 to 5 carbon atoms, which can optionally be substituted with hydroxyl groups and contains a bleach activator.

The alkali percarbonate contained in the agent according to the invention is preferably sodium percarbonate. Due to the production process, the alkali percarbonate can contain small amounts, normally below 15% by weight, based on the alkali percarbonate, of phosphate and optionally further salts, in particular carbonate, silicate, borate and / or chloride. The percarbonate can be present as a crystallized powder or, optionally with the aid of granulation aids, granulated powder. The alkali percarbonate is preferably used in an amount of 5 to 75% by weight, in particular 15% by weight to 35% by weight.

An agent according to the invention contains an alkali metal salt of a lower alkyl carboxylic acid which may have hydroxyl groups and has a total of 1 to 5 carbon atoms. The alkyl carboxylic acid can carry up to 4 carboxyl groups. Such carboxylic acids are in particular saturated mono-, di- and tricarboxylic acids and preferably formic acid, acetic acid, propionic acid, butanoic acid, glycolic acid, lactic acid, malic acid and tartaric acid and mixtures thereof. In a preferred embodiment, the agent according to the invention contains 1% by weight to 25% by weight, in particular 2% by weight to 10% by weight, of alkali acetate, sodium acetate being preferred. The salts of lower alkyl carboxylic acids used can be used as anhydrous compounds or as compounds containing water of crystallization. The salts of lower alkyl carboxylic acid used according to the invention stabilize the percarbonate. The water contained in the composition according to the invention usually reacts with the percarbonate by hydrolyzing the percarbonate and releasing the oxygen, thereby reducing the bleaching effect of the percarbonate. Surprisingly, it was found that the salts of the lower alkyl carboxylic acids Storage stability of alkali percarbonates can increase, even if these are stored in the presence of amounts of water which are above 5% by weight. The bleaching agent and detergent according to the invention can thus also contain residual water, which can be introduced, for example, by substances which are obtained by spray drying processes, for example in an amount of 5% by weight to 15% by weight, in particular 8% by weight .-% to 13 wt .-%. The water quantities of the powder components given here refer to water which can be expelled when heated to a temperature of 200 ° C.

As a further component, the bleaching and washing agent according to the invention contains at least one bleach activator. Suitable as bleach activator component is any powdery or powdery ready-to-use compound that provides organic peracid under perhydrolysis conditions. These include, in particular, N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, N-acylated triazines, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-tria- tin, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfuryl amides and cyanurates, and also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononylanononoyl phenol Sugar derivatives, especially pentaacetyl glucose. The bleach activator can be coated with coating substances in a known manner or, if appropriate using granulation aids, it can have been granulated and, if desired, contain further additives, for example dye. A bleach activator is preferably used which forms peracetic acid under the washing conditions. Among these, tetraacetylethylenediamine (TAED) granulated with carboxyethylcellulose and having average grain sizes of 0.01 mm to 0.8 mm, as can be prepared by the process described in European Patent EP 037 026, is particularly preferred. TAED is preferably contained in the bleach activator component in amounts of 94% by weight to 99% by weight. The bleach activator component is preferably present in an amount of up to 15% by weight, in particular from 2% by weight to 10% by weight, in the agent according to the invention. The agent according to the invention can contain surfactants which can be selected from the group of synthetic anionic and / or nonionic surfactants and soaps. If appropriate, they can be present in an amount from 2% by weight to 40% by weight, preferably in amounts from 2% by weight to 30% by weight, in particular from 5% by weight to 20% by weight .

Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyana iden or salts of ether carboxylic acids, as are obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used become. The anionic surfactants are preferably used in the form of the sodium salts.

Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, ie of fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the Cin to C20 "0 ^" alcohols and In addition, the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 10 mol of ethylene oxide are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

The surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C9 to C15 alkyl groups, sulfosuccinic acid monoesters and diesters with 6 to 22 C atoms in the alcohol parts and the esters of α-sulfofatty acids, for example the α-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Other useful surfactants of the sulfonate type are the alkanesulfonates which can be obtained from C12- to Ciss-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and also the olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from long-chain monoolefins with a terminal or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

Particularly preferred synthetic anionic surfactants are the alkylbenzenesulfonates with linear Cg to C15 alkyl groups, the fatty alcohol sulfates with 12 to 18 C atoms and mixtures of these surfactants. Anionic surfactant can be contained in the agent according to the invention in amounts of 2% by weight to 40% by weight, in particular 3% by weight to 24% by weight.

Soaps are particularly suitable as further anionic surfactants, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and from natural fatty acids, e.g. Coconut, palm kernel, or tallow fatty acids, derived soap mixtures are suitable. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-Cιg fatty acid soaps and 0 to 50% by weight of oleic acid soap. The detergents according to the invention preferably contain the soaps in amounts of 0.1 to 4% by weight, in particular 0.1 to 3% by weight.

Suitable nonionic surfactants include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear and branched chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 atoms. The degree of alkoxylation of the alcohols is between 1 and 20, preferably 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. In addition, corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal iols and carboxamides, which correspond to the alcohols mentioned with respect to the alkyl ei1s, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can be used. Non-ionic surfactant is preferably in amounts not exceeding 15% by weight, in particular Special from 0.5 wt .-% to 6 wt .-%, based on the finished agent.

An agent according to the invention, in particular if it is a finished detergent, can contain builders as a further constituent. The builders are water-soluble or water-insoluble compounds or a mixture of two or more such compounds. Commercial builder substances can be used. Suitable builder substances are, in particular, those from the classes of polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, phyllosilicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali silicates, in particular sodium silicate, and alkali carbonates, in particular sodium carbonate. The aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts. The preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof. Among the alkali silicates, those with molar ratios of SiO 2 to alkali oxide in the range from 1.5 to 3.0 are preferred. Such builder substances are preferably contained in the composition according to the invention in amounts of 20% by weight to 75% by weight, in particular 25% by weight to 65% by weight.

The individual components of the compositions according to the invention can be mixed and packaged in a manner known per se, the thermally resilient ingredients of the compositions being able to be converted into partial products, so-called compounds, by spray drying an aqueous suspension or slurry, which then subsequently with the thermally sensitive components, in particular the percarbonate. If the agent according to the invention contains nonionic surfactant, it can be sprayed as part of the aqueous slurry or sprayed onto the powder in a known manner after the other components have been spray-dried. If the preparation according to the invention comprises a spray drying step, care must be taken during drying that the spray-dried powder obtained preferably has a water content of 8% by weight to 15% by weight, in particular 8% by weight to 13% by weight. This spray-dried product is preferably produced in such a way that an approximately 30th % By weight to 65% by weight of water-containing suspension of builder substances and surfactant is heated to temperatures from approximately 40 ° C. to 100 ° C. and by means of nozzles under an atomizing pressure of approximately 20 to 120 bar, in particular from 30 to 60 bar a drop chamber is sprayed, into which drying gases are introduced in cocurrent or preferably in countercurrent and have inlet temperatures of from about 150 ° C. to about 350 ° C., in particular from 200 ° C. to 250 ° C. The agent according to the invention preferably has a bulk density of not more than 850 g / 1, in particular from 250 to 800 g / 1 and particularly preferably from 400 to 750 g / 1. It is preferably used as an additive to detergent-containing liquors, in particular in the temperature range from 30 ° C. to 60 ° C., to enhance the bleaching effect (bleach booster). However, it can also be used as the sole detergent-active agent in the wash liquor, in particular if textiles which are to be cleaned are to be cleaned only with relatively small amounts of non-bleachable soiling.

In a preferred embodiment, the agent according to the invention contains, in addition to the salt of the lower alkyl carboxylic acid defined above, an anhydrous or crystal water-containing alkali citrate, in particular sodium citrate 2-hydrate, which can increase the stabilizing effect of the salt of the lower alkyl carboxylic acid. Such alkali salt of citric acid is preferably contained in agents according to the invention in an amount of 1 to 25% by weight, in particular 1 to 10% by weight.

In addition to the above-mentioned components, the washing and bleaching agent according to the invention can contain water-soluble salts as a further powdery component which do not give off water of crystallization in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C. These salts include in particular sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium sulfate and mixtures thereof. Such powdery components are preferably not contained in the agents according to the invention in excess of 35% by weight, in particular from 5% by weight to 25% by weight.

In addition to the constituents mentioned hitherto, the agent according to the invention can contain complexing agents for heavy metals, which have both the storage stability, in particular the percarbonate component, and that Increase the bleaching effect of the bleaching agent according to the invention under conditions of use. Suitable complexing agents include aminopolycarboxylic acids, in particular nitrilotriacetic acid, ethylenedia intetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and l-hydroxyethane-l, l-di-phosphonic acid and their alkali metal salts, in particular their Sodium salts. Such complexing agents are preferably present in amounts not exceeding 10% by weight, in particular from 0.1% by weight to 2% by weight, based on the finished composition. They can be added in any way and are preferably incorporated into the spray-dried powder of builder and surfactant, in which they can be present in particular in amounts of 0.1% by weight to 10% by weight.

The agent according to the invention can also contain further additives customary in bleaching and washing agents, such as enzymes, dyes, optical brighteners and / or fragrances. These constituents are preferably present in amounts of not more than 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total composition. They can be part of one or more powder components or more or less homogeneously distributed over all powder components.

The preparation of the agents according to the invention does not require any major technical effort. Simple mixing apparatuses, such as paddle or drum mixers, in which the powdery components can be mixed, are usually suitable. The use of automatically operating belt scales in combination with free-fall mixers is also possible and is preferred for continuous production of the agents according to the invention. If necessary, the mixture can be carried out with simultaneous spraying of colorants and / or fragrances or liquid enzyme preparations.

In a preferred embodiment, the agent according to the invention contains 20% by weight to 35% by weight of alkali percarbonate, 2% by weight to 10% by weight of alkali metal salt of a lower alkyl carboxylic acid with a total of 1 to 5 carbon atoms, which may also be present Hydroxyl groups can be substituted, 5% by weight to 10% by weight of bleach activator, 5% by weight to 15% by weight of anionic surfactant, 0.1% by weight to 2% by weight of nonionic surfactant, 0.5% by weight up to 2% by weight of soap, 25% by weight to 40% by weight builder, 1 to 6% by weight alkali citrate, 8% by weight to 15% by weight water, 10% by weight to 22 % By weight of water-soluble salts, 0.2% by weight to 3% by weight of complexing agent and 0.1% by weight to 0.5% by weight of optical brighteners.

Examples

A tower powder with the components listed in Table 1 for the tower powder I was mixed with the other components listed in Table 2; the storage stability and the water content of this composition were investigated. The results of the storage tests are given in Table 3. The test results show that the agents according to the invention (Example 1 and Example 2 in Table 3) had a significantly higher content of alkali percarbonate and bleach activator after storage times of 24 weeks than the agents which did not contain an alkali salt of a lower alkyl carboxylic acid.

Essentially the same results were obtained with Tower Powder II, i.e. H. with a higher water content, and with an agent containing only bleach, sodium acetate and bleach activator.

Table 1: Tower powder composition (amount of components in% by weight):

Tower powder I Tower powder II

Component quantity quantity

Alkylbenzenesulfonate 16 16

FA + 5 EO units 1 1 soap ¹ 2 2 optical brightener * ^ 0.3 0.3

Soda 23 20

Magnesium silicate 2 2

Complexing agent'- '1 1

Water glass 3.0, unfiltered. 7 7

Zeolite ⁴ 25 25

Polycarboxylate ^ 7 6.7

Sodium sulfate 3.1 3

Water 12.6 16 1 Edenor HT 35 (manufacturer Henkel)

2 Blankophor ( ^R ) MBBH-766 (manufacturer Bayer AG) and Tinopal ( ^R ) CBS-X (manufacturer Ciba Geigy)

3 Turpinal 4 NL (manufacturer Henkel KGaA)

4 Sasil ( ^R ) (manufacturer Henkel KGaA)

5 Sokalan ( ^R ) CP 5 (manufacturer BASF)

Table 2

Composition Comparative-Comparative-Example Example Example 1 Example 2 1 2

Tower powder I 73 66 46 46 Na percarbonate 27 27 27 27 TAED granules - 7 7 7 Na acetate, H2θ-free - - 20 10 Na citrate-2 hydrate - - - 10 water content [%] (according to Fischer) 10.6 9.8 6.6 9.2

Claims

claims

1. Powdery bleaching and washing agent containing alkali percarbonate, an alkali salt of a lower alkyl carboxylic acid with up to 4 carboxyl groups and a total of 1 to 5 carbon atoms, which can optionally be substituted with hydroxyl groups and a bleach activator.

2. Powdery bleach and detergent according to claim 1, characterized ge indicates that it contains 5 to 75 wt .-% alkali percarbonate.

3. Powdery bleach and detergent according to claim 1 or 2, characterized in that it contains 1 to 25 wt .-% of an alkali salt of a nie¬ whose alkyl carboxylic acid with up to 4 carboxyl groups and a total of 1 to 5 carbon atoms, which optionally with hydroxyl groups sub¬ may be substituted.

4. Powdery bleach and detergent according to one of claims 1 to

3, characterized in that the lower carboxylic acid is selected from the saturated mono-, di- and tricarboxylic acids, in particular from formic acid, acetic acid, propionic acid, butanoic acid, glycolic acid, lactic acid, malic acid and tartaric acid and mixtures thereof.

5. Powdery bleach and detergent according to one of claims 1 to

4, characterized in that it contains 2 wt .-% to 20 wt .-%, in particular 2 wt .-% to 10 wt .-% bleach activator.

6. Powdery bleach and detergent according to one of claims 1 to

5, characterized in that the bleach activator is a compound which forms peracetic acid under washing conditions, in particular N, N, N ', N'-tetraacetylethylenediamine, 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5 -triazine, tetraacetylglycoluril and pentaacetylglucose.

7. Powdery bleach and detergent according to one of claims 1 to

6, characterized in that it additionally contains an alkali citrate, in particular sodium citrate 2-hydrate.

8. Powdery bleach and detergent according to one of claims 1 to 7, characterized in that it contains 2 wt .-% to 40 wt .-%, in particular 2 wt .-% to 30 wt .-%, surfactant.

9. Powdery bleach and detergent according to claim 8, characterized ge indicates that it 3 wt .-% to 24 wt .-% anionic surfactant and / or up to 10 wt .-%, in particular 2 wt .-% to 6 Wt .-% contains non-ionic surfactant.

10. Powdery bleach and detergent according to one of claims 1 to

9, characterized in that it contains, as an additional component, up to 35% by weight, in particular 5% by weight to 20% by weight, of a water-soluble salt in powder form which does not give off water of crystallization from 1 ° C to 45 ° C and whose melting point is above 45 ° C.

11. Powdery bleach and detergent according to one of claims 1 to

10, characterized in that it contains 20 to 90 wt .-% builder.

12. Powdery bleach and detergent according to one of claims 1 to

11, characterized in that it contains 20% by weight to 35% by weight of alkali percarbonate, 6% by weight to 18% by weight of alkali salt of a lower alkyl carboxylic acid with a total of 1 to 5 carbon atoms, which if appropriate may be substituted with hydroxyl groups, 5% by weight to 10% by weight of bleach activator, 5% by weight to 15% by weight of anionic surfactant, 0.1% by weight to 2% by weight of nonionic surfactant , 0.5 wt% to 2 wt% soap, 25 wt% to 40 wt% builder, 1 to 6 wt% alkali citrate, 8 wt% to 15 wt% water , 10% by weight to 22% by weight of water-soluble salts, 0.2% by weight to 3% by weight of complexing agent and 0.1% by weight to 0.5% by weight of optical brighteners.