DE2365268A1 - Storage -stable granular washing powder ingredients - coated with fatty acid or alcohol, polyglycol and cellulose deriv - Google Patents

Abstract

Storage stable, easily-soluble washing agent additives with a washing-, germicidal- or bleaching acceleration effect contain a non-active component consisting of (a) 20-70 wt.% >=1 fatty acid or fatty alcohol with a m.pt >30 degrees C; (b) 10-50 wt.% of >=1 water-sol. cpd. chosen from polyglycols and non-ionic or anionic wash-active agents and (c) 1-40wt.% of >=1 water-sol. or water-swellable cpd. chosen from partially degraded cellulose and cellulose ethers, with a wt. ratio A:B = 5:1 to 1:2, esp. 3-1:1. The additives are useful in washing agents, made eg by extrusion, so that the active ingredients become coates with the compsn. which provides protection against atmospheric air and moisture yet dissolves rapidly on contact with water to release the active agents.

Description

Henkel. & Cie GmbH

Patent department

4000 Düsseldorf, December 27, 1973 Dr. Wa / Ka Henkelstrasse 67

Patent application D 4865

"Durable, easily soluble detergent additive and process for its production "

Detergents containing ai granules are known _for these granules embedded from an extrusion> arene solid and a :, is made against decomposition protected substance from the Belgian Patent 707,285 (jntsprechend Dutch Patent Application 139,356 and Austrian Patent 298 642). As substances to be protected against decomposition, optical brighteners, germicides, enzymes .. fragrances and bleach activators are mentioned, i.e. substances that are not indefinitely resistant to atmospheric oxygen, moisture, alkalis or bleaching agents. The extrudable protective substances used for embedding consist, for example, of fatty acids, polyglycols, soap and other anionic and, in particular, nonionic. Surfactants and starch swollen with water, gelatine and cellulose derivatives. However, it has been shown that the shelf life and the dissolving properties of such granulates are unsatisfactory in many cases. The protective effect of water-soluble or water-vapor-permeable embedding materials, e.g. of polyglycols, cellulose and starch derivatives and surfactants when using enzymes and especially bleach activators, if the detergent contains compounds that have a bleaching effect at the same time, e.g. perborates. Coating substances which are insoluble in water or impermeable to water vapor , such as fatty acids or fatty alcohols, are not dissolved or only dissolved very slowly in cold or moderately warm washing liquors, e.g. those below 60 C, - so that the embedded active ingredient is not dissolved to the required extent or is released in the time available for a washing process. The undissolved particles settle on the washed textile and lead to the formation of stains. ,.

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DAS 1 162 967 states that bleach activators can be coated with fatty acids, polyglycols, water-soluble ones Polymers, fatty alcohols and fatty acid alkanolamides against decomposition in detergents containing bleach. However, effective protection is only achieved if, as above described, waterproof envelope materials used and the envelopment of the particles is complete. It surrendered the same difficulties as described above arise during the dissolution.

DOS 2 138 584 describes a bleaching aid that consists of spherical-- to droplet-shaped particles with a content of iottic acids, water-soluble polyglycols and an embedded B. \ eichaktivator consists of spraying the molten Mixture is available by means of an atomizer disc or a nozzle. These products have a long shelf life and are sufficiently soluble in warm wash liquor * in the fine or cold wash, i.e. at temperatures However, below 40 - 50 ° Cf it can happen that larger resp. coherent particles with relatively short washing lengths cannot be fully resolved. It was therefore the task to develop a suitable covering material that the embedded Active ingredient effective even in unfavorable storage conditions Decomposition protects and already at low temperatures within leads to complete dissolution of the granules and release of the active ingredient in a short time.

The invention relates to a storage-stable, easily soluble Detergent additive in particulate form which contains an active ingredient that enhances the detergent, bleaching or germicidal effect and characterized in that the non-active ingredient to ... . .

A) 20 - 70% of at least one compound from the class.; .. of saturated fatty acids and fatty alcohols with

a melting point above 30 ° C, '

• '.' ■■ · ■ ': ■. '■ ι . - 3 -

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B) 10-50% of at least one water-soluble compound

from the class of polyglycols and nonionic and anionic washing active substances

C) 1 - 40% of at least one water-soluble or water-soluble

Water-swellable compound from the class. the partially degraded cellulose and cellulose

seether exists,
wherein the weight ratio of component A: B 5: 1 to

1: 2, preferably 3: 1 to 1: 1.

Suitable «. Fatty acids in the component mentioned under A. are saturated fatty acids and saturated hydroxy fatty acids with 1O to 24th carbon atoms and their mixtures, like Capr-n-, Laurin-, Myristin-, Palmitxn-, Stearin-, Arachin-, Behenic and lignoceric acid as well as oxystearic and dioxystearic acid. If mixtures of naturally occurring or hydrogenated fatty acids are used, these can also be saturated Contains fatty acids with 8 to 10 carbon atoms or unsaturated fatty acids, e.g. oleic acid, but the proportion of low molecular weight or unsaturated seeds less than 20% by weight and especially less than 10% by weight of the total present Fatty acids. The composition of the fatty acid mixtures should be dimensioned so that the softening or melting point is above 30 ° C., preferably above 38 ° C.

In component A, instead of the; Fatty acids, but preferably mixed with. these, fatty alcohols or fatty alcohol mixtures with .12 to 24 carbon atoms are present. Lauryl, myristyl, cetyl and stearyl alcohol and their mixtures are particularly suitable. If mixtures with fatty acids are used, the weight ratio in component A should be 1 ^? ott- "alcohol to fatty acid J.:" 4 to 1: 1, preferably 1: 3 to 2: 3. The composition should be such that the melting point is above 30.degree. C., preferably above 38.degree. ; . . · '.

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Water-soluble polyethylene glycols which melt at a temperature above 30 ° C. and have a molecular weight of 1,000 to 20,000, preferably 2,000 to 10,000, are suitable for component (B). Plasticizable anionic and / or nonionic surfactants can also be used instead of the polyglycols or in a mixture with them. Suitable anionic surfactants include primarily fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates, which are derived from saturated and / or unsaturated fatty alcohols having 12 to 18 carbon atoms and, in the case of glycol ether sulfates, contain 1 to 4, preferably 2, ethylene glycol ether groups. Further useful anionic surfactants are alkylbenzenesulfonates with linear C ₉ -C ₁ . .-Alky! Groups, olefin, consisting of primary Cj ₂ -C ₁ "olefins by SO ₃ -SuIfonierung undanschlieSende alkaline hydrolysis are available, as well as CC" SuIfofensäureester, derived from saturated C _lo -C _1g fatty acids and C-- Derive C. Alcohols The anionic Tens: .cle are preferably in the form of sodium salts.

The nonionic surfactants suitable for use in component B are primarily polyglycol ether derivatives of alcohols, fatty acids, fatty acid amides and alkylphenols which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Particularly suitable are polyglycol ether derivatives in which the number dej: ethylene glycol ether groups is 5 to 15 and whose hydrocarbon radicals are straight-chain, primary alcohols with 12 to 18 carbon atoms or alkylphenols with a straight-chain , .. B. to derive an alkyl chain containing up to 14 carbon atoms «■ ■; ..- '· -. ''. -

So much for mixtures. from polyglycols and asionic bzvr. not- · ionic surfactants are used, the weight " .Relationship. from polyglycol, to surfactant IO j- 1 to 1s 5.

Component C is partially degraded, so-called microcrystalline Cellulose in question, as obtainable, for example, by thermal degradation of cellulose in the presence of acid and a fiber length of 1 to 150 microns, especially "1 to 50 microns, has »Short-grained or finely ground ones are also suitable native celluloses, the fiber length of which corresponds to that of microcrystalline cellulose. Cellulose ethers can also be used, in particular carboxymethyl cellulose in the form of the alkali salts, preferably the sodium salt, their degree of substitution for example 0.2 to 1 carboxymethyl groups per anhydroglucose unit amounts to. Methyl or hydroxyethyl cellulose or mixed ethers, e.g. methyl carboxymethyl cellulose, are also suitable. Mixtures of different types of cellulose or cellulose ethers can also be used.

As active ingredients which, together with the aforementioned components, are processed into homogeneous particles ·; be, count bleach activators, Egymes, optical brighteners and germicides as well as fragrances. Preferred ingredients are bleach activators and enzymes.

As bleach activators, those with per compounds, in particular Perhydrates, forming peracids, are suitable N-acyl, O-acyl compounds as well as carbonic acid or pyrocarbonic acid esters, whose activation value for the per compounds (= titer) at least 3, preferably at least «1.5. This activation value is determined in the following way:. -.

■■ '"· ■.' ■ ■. - ■ "." ■■ - 6 - ■

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"The 0.615 g / l NaBO ₂ · HgO ₂ · 3 HgO (4 mmol / l) and 2J5 g / l Na ^ PgOy x 10 HgO include solutions, after heating to 60 ⁰ C and 4 mmol / offset l activator and Maintained the specified temperature for 5 minutes with stirring, then add 100 ml of this liquid to a mixture of 250 g of ice and 15 ml of glacial acetic acid and, immediately after adding 0.35 g of potassium iodide, titrate with 0.1 η sodium thiosulphate solution and starch as an indicator ·; The amount of thiosulphate solution used is in ml. D3r activation value (= titer); with a 100% activation of the peroxide used, it would amount to 8.0 ml.

From the bottom to be described types of activators are especially compounds having a melting point of at least 70 ⁰ C, preferably at least 100 ⁰ C and in particular vcn Furthermore, at least I50 C. to the · equivalent weight of these compounds (to be entgewicht under Äquiva ^ the quotient from the molecular weight and the number of acyl residues or carbonic acid or pyrocarbonic acid residues present in the molecule) be at most 170, preferably at most 130 and in particular at most 110. The activators which can be used according to the invention include - ■■ '.':

a) the N-diacylated and N, N * -tetraacylated amines known from the DBP publications 1 162 · 967 and 1 29I 317, such as Ν, Ν, Ν ¹ , N'-tetraacetyl methylenediimine or -ethylenediamine , N, N-diacetylaniline and N, N-diacetyl-'3-toluidine or 1,3-diacylated hydantoins such as the compounds l, 3-diacetyl-5,5 ~ di ~ _i iiethyl hydantoin and 1,3- Dipropionyl hydantoin; / c-_. ;

• - "■ - mm" 7 -

· Ι? O HD

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b) the N-alkyl-N-sulfonyl-carbonamides known from British patent specification 1 003 310, for example the compounds N-methyl-N-mesyl-acetamide, N-methy 1-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamidj

c) those described in Swiss patent specification 407 387. N-acylated cyclic hydrazides, acylated triazoles or urazoles such as Monoacetylmalei.nsäurehydrazidj

d) the Ο, Ν, Ν-trisubstituted described in the DP application P 17 I9 574.3-43 Hydroxylamines such as O-Benzoyl-NjN-sueeinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine, O-p-met.ioxybenzoyl-N, N-suecinyl-hydroxylamine, O-p -nitrobenzoyl-N / N-succinyl hydroxylamine and 0, N, N-triacety .1-hydroxylamine; ·

e) the N, N- '-diacylsulfurylamides known from DOS 1 8OI 713, for example NiN'-dimethyl-N, !! ¹ -diacetyl-sulfurylamidj and Ν, Ν ¹ -dläthyl-Ν, Ν'-dipropionyl-s-ilftirylamidj

f) the triacylcyanurates, for example Triacetylcyanura ·; and Tribenzoyl cyanurate from DAS 1,294,919;

g) those from Swiss patent specification 347 93Ο or the DBP publication 893 049 or the DOS 1 444 00.1 known carboxylic acid anhydrides such as benzoic anhydride, in-chlorobenzoic acid-. anhydride, phthalic anhydride, 4-chlorophthalic anhydride,

li) those known from Swiss patent specification 348 682 Sugar esters, for example glujose pentaacetate;

1) the 1,3-1> iacyl-4,5-diacyloxy-im ^ aazolldine of DOS 1 80I 14l, i for example the compounds l,> - 1> iformyl-4,5-diacetoxy-imidazolidine, i ^ -diacetyl ^^ - diacetoxy-irnicJazolidin, 1,3-diacetyl-, 4,5-propionyloxy-imidazolidinji .. ... _: . . ·

J) the * compounds tetrisacetylglycoluril and tetrapropionylglykolurili ',' known from DOS 1 594 865. ■ ;: '?. ν · |

k = the DP in the application described P) 20 38 106.0 diacy- "· profiled 2,5-Diketopiperaaine such as l _J ~ 4-diacetyl 2,5-diketo" li-4-Dlpropionyl-a, 5 -diketopipepazin;. '■ .... "-_ t

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1) the acylation described in DP application P 21 12 557.5 products of propylenediurea or 2,2-dimethyl-propylenediurea (2,4,6,8 ~ Tetraaza ~ bicyclo- (3,>, l) -nonane-2,7-dione or its 9,9-Dime thy Ideriva t) in particular the Tetraacetyl or the tetrapropionyl propylene diurea or their dimethyl derivatives, *. . . ■.

m) the carbonic acid esters of DOS 1.khh 024, for example the sodium salts of p- (Kthoxycarbonyloxy) -benzoic acid and, p- (Propcxycarbonyloxy) -benzenesulfonic acid »'

Those mentioned under j) are of particular practical interest acylated glycolurils.

Should iichaktivatoren the Gehe.lt the particulate ttaschmittelzüsätze to Bl <75 wt -.% 'Does not exceed. It is preferably 30 to 60% by weight.

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-a *

Optical brighteners for cotton, for example, the appropriate derivatives dör diaminostilbenedisulfonic acid or alkali metal salts in Frage..Geeignet are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3 _i 5-triazin-6- yl-amino) -stilbene-2,2 ^1- disulfonic acid or similarly structured compounds which, instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Suitable brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -> - (p-chlorophenyl) -2-pyrazoline and similarly structured compounds which instead of the sulfamoyl group, for example, the methoxycarbonyl, 2-methoxyethoxycarbonyl, acetylamino or vinyl sulfonyl groups carry. The substituted amino coumarins, for example 4-methyl-7-dirnethylamino- or 4-methyl-7-diethylaminocoumarin, are also useful polyamide whiteners. Furthermore, the compounds 1- (2-benzimidazolyl) ~ 2 » (L-hydroxyätl: yl-2-benzimidazolyl) -äth3 (len and l-ethyl-jJ-phenyl-T-diethylamino-carbostyril can be used. The compounds 2,5-di- ( 2-benzoxazolyl) thiophene, 2- (2-benzoxazolyl) naphtho [2,3 ~ b ^ 3-thiophene and 1,2-di (5-methyl-2-benzoxazolyl) ethylene are also suitable Type of substituted 4,4'-distyryldiphenyl may be present, for example the compound 4,4'-bis (4-chloro-3-sulfοεtyryl) -diphenyl.

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The enzymes to be used are usually a mixture of proteases, Amylases and lipases. Of particular interest are those from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis or Streptomyces.griseus Proteases or amylases, which are relatively resistant to alkali, percompounds and anionic surfactants and are still effective at temperatures up to 70 ° C. Combinations too of enzymes of various origins, in particular of proteases and amylases, are suitable.

Enzyme preparations are usually referred to by the manufacturers as * aq: .ge Solutions of the active ingredients or as powder, granules or as cold-atomized products on the market. They contain frequently used as extender sodium sulphate, sodium chloride, Alkali ortho-, pyro- or polyphosphates,, calcium and magnesium alae as well as dust-binding oily or pasty light ionic surfactants. These constituents adversely affect the joints of the compositions according to the invention not.

The enzyme content of the particulate detergent additives should not exceed 75% by weight. Preferably it is 1 to 60% by weight.

As Geruicide Halogenated carbanilides, salicylanilides, diphenylmethane, diphenyl ether and DiphenylsulfIcIc ₁ are suitable, furthermore substituted thiuram disulfides and pyridinethiones. Examples are: 2,2 * -dihydroxy-3,3 ', 5,5', 6,6 "-hexachlorodiphenylmethane, 2,2 * -dihydroxy-3,3 ', 5,5'-tetrachlorodiphenylmethane, 2,2 '-Dihydroxy-3,3'-dibromo-5,5'-dichlorodiphenyl methane, 2,2'-dihydroxy-3,3 ·, 5,5 · -tetrachlorodiphenyl sulfide, 2-hydroxy-4,4'-dichlorodiphenyl ether, 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether and 2-hydroxy-3,5,5'-tribromodiphenyl ether »· ^;

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It is also possible for several of the above-mentioned active ingredients to be present together in the particulate agents, for example optical brighteners together with enzymes or germicides. Bleach activators are preferably not used in a mixture with other active ingredients / to ensure direct contact with these to avoid.

The amount of optical brighteners and germicides in the particulate detergent additives should expediently be 60% by weight do not exceed. It is preferably 1 to 40%.

Those from components A, B / C and the aforementioned active ingredients composite particles can be in the form of flakes, There are needles, small pellets or granules, with their diameter on average 0.1 bit. T should be mm. Such particles can be produced in a manner known per se, for example by rolling, extruding or granulating, which is followed by grinding if necessary and sifting out the too fine and too coarse. Parts connects. For example, those customary in the tire industry are suitable Devices for the production of soap powder, flakes or needles. Vifeiter can be extruded, cylindrical or needle-shaped or irregularly shaped particles in roll drums approximated to " spherical particles, and thereby deform the surface downsize in favor of a longer shelf life.

The particles should preferably be approximately in the form of droplets to spherical shape and at least 70% by weight, preferably more than 90% by weight have an average diameter of 0.1 to 1 mm. Their composition should be largely homogeneous and the surface should be smooth. Powder particles containing this " Meet the requirements are available in such a way that. the active ingredient and the other components at a temperature those above the melting point of component A and B is, homogenized and, for example, sprayed by means of a nozzle under high pressure into a fall space in which a temperature

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door prevails, which is below the freezing point of the mixture _:. The opening of the spray nozzle should have a diameter of 0.3 to 2.5, preferably 0.6 to 1.8 mm. Of the. The pressure at which the melt is fed to the nozzle should be 10 to 30, preferably 15 to 25 kg / cm. Instead of a nozzle, a rotating spray disk, which can be provided with round or slot-like outlet openings, can also be used. The peripheral speed of such a disk, which usually has a diameter of 150 to 300 mm and rotates at 800 to 1,000 revolutions per minute, should be 5 to 150 m / sec, preferably 10 to 100 m / sec. be. The falling space in which the sprayed particles solidify expediently consists of a cylindrical chamber which is equipped with inlets for cooling air and a discharge device for the powder arranged on the conical bottom of the chamber. The cooling air, the temperature of which is at least 1O C below the initialization temperature of the mixture and, for example, -10 ° bi *; + 40 ° C, can be conducted in cocurrent or countercurrent. .

When using raw materials with technical purity the sprayed particles can have their own color by adding dyes or color pigments before atomization or dusting the resulting grains with pigments, for example titanium oxide, can cover or cover the inherent color. be changed. . .

The "particulate." Detergent additives can be mixed with powdery, in particular granular, substances composed in the usual way be mixed. Detergents in which the grain size of the detergent particles corresponds to the grain size are particularly suitable corresponds to the means according to the invention. ; "". ··.

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The detergents can be customary anionic, zwitterionic and nonionic surfactants, water-softening and complexing agents active builders, washing alkalis and anti-graying agents Funds included. Preference is given to using detergents which contain percompounds with a bleaching effect, in particular sodium perborate contain. In such bleaching mixtures, the detergent additives according to the invention have a high level Storage stability, if necessary, the detergents several of the additives according to the invention of different composition and with different active ingredient content were also added v / earth. '

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B e 1 s ρ 1 e 1 e

Examples 1 to 6

According to the composition given in Table 1 were technically pure palmitic acid, containing 2.5% by weight of myristic acid and 5 wt .-% stearic acid (component A) and polyethylene glycol, which had a molecular weight of 10,000 and a melting point of 63 ° C (component B), melted at 70 ° C and then dispersed the additives listed in the table therein. The melt was through a nozzle With an opening diameter of 1.5 mm, it is sprayed into an atomization chamber with a pressure of 20 atm. The temperature of the entering . countercurrent cooling air was 19 ° C, the exiting air 21 C. The spray powder had predominantly a spherical structure and resulted in a sieve analysis. the following particle size distribution: over 1.6 mm = 3% .; 1.2-0.2mm = 96.5%; below 0.2 mm = 0.5%. The mean grain size was 1.3 µm. '.

The solution properties were determined in such a way that 2 g of the spray powder obtained in 1 liter of tap water of 16 ° dH or in 1 liter of an aqueous solution containing 0.2% by weight of pentasodium tripolyphosphate and 0.1% by weight of sodium n-dodecylbenzene sulfonate contained dissolved (so-called WAS solution), entered. The temperature of the water or the solution was 40 ° C. After 30 minutes, the liquid was stirred with a magnetic stirrer (length of the Teflon-coated stirring rod 30 mm, diameter 7 mm) at a speed of 300 revolutions / Minute was stirred, the liquid was filtered through a metal sieve with 0.1 mm mesh size. After drying, the proportions remaining on the sieve were determined gravimetrically. For comparison, a spray produced in the same way. Product used that does not contain component C. The results are shown in Table 1. The percentages mean percentages by weight.

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The carboxymethyl cellulose (CMC) used had a degree of substitution from 0.5 to. The abbreviation TAGU stands for .Tetraacetylglycoluril.

composition - 1 2 at s ρ i 26th e 1 5 6th 30th 29 27 3 4th 0 40 40 % Fatty acid "' 20th 20th 18th 24 29 30th 30th % Polyglycol - 1 5 16 20th 10 9 % CMC _ _ _ 10 - _ 1 % microcrystalline
Cellulose 50 50 50 _ 1 - - % TAGU "- ■ - - 50 50 20th 20th % Protein .ase - - - " Solution behavior
(% Residue) 68 41 28 16 12th 40 ° C water 35 2 0 20th 0 0 40 ° C WAS solution 0

Tab. 1

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The following devices were used to test the shelf life: produced (in% by weight):

20., 0% spray product according to Example 3 10.0% sodium perborate tetrahydrate

7.0% n-dodecylbenzenesulfonate (Na-Salz)

2.0% oleyl alcohol with 10 ethylene glycol ether groups 35.0% pentanatriurate triphosphate

6.0% soda

3.5% sodium silicate (NaO: SiO ₂ = 1: 2)

2.5%. Agnesium silicate

0.2% Na-A "thy lendiaminotetraacetat 0.3% c-ptische brighteners

1.0% iv sodium carboxy ethyl cellulose '7.5% wetter

The components listed in positions 3 to 10 were through Hot spray drying of a liquid concentrate in powder form been convicted. The mixture was included in folding boxes 65Og content bottled and at 20 ° and -70% relative humidity stored. During the observation period of 10 weeks there was no decrease in the available active oxygen a. '

The packages were heated in the climatic cabinet for comparison tests Stored at 30 C and 80% relative humidity. For comparison, (a) a detergent of the same composition was used, in which the tetraacetylglycoluril, however, is not melted into the powder particles consisting of fatty acid and polyglycol, but was added to the detergent before spraying the liquid concentrate.

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In a second comparative experiment (b) a with stearic acid coated tetraacetylglycoluril used, for the production of which 75 g of tetraacetylglycoluril on a granulating · plate with a solution of 25 g of stearic acid in 75 ml of carbon tetrachloride sprayed and post-granulated until the solvent was removed. The number of sieves of this granulate are: over 1.6 im = 1% j 1.6 - 0.2 ram = 55%; less than 0.2 nim = 44%. '

In a further comparative experiment (c) not belonging to the state of the art, 40 parts by weight of tetraacetylglycoluril were dispersed in 60 g of molten polyethylene glycol with a molecular weight of 10,000 and sprayed in accordance with the procedure given in the example. Sieve analysis of the spherical particle powder found: over 1.6mm ~ 1%; 1.6-0.2mm 98 %; below 0.2mm ~ 1%.

In the same way, 50 parts by weight of tetraacetylglycoluril were dispersed and sprayed in a melt of 50 parts by weight of a coconut fatty alcohol (chain length C _? -C _ir ) reacted with 30 mol of ethylene oxide (experiment d). The following sieve fractions were obtained: over .1.6 mm = 1%; -1.6-0.2mm = 97%; below 0.2 mm = 2%.

The proportion of the still effective perborate was determined titrimetrically at weekly intervals. The results are in label-Ie 2 compiled.

at component 1 % Perborate after 3 Weeks 5 game (see example) 08 2 92 4th
• 68 ' 3 - 82 . 96 23 85 - ■ a "'Itearic acid 86 54 22nd 1 . - - b Polyglycol fiO 59 20th 3 - C. ethoxylated fat
alcohol 77 65 5 - - - d 27

Tab. 2

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The comparative tests show the superiority of those according to the invention Middle.

Examples 7-9

The following mixtures were prepared by melting and spraying in the manner indicated in Example 1 (ÄO means deposited ethylene oxide).

TAGU

(A) palmitic acid

(A) stearic acid

(A) TcJ alcohol

(B) TeJgalcohol + 5 KO

(B) Nc ^ coconut fatty alcohol sulfate

(C) carboxymethyl cellulose

at games 9 7th 8th 50 50 50 15th 18th 15th 15th 17th 15th 7.5 10 -

10

10

7.5

Tab. 2 -

The agents dissolved within 10 minutes in a solution heated to 40, 0.2% sodium tripolyphosphate and 0.1 % Na-dodecylbenzoisulfonate, so that when filtered through i'-in sieves with 0.1 mm mesh size none Residues were left behind.

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Claims (1)

Claims For storage-stable, easily soluble detergent additive in particle form, which contains an active ingredient which enhances the wanching, bleaching or germicidal effect, characterized in that the active ingredient-free component is added A) 20-70% from at least one compound from the class of saturated fatty acids and fatty alcohols with a melting point above 30 ° C, B) 10-50% of at least one water-soluble compound from the class of the polyglycols and the niclr'zionisehen and anionic washing active substances C) 1 - 40% of at least one water-soluble or water-soluble Water-swellable compound from the class the partially degraded cellulose and cellulose ether consists, where the weight ratio of component A: B 5: 1 to 5 1: 2, is preferably 3: 1 to 1: 1. 2. Agent according to claim 1, characterized in that the mixture of components A and B has a melting point of above 30 ° C, preferably above 38 ° C. 3. Composition according to claim 1 and 2, characterized in that component B consists of a polyglycol with a molecular weight of 2,000 to 10,000. 4. Means according to claim 1 'and 2, characterized in that component B consists of a fatty alcohol sulfate or fatty alcohol polyglycol ether sulfate consists of saturated and / or unsaturated fatty alcohols with 12 to 18 carbon atoms. . conduct and in the case of ether sulfates 1 to 4 ethylene glycol ether groups contain. . · 5 0.9828 / 100 3 Hang! SCie GmbH Sheet 2CT for patent application D 4865. - - Patent Department Agent according to claims 1 and 2, characterized in that component B consists of polyglycol ether derivatives / in which the number of ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals are straight-chain, primary alcohols with 12 to 18 carbon atoms or alkyl Derive! phenols with a straight-chain alkyl chain containing 8 to 14 carbon atoms. "6. Means according to claim 1, characterized in that the Component C from carboxymethyl cellulose in the form of the sodium. salt is made. ■ - 7. Means according to claim 1 to 6, characterized in that the active ingredient which increases the washing, bleaching or germicidal action from at least one compound from the class of Bleach activators, enzymes, optical brighteners and the Gerraicide- consists. 8th'. Means according to claim 7, characterized in that the Bleach activator consists of tetraacetylglycoluric1. ■ - 9. Means according to claim 8> characterized in that the content of bleach activator is 30-60% by weight. SO 9828/100 3 Henkel & Cia & nbH Sheet 2f] to the patent application D 4 Q 55 patent department -; -; - .: ■ · 1G. Process for the production of the agents according to Claims 1 to 9, characterized in that the melted, homogeneous fish kettle ^; "a nozzle, the opening of which has a diameter of .-: "- '. - ■" - "' ■ -: 0/3 ibxs .2 ^ 5 Tim -, - preferably from 0.6 to 1.8 mm, under 'R .. · - -eineiü PRINT ¹ M ¹ of IO to 30 kg / cm, preferably 15 to 25 kg / c sprayed in a case space in which prevails a temperature mi: lies". 2 2 a pressure of 10 to 30 kg / cm, preferably 15 to 25 kg / cm, a 's
which is at least 10 C below the freezing point of the mixture 11. Process for the production of the means according to claim 1 to 9, characterized in that the melted, homogeneous Ge. mixed by means of a spray disc that runs at a peripheral speed. speed from 5 to 150 m / sec. , in front of teenagers from 10 to 100 it / sec. rotates, displaced into a fall chamber in which a temperature prevails, which is at least 10 C below the freezing point c'es Mixture lies. '_ ■. · ■ ·.