DE2365269A1 - Adding active ingredients to detergents - with melt-sprayed mixt contg colloidal silica or aluminium silicate swelling in water - Google Patents

Abstract

Particulate active ingredient-free component of detergent additive consists of (A) 20-70% of >=1 satd. fatty acid or fatty alcohol having m.pt. >30 degrees C, (B) 10-50% of at least one water-soluble polyglycol or non-ionic or anionic tenside and (C) 1-20% colloidal SiO2 and/or water-contg. Al silicate, pref. MgAl silicate with ribbon or tubular configuration of the silicate and aluminate gps, capable of swelling in water. Wt. ration (A) : (B) is 5 : 1 to 1 : 2 (3 : 1 to 1 : 1) and mixt. of (A) and (B) pref. has m.pt. > 38 degrees C. Used as additive contg. an active ingredient enhancing washing, bleaching or germicidal activity of powdery detergent compsn. Detergent additive (i) resists storage, e.g. active perborate content of detergent contg. tetraacetyl glycoluril (I), added as bleach activator in additive compsn., is improved from 1% to 85% after 4 weeks at 30 degrees C and 80% RH, w.r.t. control contg. (I) added to liquid concentrate before spraying; (ii) dissolves easily.

Description

Handle ö; Ca * G

Patent department

4000 Düsseldorf, December 27, 1973 ^Dr * ^Wa / ^Ka

Henkelstrasse 67

Patent application D 4866

•? Shelf-life, easily soluble detergent additive and process for its production "

From the Belgian patent 707 285 (corresponding to Dutch patent application 139 356 and Austrian patent 298 642) detergents with a content of granules are known, where these granules consist of an extrudable solid and an embedded substance protected against decomposition. Optical brighteners, germicides, enzymes, fragrances and bleach activators are mentioned as substances to be protected against decomposition, i.e. substances which are not unlimitedly resistant to atmospheric oxygen, moisture, alkalis or bleaching agents. The used for embedding, extrudable protection materials consist for example of fatty acids, polyglycols _r soap and other anionic and in particular nonionic surfactants and water-swollen starch, gelatin and cellulose derivatives. It has been shown, however, that the shelf life and the dissolving properties of such granules are unsatisfactory in many cases. This is the protective effect of water-soluble or water-vapor-permeable embedding materials, for example of polyglycols, cellulose and starch derivatives and surfactants. when using enzymes and, in particular, bleach activators, usually too little if the detergent contains compounds that have a bleaching effect at the same time, for example perborates. Water-insoluble or impermeable to water vapor coating substances, such as fatty acids or Fettaikohole _t in cold or moderately warm wash liquors, for example those below 60 C, do not or only very 'dissolved slowly, so that the' - embedded active substance not to the extent required or in for a laundry process. Available * time is released. The undissolved particles settle on the washed textile and lead to staining. ■ ■ ■ ■ 'p

S09828 /; t0O4

Henkel &Cs;; Gr ^ bH

Patent department

DAS 1 162 967 states that: bleach activators by a coating of fatty acids, polyglycols, water-soluble polymers, fatty alcohols and fatty acid alkanolainides against decomposition in detergents containing bleach _; can protect. Effective protection is only achieved if, as described above, water-impermeable covering materials are used and the particles are completely covered. The same difficulties arise during the dissolution as described above. ■ - -, -

DÖS 2 138 584 describes a bleaching aid that consists of spherical bis droplet-shaped particles with a content of fat ■ acids, water-soluble polyglycols and one embedded therein ΒΐΞ-ichaktivatpr consists and that by spraying the; melted Mixture is available by means of an atomizer disk or a nozzle. These products have a long shelf life and are sufficiently soluble in warm detergent solutions. In the fine or cold wash kingdom, i.e. at, temperature en However, below 40 - 50 C * it can happen that larger resp. coherent particles cannot be completely dissolved with relatively short washing times. The task was therefore to develop a suitable shell material that is effective against the embedded active ingredient even under 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 particle form, one of the detergents, Contains bleaching or germicidal action-enhancing active ingredient and is characterized in that the active ingredient-free component to ■ - "..-.- \"

A) 2 (X - 70% from at least one compound from the class

of saturated fatty acids and fatty alcohols with ■; - ".- a melting point above 30 ° C,

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. Henkel & Cie GmbH

: - ^; ■ Patent Department

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

from the class of Bolyglycols and the - hichtlortisehen and anionic washing active substance » ^,.

C) 1 - 20% from a compound that swells in water

the class of colloidal silicic acid and hydrous aluminum silicates,

the weight ratio of component A: B being -5: 1 to 1: 2, preferably 3: 1 to 1: 1.

Suitable fatty acids in the component mentioned under A. are present, saturated fatty acids and saturated hydroxy fatty acids with 10 to 24 carbon atoms and their mixtures, such as capiin, laurin, myristic, palmitin, stearin, arachin, Behen- unä lignoceric acid as well as the oxystearic and dioxystearic acid. If mixtures of naturally occurring or hydrogenated fatty acids are used, these can also be saturated Fatty acids with 8 to 10 carbon atoms or unsaturated ' Contains fatty acids, e.g. oleic acid, but the proportion of low molecular weight or * unsaturated acids less a, ls 2C wt .-% and especially less than TO% by weight of the total present Fatty acids. The composition of the fatty acid mixtures should be such that the softening or melting " point above 30 C, preferably above 38 ° C.

In component A, instead of the fatty acids, but preferably in a mixture with them, fatty alcohols or fatty alcohol mixtures having 12 to 24 carbon atoms can be present. Lauryl, myristyl, cetyl and stearyl alcohol and mixtures thereof are particularly suitable. If mixtures with fatty acids are used, the weight ratio in component A of fatty alcohol Z; U fatty acid should be 1: 4 to 1: M _f, preferably 1: 3 to 2: 3. The composition should be such that the melting point is above 30 ° C., preferably above 38 ° C. ■ '·. - ^:

509828/1004

:, '.-; .., Henkel & Cie GmbH

■■; · ^! ,;. ί! ^ i · - '-''hi-Ai; Patent department

Suitable for component (B) are water-soluble Polyäthy- • lehgi ^ köie ^ die ^ bei ^ elÄer '^ eliiperätür''' abäiÜaW 3b ^Of C ^ scHineizen and a Moiekuia'rgfewicht "" from ¹ 1 IDÖO to 20 OÖÖ, vbrzucfswii.se 'from 2 ÖOÖ to 10 ÖÖÖ " äüfweitsen. ^ ristelle' der ■ Pöi ^ gtykole ödör 'imrGeffiisch. with ^J these' konhiati äüch" pXast: ifizierb ^ re ähiöniscne "* and / or non-ionic" surfactants are used. " To '3eri "' geeignetenaniönisehen ierisiden count in eirster line Fet € alköHolsuifäte and Pettalkohölpb ^ lyglykoläthersuifate extending 'saturated by ■ and / barren unsaturated Fettaikohoieh with" Derive 12 to • 18 carbon atoms and in the case of Giykoläthersulfate 1 to 4, ilthylenglykoiathergruppen preferably 2 contain. Other useful anionic surfactants are alkyl benzene sulfonates with linear C ₉ -C _1. -Alkyl groups, olefin sulfonates ^ which are obtainable from primary C ^ - C ^ g-olefins by SQ ₃ -Sulfonierung.and subsequent alkaline hydrolysis / and CC sulfo fatty acid esters _t which are derived from saturated C ₁₀ -C fatty acids and C -C alcohols. The anionic surfactants 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 alky! phenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon ■ atoire contained in the residual hydrocarbons. Polyglycol ether derivatives in which the number of deft thy lengl ycol ether groups is 5 to "5 and the hydrocarbon radicals of which are derived from straight-chain, primary alcohols are particularly suitable with 12 to 18 carbon atoms or of alkylphenols with a straight-chain, 8 to 14 carbon atoms Derive an alky chain. , λ

As far as mixtures of Polyglykolenfuhd anionic or nonionic. Surfactants are used, the weight ratio of polyglycol to surfactant can be 10: 1 to 1: 5.

-S-

509828/1004

Henkel & Cie GmbH

i "l "} - '' ■ - .- - ^l K "·„ -.-.-. ■ - ■■: patent department

As a component, ς are suitable in water swelling bears ,; siliceous Compounds, for example colloidal silicon dioxide, as obtained by thermal decomposition of silicon tetrachloride or by precipitation from alkali silicate solutions * Suitable are also hydrous magnesium aluminum silicates, in particular those with a predominantly ribbon or tubular arrangement .the silicate and aluminate groups., They differentiate differ from those predominantly present in a layer lattice structure Montmorilioni th and Bentonites. Let me give you an example commercially available preparation under the name "Veegum" called.

Koiloida3.es silicon dioxide and magnesium aluminum silicate can can also be used together.

As an active ingredient it, together with the aforementioned components are processed into hbmboerien particles, include bleach activators, Enzymes, optical brighteners and germicides and fragrances. Preferred ingredients are bleach activators and enzymes.

Suitable bleach activators which form peracids with per compounds, in particular pernydraters , are N-acyl, O-acyl compounds, and carbonic acid or pyrocarbonic acid esters whose activation value for the per compounds (= titer) is at least 3, preferably at least 4.5 This activation value is determined in the following way:

509828/1004

Henkel & Cie GmbH

Patent department

Solutions * · the "0.615 g / i ^^^

2.5 g / l Wa ^ P ^ O ^ '· 10 H ^ Ö-contained, weMen'hä'öh: Warming: -to .. _: 60 "^ C' with 4 inMöi / l ^: ÄktivaiSor; Ver ^ tzt Huh% ^s 5 ^{': MinatfeTi:} _.Among: .--: ■■ - .. ■ Rifei'eh- AUEF ^v the angegebenen''Temperatur "gehaite &";; ^dana: you gibt- - .; IOP -ml of this liquid.,. On -ein, mixture. vpn _f . 2-5A, g ice and .. 15r ml glacial acetic acid, undy titrated. immediately after adding, yon P, Jfe g. Potassium jpiid with 0.1% Na rivimthiosulfa solution and strength as an indicator; the amount of thiosulfate solution consumed in ml is the activation value (= titer); if the peroxide used were to be activated more than once, it would be 8, Ό * ml?

Of the types to be described below 'vörr Äktivatören · especially compounds mif.einem ^ Schmeizpunkt suitable vbn ^{5 J'} is at least 70 ⁰ C, preferably wenigstensi 100 * ^Q C- / and:; par-:. those of at least 150 ° C. · Next hia soiLl ·: d.äs' Äqüivalejatge-. The weight of these compounds (here, the quotient of the molecular weight and the number of acyl residues or carbonic acid. and in particular be 110 at most. Among the ^{e'rfindungsgemäß:;} useful activators. '- - ^v .

a) the aps of the DBP publications 1 162-967. and 1 2 $ 1 .3I.7 known 'N-diacylated and N, N ¹ -tetraacylxerten amines such as NjNjNSi ^ -Tetraacetyl-methylenediamine or -äthylenediamine -N, N -Diacetylaniline and N, N-diacetyl-5-toliiiäiri or / - l ^ -diacylated hydantoins, such as the compounds l, 3-Diae ^: ethyl-5> 5-dimethyl ^ hydantoin and 1,3-DipFopionyl-hydantoin! ,: ". ■ .. ^ ■

509828/1004

■ '■ - - - - "' '' Patent department

Henkel & Cie GmbH

Patent department

b) the -W- Alkyl · -N.-sulfohyi.-c.arbGnömJd: e · w for example the. compounds - known from (der • toKifcisehe.n ^ Pate ^ tSiChrif ^;:!; 003? N- methyl-N -me sylr.ac0it amid *; jN --Me thy l.-N-nie sy 1 -benzamid , N -Me thyl -;. N-mesyl ~ p-nit.robenzam.id.jfc : and., N-Meth / l-Nrmesyl-p-methoxybönzamid '> :

c) the 407,387 described in the Swiss patent specification is EIIen N-acylierteh cyciischeh HydräzideV ^{r-ac-ylferten} triazoles or tFrazple as z.BY'das Morioa'ce ^ ^^ ■ "■ ... .-

d) those in the DP prefix P '■ _. 17 19 574.3-43 described 0, N, N-trisubstituted hydroxylamines such as, for example, O-benzoyl-NyN-succinylhydroxy.lamin, O-acetyl-NiN-succinyl-hydroxylamine, Op-methoxybenzoyl-Η.,. NS ₁ UCCinyl-hydroxylamine , .Op-nitrobenzoyl-N, N-succinyl · hydroxylamine and 0, N, N-triacetyl-hydroxylamine;

e) the lüs der-DQS 1 .801. 713. known N ^ N'-diacyl-sulfurylamide. b & ispie Lweise NVN'-Dimethyl'i-NiN'-diacetyl-sulfurylamide, and.

N, N ¹ -diithyl-Ν, Ν ¹ -dipropionyl.-sulfurylamide;

f) the triacylcyanurates, for example Trlacetylcyanurai; and
Tribenzoylcyaehurate of DAS 1 294 919;

g) those from Swiss patent specification 347 930 or the
DBP publication 893049 or DOS 1 444 001 known carboxylic acid anhydrides such as benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride;

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

i) the _{1,3-diacyl-4 rf} 5-diacyloxy-imidazolidines of DOS 1 80I 14l, for example the compounds l _i 3-X ^> ii'ormyl-4,5-diacetoxy-imide-

4,5-dipropionyloxy-imidazolidinj: ..... ■

J) the compounds tetraacetylglycoluril known from DOS 1 594 865 and tetrapropionyl glycoluril; · -.,.: '- · -

k) the diacylated 2,5-diketopiperazines described in DP application P 20 38 IO6.O, such as, for example, l ^ -diacetyl ^^ - diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine; , · "- ··"
1,4-Dipropionyl-3 # 6-dimethyl-2,5-diketopiperazine ^ ^v

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509828/1004 '. · ·.

Henkel & Cte GmbH

Patent department

i) those in the DP ÄnineldunK P ^; 21 12 557.5 b & WehrieTDeneii 2 lierüngsprodukte / von ^ rbpyiendiharnstöff or ^! '2 ^ 2-Diifietnyl-: ■ propylenediurea (2,4,6,8-ΐβträazä-bicyclo- (^, J, 1) -nönan-3,7-dione or its 9i9 ~ ^ imethyiderivat} especially the tetraacetyl or the tetrapropionyl propylenedinurea or their dimethyl derivatives;

in) the carbonic acid esters of DOS 1 hhh O2.K, for example the sodium salts of p- (ftthoxycarbonyloxy) benzoic acid and; p-CPropxycarbonyloxyJ-benzenesulfonic acid * _{: Λ}

Of particular practicality. Interest are those mentioned under j) ' acylated glycolurils. ■

The bleach content of particulate detergent additives aktivat.oren should not exceed 75% by weight. Preferably it is 30 to 60% by weight.

509828/1004

Hang! & Cie GmbH

As. Optical brighteners can be used, for example, the derivatives of piaminostilbene disulphohic acid or their alkali metal salts which are suitable for cotton. Suitable are, for example. Salts of. 4., 4 '-Bis (2-anilino-4 ~ morphQlino-1,3,3 ~ triazin ~ 6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the morpholino group Diethanolamino group, a methylamino group or a 2-methoxyethylamino group are sluggish. Brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) ~ 5- (p-chlorophenyl) - 2-pyrazole and similarly structured compounds which, instead of the sulfampy group, have, for example, methoxy carbonyl, 2-methoxyethoxycarbonyl, dioacetylamino or vinylsulfonyl groups. Polyamide brighteners which can also be used are the substituted aminocoumarins, for example 4-methyl-7-dimethylamino or 4-methyl, -7-dläthylamino-coumarin. The compounds 1- (2-benzimldazolyl) -2- (l-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-5-phenyl-7-diethylamino-carbostyril can also be used as polyamide brighteners. As brighteners for polyester and polyamide fibers, the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,; 5-b] -thiophene and l _i 2-di- (5-methyl-2-benzoxazolyl) -ethylene suitable. Furthermore, brighteners of the substituted 4,4'-distyryldiphenyl type can be present; e.g. di3 compound 4,4'-bis (4-aalor-5-sulfostyryl) -diphenyl. Mixtures of the abovementioned brighteners can also be used.

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509828/1004

Henkel & C're GmbH

Patent department

The enzymes to be used are mostly a combination of proteases, amylases and lipases. Of particular interest are the proteases or amylases obtained from bacterial strains or fungi, such as ßacillus subtilis, Bacillus licheniformis or Streptomyces, .griseus, which are relatively resistant to alkali, percompounds and anionic surfactants and are still effective at temperatures of up to 70C -are. Combinations of enzymes of different origins, in particular of proteases and amylases, are also suitable ■ - _{; t} :, ... ·:

Enzyme preparations are usually marketed by the manufacturers as aqueous solutions of the active ingredients or as powders, granulates or as cold-atomized products. She; They often contain sodium sulfate, sodium oxide, alkali ortho-, pyro- or polyphosphate / gallium and magnesium salts, as well as dust-binding oily or paste-like rectifying surfactants, as extrusion agents. These components affect the _; Properties 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.

Suitable germicides are halogenated carbanilides, salicylanilides, Diphenylmethanes, Dipheryläther and Diphenylsulfide , also substituted Thiuramdisulfide and pyridinthiones. Examples include: 2,2'-dihydroxy-3,3 ', 5,5', 6. 6'-hexachlorodiphenylmethane, 2,2'-dihydroxy-S ^ '^ S ^ S'-tetrachlorodiphenylmethane, 2,2'-dihydroxy-3,3' -dibromo-5,5 '-dichlorodiphenylmethane, 2,2 · dihydroxy -3,3 ·, 5 ", 5 '-tetracii.lorai.phenylsulfid, 2-hydaroxy-4,4' -dichlorodiphenylether,. 2-Hydroxy ~" 4, 2 ; ', 4 · -trichlorodiphenyläther and 2-Hydroxy -3.5.5 '"tribromodiphenyl ether.

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509828/1004

-'- "' -" ■■ "'" - ' ^{: o} "' ■■ · ■""^. Henkel & Cie GmbH

■ ■. 'Patent Department

^ c-Wr - ■ '". * -' S" '"2365269 ·.

Several of the above-mentioned active ingredients can also be used together "are present in the particulate agents, for example optical "brighter" together with "enzymes or germicides" Bleaching agents are preferably not mixed with other active ingredients used to "make" direct contact with these to avoid.

The optical content of the particulate detergent additives Brighteners and germicides 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, needles, small compacts or granules, '■ where. whose diameter should be on average 0.1 bi & Im. Such particles can be produced in a manner known per se Manner, 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. You can also use extruded, cylindrical or needle-shaped or irregularly shaped particles in rolling drums approximated to "too" deform spherical particles and thereby the surface downsize in favor of a longer shelf life.

The particles should preferably be approximately in the form of drops to spherical 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, the surface must be smooth. Powder particles containing this Meet the requirements are available in such a way that the active ingredient and the other Koaiponenten at a temperature which is above the melting point of components A and B, homogenized and e.g. using a nozzle below sprayed under high pressure into a fall space in which a temperature

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509828/1004

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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. 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 up to 300 mm and rotates at 800 to 10,000 revolutions per minute, should be 5 to 150 m / sec, preferably 10 to 100 m / sec. be. The fall space in which the sprayed particles solidify expediently consists of a cylindrical chamber, which is equipped with inlets for cooling air and one on the conical. see bottom of the chamber arranged discharge device for the powder is equipped. The I.ühlluft, the temperature of which is at least 10 C below the solidification temperature of the mixture and, for example, -1O ° to. + 40 ° C can be carried out in cocurrent or countercurrent. "

If starting materials of technical purity are used, the sprayed particles can have their own color on iron. By adding dyes or color pigments before atomization or dusting the obtained grains with pigments, for example titanium oxide, the intrinsic color can be covered or changed »

The composite in the manner according to the invention. particulate Detergent additives can be mixed in the usual way with powdery. especially granular detergents; mixed will. Detergents in which the grain size of the detergent particles corresponds to the grain size are particularly suitable corresponds to the agent according to the invention. '

509828/1004

: Henkel & CIe GmbH

It

Patent department

The detergents can be customary, anionic or zwitterionic and nonionic surfactants, water-softening, .and complexing active builders / washing alkalis and anti-graying agents Funds included. Detergents are preferably used that contain bleaching per compounds, in particular sodium perborate. In such bleaching mixtures the detergent additives according to the invention have a high Shelf life. Optionally, the detergents also, several of the additions according to the invention are different Composition and added with different active ingredient content will.

509828/1004

Henkelt Ge GmbH

. Patent department

Correspondingly: the 'composition given in table Ί was. the technically pure PalraitinsSure, containing ^: 2; 5 wt .-% myristic acid and 5 wt / -% stearic acid (itoinponenteÄ) and polyethylene glycol , which had a molecular weight of 10,000 and a melting point of 63 C (component B), melted at 70 ° G and then the additives listed in the table "dispersed therein. The melt was sprayed through a nozzle with 1.5 mm opening diameter at a pressure of 20 atm The cooling air was 19 ° C, the exiting air 21 ° C. The spray powder had a predominantly spherical structure and a sieve analysis revealed the following particle size distribution: over 1.6 now -3%; 1.2 - 0.2 now = 96, 5%; less than 0.2 mm - 0.5%. The mean grain size was 1.3 mm «.

The solution properties were in the; Way determines that, 2 g of the spray powder obtained in 1 liter of tap water from 16 dH or in 1 liter of an aqueous solution containing 0.2% by weight Pentasodium tripolyphosphate and 0.1% by weight Na-n-dodecylbenzenesulfonate contained dissolved (so-called. WAS solution), entered. the The temperature of the water or the solution was 40 ° C. After 30 Minutes. During which the liquid with a magnetic stirrer (Length of the Teflon-coated stirring rod 30 mm, diameter 7 mm) with. a speed of 300 revolutions / minute was stirred, the liquid was filtered through a metal sieve with Q1 / 1 mm mesh size. After drying, the were on The proportions remaining on the sieve are gravimetrically determined. A spray product produced in the same way was used for comparison used, which did not contain component C. The results are shown in Table 1. The percentages mean percentages by weight *

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5 09828/1004

Henkel & Cie GmbH

Patent department

The SiO used was what it was. is a finely divided silica (Aerosil) produced by pyrolysis of SiCl _4. The product labeled Mg-Al-Silicate was a water-containing product with approx. -61% SiO; 14% MgO; 9.5% Al ₉ O-; 2.7% CaO; 2.9% Na ₀ O and 7.2% H ₀ O (, ReSt ₁ Fe ₀ O-, TiO ₀ , K ₀ O). The abbreviation TAQU stands for Tetraacetylglycoluril »

composition 30th 1 2 B e i s 4th P. i e 1 18th 6th 7th 20th 27 24 3 28, 5 0 40 40 % Fatty acid "" - 18th 16 1 £ < 19th 5 26- 35 30th % Polyglycol "" - ■ - _ .- 12th 2, 17th - .- % SiO ₂ 50 5 10 ~ - 5 2 5 10 % Mg-Al-Silicate "- ' 50 50 20th 50 5 - - % TAGU "· ■■ '■ - - 50 - 50 20th 20th % Protease - - Solution behavior 68 (% Residue]" 35 29 .19 38 22nd 14th 40 ° C water Q- 0 2 ' 0 0 0 40 ° C WAS solution O

Tab. 1

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509828/1004

Patent department

The following mixtures were used to test the storage stability produced (in weight S): '

20.0% spray product according to Example 3, '- ■ "^; ■ · .; - · 10.0% sodium perborate tetrahydrate?. ■; ... ... ν ■■■: .. · -.

7.0% n-dodecylbenzenesulphonate (sodium salt) "-;; ^: ' ^: 2.0% oleyl alcohol with 10 ethylene glycol ether groups, 35.0% pentasodium triphosphate
6.0% soda '.. · ..' ■ '- ■ - ■ --- -. ^: · "■;'

3.5% ■ sodium silicate (Ka ₂ O: SiO ₂ = 1: 2).; . ο

2.5% magnesium silicate ^: '■' · ""'-

0.2% Na ethylenediaminetetraacetate '' - - - '^;

0.3% cptic brighteners. '·.

1.0 % atrium carboxymethyl cellulose ^{; :}

7.5% cash ^: - "-.""

The constituents listed in positions 3 to 10 were converted into powder form by hot spray drying of a liquid concentrate. The mixture was filled into folding boxes with a content of 65O g and stored at 20 ° and 70% relative humidity. During the observation period of 10 weeks there was no decrease in the available active oxygen. "

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

5098 2 8 / 100A

"■■■ - · .- ^: -v-- ^: ■.. ·. Henkel & Cie Gi abH

. ·; -: -.-: 'Patent Department

In a second comparative experiment (b) a stearic acid, letraacetylglycoluril used, for its production 75g 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 1.6mm ~ 1%; 1 ■, 6 - 0.2 now = 55%; less than 0.2 nim

In a further comparative experiment that is not considered state-of-the-art (c) were, according to the given in the example Method of operation ^ 40 parts by weight of tetraacetylglycoluril dispersed in 60 g of molten polyethylene glycol with a molecular weight of TO 000 and sprayed *. The sieve analysis of the spherical Particles "· existing powder found: over 1.6 ram .-- · 1%; 1.6 - 0.2 now 98%; below 0.2 ram = 1%. . ._-..._

In. That, c corpses ^ white, .. vnarden 50 parts / parts of tetraacetylcycoluril- in a 50% melt; i part of a fatty alcohol mixed with 30 moles of ethylene oxide (chain length C. , -C, - _c ) dispersing and spraying (experiment d). There were the following. Received sieve fractional amounts; over 1.6mm = 1%; -1.6 - 0.2 rinm = .97. $ i un1; er Q ,, 2 ''

At weekly intervals the proportion of the still effective Per bor at. S titrimetrically determined, the results are in .Table le 2 put together

■ - ^l - - '' ■ '-: ■ .- ------.',. ..: .. ", ■ ■ •% - .. ■. after 3 • Cook 5 .- -. at - ': ■ - ''■' ■■ . "- ■. ;; :,:. · ... ; .. •. . . 1 ....... Perborate 92 4- · 68 ' game "- '. ■ - ■' ■ '- component-'^;; 2 Γ:. 23 85 \ - 3 (.see example) - 82 22nd 1 - a -. - - 86 54 20th 3 i>, Stearic acid 90 59 5 - - C. Polyglycol 77 65 d ethoxylated fatty
alcohol 27

Tab. 2

509828 / 10QA

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. · '· Henkel & Cie GmbH

- "· ■■""· ^Γ - Patent Department

The comparative tests show the superiority of those according to the invention Medium .. ■ --—-----

The following mixtures were obtained by melting and spraying in the manner indicated in Example 1,, h ^ posed. JÄO_ means deposited ethylene oxide).

TAGÜ ^; ■■ '. . '. ■■ - ■: ■ .-: ■■. ---- .-. so ^ci "· ^Ί " ° iö ^f 50 (A) Palmitic acid ': 18 ^{J Mu :;:} Ϊ5 ^β 15th (A) stearic acid ". 17 "" ^Χ0 · ' ^ίε - fs ^ *. ^{; ::} "15 (A) Tallow alcohol 7.5 (B) Tallow alcohol + 5 * & 0 - ■ (B) Na coconut fatty alcohol sulfate 7.5 (C) Mg-AJL silicate
■ - "...... ■ ^. ■ h: u..h ^, ..-.- ·. - ■ - ■■ - ■ - -5 -

The funds dissolved within 10 minutes. in a at 40 _C, C, heated to, solution, 0.2 * sodium tripolyphosphate and 0 _f 1% .na dodecylbenzenesulfonate containing, .so that during filtration through a sieve having O, 1 itmi mesh behind no residue remained. .

^: - 19 -

509828/1004

Claims (11)

Henkel & Cie GmbH -. '■■ "Patent Department P a t e η t a n Proverbs Storage-stable, easily soluble detergent additive in particle form, one the washing, bleaching or germicidal effect ■ reinforcing active ingredient, characterized in that the restaurant part free of fuel 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) TO - 50% of at least one water soluble compound from the class of polyglycols and the non-ionic and anionic washing active substances C) 1 "* ■ 20% from a compound that swells in water consists of the class of colloidal silicic acid and hydrous aluminum silicates, where the weight ratio of component A ': B S: 1 to 1: 2, is preferably 3: 1 to 1: 1 ,. 2. Means according to claim 1, characterized in that the mixture of components A and B has a melting point of above 30.degree. C., preferably above 38.degree. "". 3. Means 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. Composition according to claim 1 and 2, characterized in that component B consists of a fatty alcohol sulfate or fatty alcohol polyglycol ether sulfate which are derived from saturated and / or unsaturated fatty alcohols with 12 to 18 carbon atoms and in the case of the ether sulfates 1 to 4 ethylene glycol ether groups contain. "■. · ■ · 509828 / 100A 5. Composition according to claim 1 and 2, characterized in that component-B consists of polyglycolate derivatives in which the number of ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals are straight-chain, primary ones Alcohols with 12 to 18 carbon atoms or of alkyl phenols with a straight chain containing 8 to 14 carbon atoms Derive alkyl chain. · 6. Means according to claim 1, characterized in that the component C consists of magnesium aluminum silicate with a ribbon or tubular arrangement of the silicate and aluminum groups. 7. Composition according to claim 1 to 6, characterized in that the detergent, bleaching or germicidal effect enhancing Active ingredient from at least one compound from the class of Bleach activators, enzymes, optical brighteners and germicides. - 8. Composition according to claim 7, characterized in that the bleach activator consists of tetraacetylglycoluril. 9. Means according to claim 8> characterized in that the content of bleach activator is 30-60% by weight. " - 21- 50982.8 / 1004 Henkel fiCiaGrril ·! Patent department 10. A method for producing the agent according to claim 1 to 9, characterized in that the melted, homogeneous mixture by means of a nozzle, the opening of which has a diameter of 0.3 to "2.5 mm, preferably from 0.6 to 1.8 mm up / down, under • 2 a pressure of 10 to 30 kg / cm, preferably 15 to 25 kg / ci sprayed into a fall room with a temperature the mi] lies; 2 2 a pressure of 10 to 30 kg / cm, preferably 15 to 25 kg / cm, ti ν
which is at least 10 C below the freezing point of the mixture 11. A method for the preparation of the agent according to claim 1 to 9, characterized in that the molten, homogeneous mixture by means of a spray disc, which at a peripheral speed of 5 to 150 m / sec., Preferably from 10 to 100 n './ sec 'rotates '. sprayed in a falling space in which the temperature is at least 10 C below the solidification point of the mixture. 509828/1004