DK147541B - PROCEDURE FOR THE INCORPORATION OF A USTABLE, PARTICULAR ADDITIVE IN A DETERGENT POWDER, ISSUE ON NON-SOAP BASE - Google Patents

Description

in 147561 o

The invention relates to a method of incorporating in a detergent powder, especially on a non-soap basis, a particulate, unstable additive to improve the whole agent's clarity, purity or germicidal activity, which additive is incorporated into an inert material such as in the form of particles. mix with the other ingredients of the detergent powder.

It is often difficult to satisfactorily incorporate an additive such as a fluorescent substance, a germicide, a clarifier, a cleanser, an enzyme or a perfume 10 into a cleaning agent. Such an additive which is incorporated in the normal manner, e.g. by spraying or melting in coatings for detergent particles, tends to degrade or discolour itself or to be separated from or cause the detergent to clump together.

15 Such additives, where these problems are particularly susceptible to arising and where they are particularly important to avoid, are fluorescent substances and enzymes. Fluorescent substances enhance the detergent's optical clarity and enzymes increase its purity, but only if they are not destroyed or degraded prematurely, especially because lack of stability.

Therefore, attempts have been made to improve particulate detergents containing such additives in various ways.

Thus, British Patent Specification No. 911,410 relates to a web powder containing an unstable additive coated with protective inert material. These detergent compositions, consisting of at least one detergent component and at least one N-chloro compound, in particular N, N'-dichloroisocyanuric acid, are designed in such a way that the N-chloro compound is particulate coated with an inert material, preferably a or more saturated fatty acids with 10-20 carbon atoms. This coating may be applied in various ways. Thus, the British patent first of all mentions that the chlorine compound is introduced into the molten coating agent which is then introduced into the washing powder in particulate form, or

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The chlorine compound can be coated with the respective coating agent dissolved in a volatile solvent which is then evaporated and the coated additive particles thus introduced into the washing powder by simple mixing 5 therewith. However, this does not achieve sufficient stabilization of the additive which is prone to excretion and / or partially destroyed by decomposition, especially after prolonged storage of the washing powder, cf. moreover, the comparative experiments set forth below with precisely the prior art from British Patent Publication No. 911,410.

Similarly, previous attempts have been made to incorporate various substances into the soap, such as volatile liquids, cf. German patent specification 82,424, enzymes cf. British Patent Specification No. 265,024 and fluorescent agents, cf. British Patent Specification No. 596,405. German patent specification No. 82,424 relates, inter alia, to preparation of a detergent by mixing soap chips moistened with salmonia and turpentine with a soap and soda powder. Furthermore, according to Danish Patent No. 64,721, attempts have been made to protect enzymes 20 for incorporation in washing powder, with enzymes being particularly susceptible to destruction by hydrolysis. This is sought to be avoided by impregnating or encapsulating the enzymes in a material which is soluble in the washing solution and is therefore expected to be removed during the use of the detergent so that the enzymes are made available. For this purpose, the enzymes are mixed with a solution (either a true solution or a colloidal solution) of the material in question and then dried. Thereby, a likely granular product is formed which is said to be suitable for admixture with soda and other components in a detergent composition. However, this method is exposed to the disadvantage that the enzymes come into contact with water during the preparation of the granules and are therefore deactivated.

British Patent Specification No. 265,024 also discloses the incorporation of enzymes into soap, namely toiletries,

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3 147541 corpses of soap. Herein, dehydration (at least in part) of the enzymes is suggested with subsequent exclusion of moisture. Thus, a special dehydration step is required to ensure that the enzymes in question retain their effectiveness. This describes tableting to form soap pieces; but as will be understood, these soaps or blocks are subjected to excessive hydration during use, whereby the enzymes are exposed to being deactivated again prematurely. Incidentally, problems with such massive soaps are not quite the same as those found in washing powder.

However, it has now been found that the above disadvantages of e.g. the coating known from British Patent No. 911,410 can be remedied by performing a mechanical processing by grinding and / or extruding a mixture of an additive and a protective material instead. Such mechanical processing by grinding and / or extrusion is not disclosed in any of the above-mentioned writings for the protection of active additives by inert or inert materials, and it is therefore to be considered surprising that instead of making a mechanical incorporation can provide a much more effective protection, cf. the comparison attempt below. On the contrary, those skilled in the art must have feared that such mechanical machining of a mixture of active substances and protective agents by grinding or extrusion preferably under pressure would damage the additive so that the intended effect could not be achieved with absolute certainty. It is noteworthy in this context that e.g. The above-mentioned British Patent Specification No. 911,410 in connection with the coating of the additive preferably indicates spraying or sprinkling thereof as gently as possible. On the contrary, it has now been found that, by a obviously far more risky mechanical processing such as grinding and / or extrusion during incorporation of the additive into the single material, before mixing it in granular form with the rest of the detergent powder, a even a very significant increase in stability, ie. preservation of the activity and improvement of accessibility, namely when mechanically machining the mixture concerned in compliance with the measures described below under points (a) and (b).

Thus, the process of the invention is characterized in that the between polyethylene oxide and polypropylene oxide, a nonionic surfactant, sodium salt of a fatty acid of 8-22 carbon atoms, or a swelling agent, to form a mixture comprising 0.1 to 50% by weight b) the mixture is mechanically processed by grinding and / or extrusion to disperse the additive into the organic extrudable solid and to form granules weighing 0.05-100 mg, and c) the granules are mixed with other constituents of the detergent powder.

These granules prepared by mechanically processing a mixture of an organic extrudable solid and additive contain the additive efficiently and uniformly dispersed throughout the granules.

The particulate detergent containing granules prepared by mechanical treatment of a mixture of an inert material such as extrudable solid and additive retains its initial clarity, purity, germicidal activity, stability and odor virtually unchanged for a very long time and thus has increased shelf life over the above known means.

Since particularly good results have been obtained by stabilizing optical clarifiers, it is preferred according to the invention that

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The additive is an optical clarifier.

Since enzymes have so far caused great difficulties to stabilize, but are now simple and easy to process by the process with good results, it is preferred that the additive is an enzyme. In particular, the remainder of the detergent powder is based on a non-soap detergent which may be an anionic, nonionic, cationic or amphoteric surfactant or a mixture thereof, or the remainder may consist of a material based on a mixture of a non-soap cleanser and soap or a soap-based material.

The process is particularly useful for the preparation of detergent powder containing a surfactant and a builder-containing powder. Among the many useful builder salts are alkaline condensed phosphates, alkaline silicates, alkali metal salts of ethylenediaminetetraacetic acid or mixtures of these builder salts. The granules will not contain such builder salts, except sometimes in very small quantities, when the salt does not act as a builder but as a preservative. Eg. For example, sodium ethylene-20 diamine tetraacetate may be used in this way.

The granules must be compatible with the detergent powder and soluble, or at least dispersible, in an aqueous solution thereof, preferably at 20 ° C. It is preferred that the additive has a solubility of less than 15 x 10 parts by weight as measured in a 0.4% aqueous solution of the detergent at 50 ° C.

The granules usually contain, by weight, between 0.2 and 49%, preferably between 0.5 and 10% of the additive.

Extrudable solid is understood to mean a solid extrudable at temperatures and pressures at which the additive does not decompose.

Examples of suitable organic extrudable solids are polyalkylene oxides, α-olefin sulfonates having 12-20 C atoms, sodium N-coconut fatty acid N-methyl taurate, polyethylene oxide and polypropylene oxide condensates, non-ions.

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147541 6 surfactants and condensates between polyethylene oxide and polypropylene oxide.

A particularly preferred organic extrudable solid is a sodium salt of a fatty acid having 8-22 C atoms. The fatty acid may be branched or straight-chain. If the fatty acid is branched, a preferred variety of compounds contains more than 70% α-methylcarboxylic acids. Branched acids often have improved solubility properties. α-Methyl carboxylic acids have improved biodegradability compared to randomly branched carboxylic acids.

Further examples of suitable organic, extrudable solids are organic substances that absorb moisture and swell, the so-called swelling agents such as starch species (corn and potato starch), pre-made starch, gelatin and cellulose derivatives.

The material forming the granules can be easily processed, which may preferably involve extrusion, to form particles suitable for mixing with the rest of the detergent powder. A particularly suitable physical form can best be described as noodles, but other forms such as shavings, flakes, pellets, strips and threads can be used. The granules can vary considerably in size. Flags may be e.g. square approx. 1 cm on each joint, though preferably square 0.4 cm on each joint, and 0.05 mm thick. Typical granules should, as mentioned, weigh between 0.05 and 100 mg, preferably between 2 and 20 mg.

The granules are obtained by mechanical processing of the mixture of organic extrudable solid and additive by grinding and / or extrusion, thereby distributing the additive uniformly and finely throughout the mass.

Separation of the granules from the particulate detergent powder is generally not a problem as the granules are similar in size to the other particles. If the granules are significantly smaller than the other particles of the detergent powder, mixing may be a problem, but this depends

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7 147541 by the nature of the granules. With granules made according to the invention, problems of excretion will be minimized as the organic extrudable solid, unlike hard inorganic particles, limits mixing.

Examples of granules are noodles with a length of 15 mm and a width of 0.5 mm, small plates with a diameter of 2.5 mm and a thickness of 2.5 mm, chips or flakes with a length and width of 4 mm and a thickness of 0.2 mm and pellets with a cross section of 2.5 mm.

The process avoids the known stability problems in slurry and in spray-drying or spray-cooling processes (difficulties due to the temperature and conditions used, which in the treatment of enzymes render spraying methods totally impracticable and for a number of fluorescent substances, germicides and perfumes cause great difficulties, to which is a considerable dust problem for very active materials, when incorporated into the slurry in a finely divided state, as this poses a danger to the health of the employed workers).

The process according to the invention makes it possible to incorporate a delicate additive into a detergent powder in a simple manner and without any problems regarding dosing, excretion or clumping. In addition, the additive is protected against degradation caused by other ingredients in the detergent powder such as peroxide-containing bleaching components.

The storage stability of the granules can be further improved by coating the granules with a suitable coating material. The coating material, which may be colored to give an attractive appearance, should be soluble or dispersible in water at a temperature of approx. 20 ° C.

In general, the granules should be dissolved or dispersed in water at 20 ° C over 10 minutes, preferably over 2 minutes. The dissolution rate is more important than the absolute solubility. By suitable selection of the ingredients, water-soluble granules can be obtained in water. Water-soluble

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The similarity can be made greater by incorporation into the granulate of a hydrotropic agent.

Suitable coating materials are e.g. sugars, non-ionic detergents and polyvinyl alcohol. In the latter case, preferably, a hydrotropic agent is coated to coat the material.

When the additive is an enzyme which is particularly suitable for incorporation in the process according to the invention, the amount of enzyme is dependent on the activity of the enzyme concerned. The 10 enzymes that can be incorporated can be proteolytic, amylolytic or lipolytic enzymes and mixtures thereof. In particular, proteolytic enzymes may be used, preferably of bacterial origin. In general, enzyme-containing granules are incorporated into detergent powder in an amount such that the final preparation has an activity of 10 -10 maltose units per day. kg of final product when using amylolytic enzymes, and 5-20 anson units per kg of final product when proteolytic enzymes are used.

The enzymes are generally added in the form of a very fine powder which adheres to some coarser powdered inorganic material such as sodium sulfate.

The granules may contain other ingredients desired in detergents, provided these other ingredients do not impair the effect of additives, e.g. dye for identification of the granules.

The granules, especially when the additive is an enzyme, preferably contain a compound which stabilizes or activates the enzyme. Eg. For example, the granules may contain a small amount of a soluble compound containing calcium ions. The compound should comprise less than 5% by weight of the granules. The calcium ion-containing compound may be inorganic. Therefore, according to the invention, it is preferred that a soluble calcium salt is also incorporated into the granules. Examples of useful compounds containing calcium ions are calcium gluconate, glycinate, acetate, butyrate and chloride.

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With amylolytic enzymes it has been found important to keep the enzyme in a reduced state. The enzyme contains groups such as sulfhydryl groups that are easily oxidized. Therefore, the granules preferably contain a small amount of a reducing agent.

With proteolytic enzymes, it has been found that the pH value of the granules is important. Their pH should preferably be below 8.

In a preferred granule for use with proteolytic enzymes, the granules consist of soap, sodium salts of fatty acids having 8-22 C atoms, containing a small amount of free fatty acids as an over-fat.

When incorporating enzymes as the additive together with organic extrudable solids to form granules, especially fatty acid soaps with 8-22 C atoms containing a small amount of free fatty acids are used.

All enzymes should be protected from moisture. It is not known how the water affects their activity; but it is believed that the water works mainly by bringing the enzymes 20 into contact with other detergent powder (in this context harmful components). When the granules are combined with soap, it has surprisingly been found that the water in the soap produced in the normal way, however, is not of particular disadvantage.

By the process of the invention, an improved detergent powder containing both oxidant and additive may be prepared, although the latter is otherwise unstable in the presence of such oxidant. Examples of oxidizing agents are dichloroglycoluril, trichlorocyanuric acid, hypochlorite, sodium perborate and mixtures of sodium perborate 30 with activators such as sodium p-acetylbenzenesulfonate and tetra-acetylethylenediamine. The detergent powder may contain between 5 and 35% by weight sodium perborate.

Any enzyme is unstable in the presence of one or more of such oxidizing agents, but amylolytic enzymes are particularly sensitive.

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Perfumes generally tend to be unstable in the presence of one or more of such oxidizing agents. Particularly influential are the perfumes derived from essential oils. The improvement achieved by the process 5 according to the invention is particularly noteworthy with low-boiling perfumes and with perfumes derived from citrus oils.

Examples of germicides which are unstable in the presence of one or more of such oxidizing agents are e.g. 3,4,4'-trichlorocarbanilide, 3-trifluoromethyl-4,4'-dichlorocarbanilide, 3,5,4'-bromosalicylanilide, 3,5,3 ', 4'-tetrachlorosalicylanilide, 3.5- dibromo-2'-trifluoromethylsalicylanilide, 2,2'-dihydroxy-3,3 ', 5,5', 6,6'-hexachlorodiphenylethane, 2,2'-dihydroxy-3,3 ', 5,5 '-tetrachloro-diphenylmethane, 2,2'-dihydroxy-3,3'-dibromo-5,5'-dichlorodiphenylmethane, 2,2'-dihydroxy-3,3', -15 5,5'-tetrachlorodiphenyl sulfide, 2 -hydroxy-4,4'-dichlorodiphenyl ether, 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether, 2-hydroxy-3,5,4'-tribromodiphenyl ether, tetramethylthiuram disulfide and 2-mercaptopyridine N-oxide ( Zn complex).

Examples of fluorescent substances which are unstable in the presence of one or more of such oxidizing agents are e.g.

2 a) 1,3-diaryl-A-pyrazolines of the general formula N in which R, R and R may be the same or different and e.g. be hydrogen, alkyl, alkoxy, sulfonamide or chloro groups.

b) 4,4'-Triazinylaminostilben-2,21-disulfonic acids or their salts 1 3

R R

V> \ J N yt ..... / N <? ^ -NH- \ -CH = CH- S X -NH- A (II)

R ^ S03H HO3S V

1 2 3 4 where R, R, R and R may be the same or different and e.g. be amino, alkylamino or alkoxy groups.

C) 7-Alkylamino coumarins such as those of the general formula R1

2 I

R -OL

vry

Wherein R, R and R may be the same or different and e.g. 25 alkyl groups having 1-4 C atoms.

d) 7-N-Substituted Quinolines.

e) β-Methylumbelliferone.

f) Sodium 4 - [(naphtho-1 ', 2', 4 ", 5") - 1 ", 2", 3 "-triazol-2" -yl] -stilben-2-sulfonate, and 30 g ) fluorescers G, see below.

Fluorescent fabrics improve the optical brightness of detergent powders as opposed to old-fashioned blue agents which impair clarity, whereas they actually counteracted yellowing of the fabrics by reducing yellow 35 more than blue.

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12

In the process according to the invention, an additive which is liable to hydrolyze either during the process or later storage can also be incorporated into a detergent powder. An example of a fluorescent substance that is prone to hydrolysis is 1- (p-methoxycarbonyl-phenyl) -3- (p-chlorophenyl) -Δ-pyrazoline (fluorescent C).

Often, an additive, when incorporated normally into a detergent powder, colors it in such a way that it cannot be used despite its other merits because the color is unacceptable to the consumer. This disadvantage is also remedied by the invention, wherein the method can be used to incorporate such an additive into a detergent powder.

Enzymes fall into this category as they are usually available in a brown color and this generally becomes 15 more potent when stored.

Examples of germicides that discolour detergents are halogenated phenolic germicides such as 2,2'-dihydroxy - 3.3 ^ 5.5 ^ 6.61-hexachloro-diphenylmethane, 2,2'-dihydroxy-3,3 ', - 5,5'-tetrachloro-diphenylmethane, 2,2'-dihydroxy-3,3'-dibromo-5,5'-dichlorodiphenylmethane, 2,2'-dihydroxy-3,3 ', 5,5'-tetra - Chloro-diphenylsulfide, 2-hydroxy-4,4'-dichlorodiphenyl ether, 2-hydroxy-4,2-41-trichlorodiphenyl ether and 2-hydroxy-3,5,4 * - tribromodiphenyl ether.

Examples of fluorescent substances are e.g. β-me-25 thylumbelliferone, and this fluorescent substance is almost completely non-substantive on textiles, as well as the fluorescent substance (fluorescent G) described in South African Patent Application No. 66/2892 having the formula 30 [0> _c 'V y = \ \ I N-- / \ -CH = (IV) \ HC = v / ^ S'SS03Na i 2 35

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As mentioned above, the problems of adding additive to a slurry of the other components of the detergent prior to spray drying or spray cooling are significant, and the addition of the additive after spray drying or spray cooling also does not provide a satisfactory solution to the problem as the additive then will sink to the bottom and be difficult to dose.

On the contrary, if the additive is added in the form of granules made according to the invention, it is much more effective than if it is added in a conventional manner, ie. before spray drying or spray cooling.

The process of the invention is particularly useful for incorporating additives which have poor solubility in a solution of the detergent. As enzymes usually have high solubility, they usually do not cause such difficulties as additives, but if an enzyme actually had such poor solubility, this aspect would be applicable. By poor solubility is meant a solubility of less than 15 x 40 5 -5 parts by weight, and especially less than 2 x 10 and even more -5 -5 less than 1 x 10 in a 0.4% aqueous solution of the detergent at 50 ° C.

Examples of such low-solubility additives are germicides, e.g. 3,4,4'-trichlorocarbanilide, 3-trifluoromethyl-4,41-dichlorocarbanilide and 3,5,3 ', 4'-tetrachlorosalicylanilide.

Examples of such low-solubility additives are also fluorescent substances, e.g. 1- (p-sulfonamidophenyl) -3- (p-chlorophenyl) -A-pyrazoline (fluorescer A), 1- (m-2-chlorophenyl) -3- (p-acetylaminophenyl) pyrazoline (fluorescer B) fluorescers C, 2-bis- (benzoxazolyl-2 '-) - thiophene (fluorescer D), 1,2-bis- (5'-methyl-benzoxazolyl-2' -) - ethylene (fluorescer E) and 2- styrylnaphth-1,2-oxazole (fluorescent F).

Although the low solubility problem occurs most frequently with fluorescent substances that are substantive on nylon, it also occurs with fluorescent substances that are substantive on cotton, especially when fluorescent substances are required.

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It is suitable for use at low temperatures, e.g. in a pre-detergent. An example of such a fluorescent substance which is substantive on cotton is', Ο-ν. = (V) i / V / (Fluorescer H) / S ° 3H 72 10 o- *

It is difficult and expensive to obtain a low solubility additive in a sufficiently finely divided state that it will readily dissolve, even in a slurry, and provide an appropriate activity. Even when a large comminution has been achieved, the additive is often clumped upon storage in the form of conventional spray-dried detergent powders. The invention reduces such problems.

20 Detergents containing fluorescent substances must be stored and packaged in light-tight cardboard packaging, as fluorescent substances are often decomposed by light when incorporated herein by conventional means. The same problem occurs with certain enzymes and germicides, e.g. 3,5,4f-tribromosalicylanilide, 2,2'-dihydroxy-3,3 ', 5.5', 6,6'-hexachlorodiphenylmethane, 2,2'-dihydroxy-3,3,5,51-tetrachloro -di-phenylmethane, 2,2 '-dihydroxy-3,3'-dibromo-5,5, -dichlorodiphenylmethane, 2,2'-dihydroxy-3,3', 5,5'-tetrachloro-diphenylsulfide, 2-hydroxy-4,4'-dichloro-diphenyl ether, 2-hydroxy-4,2 ', 4'-trichlorodiphenyl ether and 2-hydroxy-3,5,4'-tribromodiphenyl ether. This disintegration reduces the efficiency of the products if stored in glass bottles, as is the practice in many housewives. It also argues that detergent powders are stored in transparent plastic bags that would otherwise be comfortable and acceptable. In the method according to the invention, such losses are counteracted when the products are exposed to light.

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In a preferred embodiment, the granules are prepared with a fatty acid soap of 8-22 C atoms, and the additive, which may be particularly low in solubility, is added to the soap prior to grinding, e.g. by rolling, usually in the last 5 steps during the preparation of the soap. The preferred method for preparing the mixture of the additive and carrier is milling by rolling chips of the mixture. This generally results in the chips being advanced between a number of rollers. Generally, the mixture is rolled several times as it emerges from the mill in the form of thin strips. In the final step of the rolling process, the thin strips are forced to undergo a ripple in order for the support materials to have a suitable shape for extrusion.

The degree of rolling has been shown to affect the improvement of the detergent, which will, however, also depend on the crystal structure and size of the additive and the solubility of the organic extrudable solid.

Enzymes suitable for use in the process of the invention are solid, catalytically active protein - materials that degrade or alter one or more types of dirt or stains and thus help to remove the dirt or stains from the fabric or fabric. object being washed. Enzymes suitable for use in the process of the invention are those which are active in a pH range of from about 4 to approx. 12, and which are preferably active in the pH range of ca. 7 to approx. 11 at a temperature in the range of approx. 10 ° to approx. 85 ° C, preferably from 24 to 80 ° C.

Hydrolases, hydrazes, oxidoreductases and desmolases 30 break down dirt to remove or make it easier to remove, and the transferases and isomerases change the dirt to make it easier to remove. Of these groups, the hydrolases are particularly preferred.

Examples of commercial enzyme products are, for example: 35 Maxatase 40,000, Maxatase 200,000 and Maxatase 300,000 (Konin 147541

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16 clinch Nederlandsche Gist - A Spiritusfabriek N.V., Delft, The Netherlands), Alcalase and Bacteria Proteinase (Novo Industri, Copenhagen, Denmark) and Protease B-400, Protease N-4000,

Protease AP, and Protease AP 2100 (Schweizerische Ferment A.G., 5 Basel, Switzerland).

Among the many surfactants that can be incorporated into the non-granular portion of the detergent powder are sodium, potassium, ammonium and substituted ammonium salts of natural and synthetic fatty acids with 8-22 C atoms, salts 10 of acylaminocarboxylic acids, wherein the acyl group is a group of 10-20 C atoms, alkylarylsulfonates where the alkyl group is branched or straight chain and contains 5-18 C atoms, salts of products obtained by sulfonation of paraffins, salts of products obtained by sulfonation of alcohols, salts of products obtained by sulfonation of olefins, especially β-olefins, condensation products of alkylene oxides, especially ethylene oxide, with a hydrophobic alkyl or aryl group such as an alcohol, a phenol, an acid, an amide or an amine; long chain tertiary amine oxides, phosphine oxides or sulfoxides; ampholytic surfactants such as long chain secondary or tertiary amines where the long. chain is substituted by an anionic group; zwitterionic surfactants such as long chain quaternary ammonium or phosphonium compounds or tertiary sulfonium compounds where the long chain is substituted by an anionic group, and cationic surfactants such as quaternary ammonium compounds containing at least one long chain substituent.

Such surfactants can be used alone or in combination, and the examples given above are only a few of the many that can be used.

The invention will now be illustrated by the following examples.

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Example 1

The basic composition of powders 1 and 2 is: Sodium dodecylbenzenesulfonate 20%

Sodium tripolyphosphate 35% 5 Sodium silicate 10%

Sodium Perborate 10%

Sodium sulphate 23%

Water the residue to 100%. The powder 1 contains 0.08% of fluorescent A dispersed in the concentrated slurry of the above composition prior to spray drying to form detergent powder.

Powder 2 is obtained by mixing a powder of the above composition with 2% noodles made 15 by rolling 4% fluorescent A into soap.

The results of storage experiments are presented in the table where the relative fluorescence activities of the powders are determined by simple nylon washing experiments, the fluorescence activity of powder 2 being set immediately to 100 immediately after preparation.

Table I

Fluorescerings activity

Storage, Powder 1 Powder 2 25 time, days_ (conventional) _ (according to the invention) 0 95 100 35 55 98 60 25 96. 115_13_92_ 30 In this experiment, it is shown that a very marked improvement is obtained when perborate is present.

Powder 1, but not powder 2, discolours yellow-green upon storage.

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Example 2 In a powder of the composition given in the table in Example 1. 0.08% of fluorescent A is dispersed by dispersing the fluorescent substance in the concentrated slurry prior to spray drying (powder 1).

Powder 2 has the same composition and contains the same amount of fluorescent substance, but this is incorporated into the soap dispensers which constitute 0.8% by weight of the entire detergent powder.

The powders are stored at 37 ° C under a relative humidity of 70% in laminated cardboard boxes. The stability of the fluorescent substance is examined as in Example 1. The following results are obtained.

Table II

Powder 1 Powder 2

Time (days) (conventional) (according to the invention) 0 100 100 7 91 106 21 80 91 20 30 76 94 50 41 91 86 5 90

The fluorescence activities of both powders immediately after manufacture are similar and set to 100.

Example 3 In a powder of the composition: Sodium dodecylbenzenesulfonate 20% Sodium tripolyphosphate 35%

10% sodium silicate

Sodium sulphate 22%

Water the residue to 100%, 0.15% fluorescent G is incorporated in the conventional manner to form powder 1: Fluorescer G is added to the slurry.

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19 147541 for spray drying. 10% trichlorocyanuric acid (TCCA) is mixed in the powder. Powder 2 is also prepared with the composition set forth in the above table, and 0.15% fluorescence G, based on the weight of the powder, is incorporated into the powder in the form of 2% soap noodles. 10% TCCA is also mixed in the powder. The powders thus obtained are stored at 37 ° C and .70% relative humidity in laminated cardboard boxes. The stability of the fluorescent substance is investigated. In the study, spent cotton fabrics are machine washed for 3 x 5 minutes at 60 ° C using 10 of 0.4% of the powder and a liquid to cloth ratio of 30: 1. The fluorescence activity of the substances is measured after 15 minutes.

The following results appear:

Table III

Shelf life 00 2 weeks

Fluorescent Activity 100 17 (Powder 1, Conventional)

Fluorescent Activity 100 96 20 (Powder 2, according to the invention)

The fluorescence activity of both powders is similar immediately after manufacture and is set to 100.

The product obtained by incorporating fluorescers G 25 into the powder in the form of noodles has the additional advantage of being acceptable in appearance, while the powder containing the fluorescent substance incorporated in the conventional manner is colored yellow and is unacceptable.

Example 4 4% fluorescence B is mixed in soap by milling on a mill using a rolling gap of 0.051 mm and the mixture is extruded to form noodles. A sufficient number of noodles is added to a non-soap detergent powder which does not contain fluorescent substance and which has the composition specified in the composition of Example 3 (no TCCA) to give a concentration of fluorescent substance of 0.08%, based on the powder. (Powder 1).

The fluorescence activity is determined using a simple nylon wash sample and compared to the activity obtained with the same non-soap detergent in which the normal solid form of fluorescence B has been incorporated in a conventional manner, i. fluorescence B is added to the slurry (Powder 2).

10 The results obtained are presented in Table IV.

Table IV

0.08% Fluorescer B 0.08% Fluorescer B / Carrier Slurry-15 Shelf-life Powder 1 gene Powder 2 (days) _ (according to the invention) _ (conventional)

Fluorescence Activity 0 100 92 150 100 77 20

Example 5

Noodles are made from soap containing 4% fluorescence B. A sufficient quantity of powder is added to the powder of the composition specified in the Table in Example 3 to achieve a concentration of 0.15% fluorescent substance based on the powder. (Powder 1).

To half of powder 1 is added 10% sodium perborate to form powder 2.

Powders 3 and 4 are prepared with the same composition as powders 1 and 2, respectively, but do not contain noodles; the same amount of fluorescent substance is added but to the slurry prior to spray drying.

The relative fluorescence activities are determined. Table V gives the results after storage in laminated cardboard boxes at 37 ° C and 70% relative humidity.

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Table V

Powder 1 Powder 2 Powder 1 Powder 2 Time (days) (According to the invention) (Conventional) 0 91 88 100 100 5 7 91 88 70 60 21 87 86 67 33 30 88 84 65 16 In this experiment it is shown that increased efficiency in the process of the invention when no perborate is present and a very pronounced improvement is achieved in the presence of perborate.

Example 6

Powders are prepared as in Example 5, except that the noodles contain 10% fluorescence B. A sufficient quantity of noodles is added to make the fluorescent substance 0.15% based on the powder. Table VI shows the results obtained as in Example 5.

Table VI

Powder + Powder + Powder +

Time Powder Noodles Perborate Noodles + Perborate (Days) (Conv.) (According to Information) (Conv.) (According to Information) 0 100 94 100 97 25 7 85 97 67 90 21 82 93 45 90 56 69 93 21 88 84 66 91 19 85 30 Example 7

Particles containing different fluorescent substances at different concentrations are prepared as follows. The fluorescent substance is solidified to a quantity of soap, coconut-ethanolamide, polyethylene glycol or high

QC

olefin sulfonate and passes through a rolling mill at difference 147541

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22 even degrees of drum space. A smaller rolling gap means a more powerful rolling process. After rolling, the mixture is converted into small particles.

Experiments are performed with the following mixtures:

5 1) Soap containing 4.0% fluorescence A

2) 10.0%

3) "" 4.0% "B

4) "4.0%" C

5) "" 4.0% "D

6) Polyethylene glycol containing 4% fluorescence A

7) Higher olefin sulfonate containing 4.0% fluorescence A

8) Coconut fatty acid ethanolamide containing 4.0% fluorescence A.

Sufficient amounts of the fluorescent substance / carrier mixtures are added to a fluorescent-free, non-soap detergent powder to achieve a concentration of fluorescent substance of 0.08% based on the powder.

The effectiveness of the fluorescent substances in these mixtures is determined by a simple nylon wash sample. The results obtained are presented in Table VII, which gives the percent dispersion efficiencies assessed together with those in which the same amount of fluorescent substance is added to the non-soap detergent powder (N.S.D. powder), in its normal solid state. These numbers are relative.

The composition of the N.S.D. powder is as follows:

Sodium dodecylbenzenesulfonate 20%

Sodium tripolyphosphate 35% Sodium silicate 10%

Sodium sulphate 22%

Water the residue to 100% 35 147541

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Table VII

Mixture of Fluorescent Roll Intermediate Fluorescent and Carrier (mm) Activity 1) \ 0.51 68 5 1) Additive Disp. ) 0.051 100 10 4) 0.051 100 5) 0.076 100 6) 0.254 89 7) 0.127 89 8) J 0.254 61 15 Normal solid fluorescence A \ on "24 n ii ii g con- H 2ø ven-" "" C - "27 n ii ii n nel H» -3 way ^ 20 The greatest efficiency of a fluorescent substance is set to 100. (The results for different fluorescent substances are not comparable).

It will be appreciated that if these fluorescent substances are added to the slurry prior to spray drying, higher fluorescence activities will be achieved, but there will be a risk of decomposition during spray drying and for decomposition and clumping during storage. In the process of the invention, these problems are minimized.

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Example 8

Powder 1 has the following composition: Sodium dodecylbenzenesulfonate 20% N sodium tripo lypho sphat 3 5% 5 Sodium sulfate 22%

Sodium silicate 10% Soap noodles containing 4% by weight

Fluorescence B 2%

Coconut Ethanolamide 2% 10 Water to 100% total

Powder 2 has the same composition but contains 10% sodium perborate.

Powder 3 contains no soap noodles, but contains the same amount of fluorescence B as powder 1 and, moreover, has the same composition. The fluorescent substance is added to the slurry prior to spray drying in the form of a dispersion in the coconut-ethanolamide.

Powder 4 has the same composition as powder 3 and is prepared in a similar manner, but contains 10% sodium perborate.

Table VIII shows the results obtained in the same way as in Example 5.

Table VIII

25 Powder 1 Powder 2 Powder 3 Powder 4

Time (days) (According to the invention) (Conventional) 0 100 100 100 100 1 100 100 90 84 17 100 90 84 71 30 36 100 89 79 59 86 100 89 80 50 110 100 86 80 26

It should be noted that adding the fluorescent substance to the slurry in a dispersion in coconut ethanolamide gives 147541

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25 ver powders with higher fluorescence efficiency than the addition of the fluorescent substance directly to the slurry, but are insufficient to ensure stability when stored in the presence of perborate.

5

Example 9

Example 1 is repeated except that both powders contain 6% tetraacetylethylenediamine.

Table IX

results

Shelf life Fluorescent activity

(days) Powder I Powder II

(Conventional) _ (According to the Invention) 15 0 95 100 7 75 95 30 34 95 61 10 90 20 Example 10

Example 3 is repeated except that the powders do not contain TCCA and instead contain 10% sodium perborate and 6% tetraacetylethylenediamine.

Table X

results

Shelf life Fluorescent activity

(days) Powder I Powder II

(conventional) _ (according to the invention) 30 0 100 100 7 95 100 30 91 98 61 85 96 35

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Example 11 Powder I

The base powder is as in the table in Example 3 and contains 0.2% fluorescent H added to the concentrated 5 detergent slurry.

Powder II

The base powder is as in the table in Example 3 and contains 0.2% fluorescent H added in the form of soap noodles containing 10 wt% fluorescent substance. Neither of the two 10 powders contains TCCA. The fluorescence activity is determined according to the test used in Example 3.

Table XI

Results 15 Storage conditions Fluorescent activity

Powder I Powder II

(conventional) (according to the invention)

Fresh product 100 100

Product stored for 2 days 50 100 20 in normal daylight in clear glass bottles

Product stored for 2 days 95 100 excluding light 26 Example 12 In a powder with the composition Weight%

Sodium tetrapropylene benzene sulfonate 5.5

Nonylphenyl-14 EO 3.0

Commercial Stearic Acid Sodium 8.0 Sodium Tripolyphosphate 36.5

Sodium silicate (anhydrous) 5.0

Sodium sulfate 9.9

Carboxymethyl cellulose 1.0

Sodium perborate 22.0 Sodium ethylenediamine tetraacetate 0.16

Fluorescent substance, perfume, water, etc. for a total of 100% 27

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T475A1 incorporates 1.1% of a proteolytic enzyme, known under the trade name Maxatase S, A) in the form of a powder, and B) in groundnut oil soap noodles, which make up 5% of the powder. The soap noodles have a thickness of 0.3 mm and a length of 7.5 mm. The solubility rate of the noodles 5 at 20 ° C in normal waterworks is 7 minutes. This proteolytic enzyme has a proteolytic activity of 1.5 anson units / g. (An anson unit is the amount of proteolytic enzyme that degrades hemoglobin under the standard conditions as described by ML Anson in "Journal of General Physiology" Vol. 22 (1938) p. 79, at such a starting rate that per minute, such an amount of degradable products which cannot be precipitated by trichloroacetic acid is produced to produce the same color intensity as 1 milliequivalent tyrosine of the phenol reagent). Both products A and B 15 are stored at 30 ° C and 80% relative humidity in normal cardboard packaging and in wax-laminated packaging. The following table shows the proteolytic activity after 1 week, expressed as% of the original activity.

Table XII

A B

(conventional) (according to the invention)

Normal cardboard 20% 63%

Adult laminated 25 cardboard 72% 96%

Example 13

The same detergent numbers as in the previous example, but containing 1.1% Maxatase 300,000 (a proteolytic enzyme 30 with a proteolytic activity of 1.1 anson units / g) are stored in normal cardboard packaging at 30 ° C and 80% relative humidity.

The proteolytic activity after 1 and 2 weeks is given in the table below, expressed as% of the original activity.

35 o 28 1Α75Λ1

Table XIII

A B

(conventional) (according to the invention) 1 week 7% 100% 5 2 weeks 0% 73%

Example 14

Noodles with a length of 5 mm and a diameter of 0.3 mm with a weight of approx. 2 mg by extrusion of a 10 mixture of 80% peanut sodium soap and 20% of a proteolytic enzyme (1.6 anson units / g). The noodles are stained with 0.003% Monastral Fast Blue.

The dissolution rate is 30 seconds in waterworks at 20 ° C.

15

Example 15

Powders are prepared as in Example 12 except that a) the noodles contain 10% free fatty acids with 8-22 C-20 atoms, based on the weight of the noodles, b) the noodles contain enough enzyme to obtain an enzyme content of 0.63% of the weight of the powder; and c) the powder containing no noodles contains 0.58% by weight of the enzyme.

The powders are winned as in Example 12. The results are as follows: 30 35

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Table XIV

Storage Boxes of wax-laminated cardboard Boxes of double cardboard ring time Enzyme in noodles Enzyme direct Enzyme in noodles Enzyme direct (weeks) (according to) (conventional) (according to inventions) (conventional) 5

Enzyme content Enzyme content Enzyme content Enzyme content _% _% _% _% __ 0 0.63 0.58 0.63 0.58 1 0.60 0.54 0.68 0.24 2 0.59 0.30 0.56 0 , 16 10 3 0.53 0.20 0.50 0.07 4 0.54 0.11 0.49 0.02 6 0.59 0.06 0.29 0.00 8_0.40_0.02_0.10_0, Example 15

Proceed as described in British Patent Specification no.

911,410 Example 3, where 1 part by weight of Ν, Ν'-dichloroisocyanuric acid (DCCA) and 2 parts by weight of lauric acid are suspended in carbon tetrachloride and the resulting mixture is spray dried.

20 This product is called additive a.

The process according to the invention is carried out in which 1 part by weight of DCCA is mixed dry with 2 parts by weight of sodium laurate, ground on a rolling mill and then extruded. The granules thus obtained are called additive b.

The two additives a and b are now separately added to a detergent powder of otherwise similar composition, which further contains 0.25% 4,4'-bis- (4-anilino-6-morpholino-5-triazine). 2-yl-amino) -2,2'-stilbene disulfonate as a fluorescent agent, and the detergent powders thus prepared are stored and then subjected to measuring the activity of the fluorescent agent and determining the content of active DCCA with the following result, wherein the respective activities are assessed in relative to the activity of the freshly prepared samples added to 100 in both cases. This gives the following 35 results: o 30 147541

Table XV

Fluorescence agent content of active _ activity (¾) __ DCCA_ a) S (convention) 5% 52% b) opf. 76% 86%

From the above values it can be seen that the additive prepared by the process according to the invention is considerably superior to that of the fluorescent agent as well as the preservation of the activity of the active chlorine compound, according to British Patent No. 911,410.

15

Example 17

Washing powder compositions are prepared by proceeding as described above in Example 7 (Experiments 5 and 8, respectively) and according to British Patent Specification No. 911,410. The concentration of the fluorescent agent is in each case 0.08% by weight. Otherwise, work as indicated in Example 16. Hereby the results given in Table XVI below are obtained:

Table XVI

Extrudable Rolling Distance Fluorescent agent solid (mm) _ activity (%) _ c) Sodium 0.254 74 laurate 30 (according to d) Sodium 0.076 98 laurate (according to d) e) Lauric acid 53 (convention) 147541

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It is seen that in both cases, however, depending on the rolling distance of the mill used for grinding, a better activity retention for the fluorescence agent with the additive prepared by the method 5 according to the invention is obtained than with the additive prepared according to the prior art.

Example 18

Proceeding as disclosed in British Patent Specification No. 911,410, an optical bleaching agent A (1- (p-sulfamylphenyl) -3- (p-chlorophenyl) - (β-pyrazoline) is stirred in molten cetyl alcohol (m.p. 49.3 ° C) until a homogeneous paste is formed. This thick paste is allowed to cool and the solid mass obtained is comminuted. The grains in question are added to a washing powder which does not contain bleach, thereby obtaining a concentration of optical bleach of 0.08%, based on the entire detergent powder. Its effectiveness with regard to the utilization of the optical bleach is ascertained by means of a simple wash sample on synthetic polyamide fabric.

Furthermore, an additive is prepared by the same optical bleaching agent A, however, grinding milling and extrusion with soap are used to reprocess the additive in the form of noodles. The additive noodles are incorporated into a washing powder of exactly the same type as the known additive and at exactly the same concentration of 0.08% calculated on the entire detergent powder.

The composition of the washing powder is otherwise as follows: Sodium dodecylbenzenesulfonate 20%

Sodium tripolyphosphate 35% Sodium silicate 10%

Sodium sulphate 22%

Water until 100% 35

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32 1475Al

The results obtained from the above wash sample are given in Table XVII below, the numbers of which are relative, with the highest efficiency being set at 5 100%.

Table XVII

Optical bleach pea in detergent powder

Additive_Additive _____. Made according to Optical prepared according to Optical Bleach British Patent Bleaching In Form Activity No. 911,410 Noodles Activity __% _; __ Ethyl Alcohol 96% 14 Soap + 4% A 68-100 * Optical Bleach A 4% ___ 15 ethyl alcohol 88% 18 soap + 10% A 90 coconut ethanolamide 8% optical bleach A 4% ___ m depending on rolling distance 1

From the above results, it is seen that the special effect is convincingly achieved with the additive according to the invention, while the additive according to British Patent No. 911,410 gives far poorer results. There are clearly different levels of activity.

Claims (4)

33 147541 o Patent claims. A method of incorporating in a detergent powder, especially on a non-soap basis, a particulate, unstable additive to improve the whole agent's clarity, purity or germicidal activity which is incorporated into an inert material such as in the form of particles are mixed with the other constituents of the detergent powder, characterized in that: a condensate between polyethylene oxide and polypropylene oxide, a nonionic surfactant, sodium salt of a fatty acid of 8-22 carbon atoms, or a swelling agent, to form a mixture consisting of 0.1-50% by weight (b) the mixture is mechanically processed by grinding and / or extrusion to disperse the additive into the organic extrudable solid and to form granules weighing 0.05-100 m g) and c) the granules are mixed with the other ingredients of the detergent powder. Process according to claim 1, characterized in that the additive is an optical clarifier. Process according to claim 1, characterized in that the additive is an enzyme. 30 Process according to any one of the preceding claims, characterized in that the additive has a -5 solubility of less than 15 x 10 parts by weight as measured in a 0.4% aqueous solution of the detergent at 50 ° C. 35