SE439780B - SUPPLY UNIT CONTAINING A DETERGENT COMPOSITION INCLUDED IN A PHASE AND PHASE FOR PREPARATION OF THE SUPPLY UNIT - Google Patents

Description

7807255-0 10 15 20 25 30 35 2 tade fabric. Phosphate substitutes previously proposed include oxidized polysaccharides, certain cellulose derivatives, citrates, nitrilotriacetates and water-insoluble sodium aluminum silkates.

A complete replacement of the phosphates has so far been realized only on a limited scale.

According to the invention, the above problems can be solved in a cheap manner.

The present delivery unit is characterized in that the bag has two compartments, and that the detergent contains: a) 5-30% by weight of one or more solid acids, which form water-soluble calcium salts and magnesium salts and / or calcium complexes and magnesium complexes, wherein at least one acid has a pK1 value in the range 2.8-4.8. b) at least 5% by weight of alkali carbonate, and c) common detergent constituents, the total amount of alkali being in stoichiometric excess relative to the total amount of acid, and the acid or acids are enclosed in one space and the alkaline or the substances in the second space, and that the contents of the space containing the acid or acids, when using a household washing machine in which the usual washing procedure is carried out starting from cold water, are released at such a rate in the washing liquid, which gradually increases in temperature, that the pH of the washing liquid is in the range 2.0-5.0 before its temperature has reached a value of 25 ° C and that the second space consists wholly or partly of a material which becomes permeable in the washing liquid or decomposes therein after the weakly acidic conditions have been maintained long enough to substantially completely dissolve the precipitated carbonates, and that the contents of this second space practically completely dissolve es before the washing liquid has reached a temperature of 60 ° C and imparts to the washing liquid a pH in the range 9.0-10.5. ... exercises se .se e _ * z! The conventional detergent compositions which are based on alkali carbonate have the disadvantage that during successive washing cycles there is a considerable growth of water-insoluble carbonates on the fabric..................................... which is washed and on the heating element of the washing machine. This disadvantage is further exacerbated by the fact that the coating or incrustation is cumulative and increases more than proportionally as a function of the number of washing cycles. As a result, the quality of the fabric treated with these compositions will be affected and the fabric will have a stiff and discoloration. to show low absorbency and hard grip. In addition, abrasion occurs As a result of aging, the carbonate precipitate also becomes increasingly difficult to dissolve.

However, it has been found that in an individual washing cycle, so little precipitation is formed on the cement and so little coating on the fabric that the above-mentioned disadvantages of heating do not exist. Use of the supply unit according to the invention results in both the coating on the fabric and the deposition of the heating element formed during a washing cycle being brought into solution at the beginning of the next washing cycle by a reaction with acid under slightly acidic conditions. The slightly acidic conditions should be maintained long enough to allow the precipitated carbonates to dissolve practically completely.

Thereafter, the washing liquid is softened as a result of the alkaline component going into solution. The presence of the alkali carbonate in the water causes the calcium ions and magnesium ions, which are present in the washing liquid, to precipitate as water-insoluble carbonates. For maximum emollient effect and optimal washing effect, the pH value of the washing liquid after almost complete dissolution of the alkaline component should be in the range 9.0-10.5. Application of the present invention does not lead to appreciable growth of insoluble carbonates or other salts on the fabric or to the formation of any harmful deposits on the heating elements. Furthermore, the use of only a relatively low percentage by weight of acid, calculated on the total amount of detergent composition, is required.

It should be added that U.S. Pat. No. 3,761,415 discloses a phosphate-free detergent composition consisting of citrates such as citric acid, alkali carbonate and a synthetic surfactant. In short, the citrate ions go into solution before the sodium carbonate and in such an amount that the formation of water-soluble calcium carbonates and magnesium carbonates is prevented. However, the composition described in the patent has the disadvantage that a relatively high proportion of citrates need to be incorporated in order to prevent the above-mentioned precipitation.

At a hardness of 6 German degrees, the washing liquid should preferably contain 0.5% by weight of citric acid and 1.0% by weight of alkali carbonate. Converted to an integrated product, the detergent compositions of Examples 33-57% by weight contain citric acid.

For economic reasons, partly due to the relatively high cost of citrates and citric acid, such a percentage is unacceptably high. In addition, the residual hardness appears to be relatively high even at low initial hardness, which, for example, adversely affects the expected cleaning effect. In addition, the present bag has thus not been disclosed.

Furthermore, it should be added that German Offenlegungsschrift No. 2,437,173 describes a process which involves successive treatments with an acidic detergent prewash composition and an alkaline detergent head washing composition based on sodium carbonate. The present invention has the advantage over the composition of German Offenlegungsschrift 2,437,173 that the prevention of substantial cumulative encrustation or coating is achieved using a single detergent composition. In addition, when using the supply unit according to the invention, it is unnecessary and in some cases also undesirable for the washing liquid to be drained in whole or in part between the acidic and alkaline phase of the washing process.

The acid in the acid component of the supply unit should be capable of forming calcium salts and magnesium salts and / or complexes, which are moderately to soluble in water.

The amount of acid should be high enough to dissolve calcium carbonate and magnesium carbonate on a heating element and in a fabric.

In practice, it has been found that an amount of 5-30% by weight, calculated on the total amount of detergent composition, is sufficient.

The acid component should be soluble to such an extent in the washing liquid, the temperature of which is gradually increased, that the washing liquid has a pH value in the range 2.0-5.0 before its temperature reaches a value of 25 ° C.

If the pH falls below 2.0, certain types of fibers can be damaged. On the other hand, a pH value above 5.0 in practice results in the carbonate taking too long to dissolve completely.

The acid pK1 value should be in the range 2.8-4.8. If the acid has a pKl value below 2.8, the pH of the washing liquid can temporarily fall below 2.0, while a pKl value above 4.8 in practice requires the use of uneconomically large amounts of acid to achieve a pH value below 5.0.

The acid component should also have the above-mentioned properties in order for the weakly acidic conditions to be maintained long enough for the precipitated carbonates to be completely dissolved.

Examples of acids which have these properties are adipic acid, succinic acid, citric acid, diglycolic acid, lactic acid and tartaric acid.

The acid component may, of course, also contain a mixture of acids. Preferably the acid component should be a mixture of adipic acid, glutaric acid and succinic acid. It has been found that such a mixture dissolves very rapidly and moreover has a beneficial effect on the dissolution \ f '' @ @ 3 Ui $ ~ * 'W “fzv-'íd g. ...., - f ^'” '7807255-0 10 15 20 25 30 35 6 the rate of the precipitated carbonates during the acidic phase of the washing process.

If the acidic constituent contains a mixture of acids, at least one acid should have a pK1 value in the range 2,8-4,8. Such an acid can be mixed with inorganic acids, such as sodium hydrogen sulfate. In combination with other acids, it is also possible to use polycarboxylic acids, such as polyacrylic acid, the acid form of oxidized cellulose and starch, mono- and polycarboxylated products obtained by substituting hydrogen atoms of starch and cellulose, such as carboxymethylcellulose and dicarboxymethyl starch.

Depending on the intended use of the detergent composition, one or more conventional ingredients may be incorporated into the acidic ingredient.

Preferably, the acidic component contains a surfactant. Its presence results in the acids, the laundry and the precipitated carbonates being wetted faster, which has a favorable effect on the dissolution rate of the carbonates.

Particularly suitable for this purpose are ethoxylated fatty alcohols.

Another category of materials that can be incorporated into the acidic component are per-compounds, such as peroxides, which have an optimal bleaching effect at a lower pH value than that at which the detergent composition exhibits optimal cleaning action. Compounds, such as peroximonosulfate, which have insufficient storage stability in common detergent compositions, may also be incorporated into the acidic component.

After the acid component has dissolved, the pH of the washing liquid may rise to a maximum value of 6.5-7.0 during the acidic phase of the washing process. This pH increase is caused by the gradual dissolution of the precipitated carbonates. The value to which the pH value increases depends on the hydrogen carbonate content and the hardness of the water, the amount of laundry, the coating on the fabric and the degree of precipitation on the heating element. The alkaline component should contain such an amount of alkali that the pH of the washing liquid is 9.0-10.5 after the alkaline component has dissolved almost completely. This pH value is required to obtain an optimal cleaning effect and effective softening. The alkali used is preferably an alkali carbonate or a mixture of alkali carbonate and, for example, sodium silicate.

The alkali content can vary within wide limits. However, the detergent composition should contain at least 5% by weight of alkali carbonate in order for the calcium ions and magnesium ions to precipitate in the washing liquid. A lower content would be ineffective even under the most favorable conditions.

In some cases it may be desirable for the detergent composition to contain as much as 65% by weight of alkali carbonate.

A suitable alkali carbonate is sodium carbonate. However, sodium carbonate and its hydrates are relatively sensitive to moisture. In the present detergent composition, this can lead to difficulties in that the present detergent composition contains both an acidic and an alkaline component. The rather high alkalinity also sometimes entails a disadvantage. For these reasons, the alkaline component may contain, in addition to anhydrous sodium carbonate, as alkali carbonate sodium bicarbonate and / or sodium sesquicarbonate. These combinations of compounds are less sensitive to moisture than sodium carbonate and its hydrate and also have lower alkalinity.

The alkaline component may additionally contain one or more common detergent ingredients, such as surfactants, bleaches, fluorescent whitening agents, enzymes, foaming agents, substances such as sodium carboxymethylcellulose, which serve to prevent dirt from re-precipitating on the surface. , bactericides, corrosion inhibitors, perfumes, colorants, etc.

The surfactants which can be used are the water-soluble salts of higher fatty acids ("soaps") or the synthetic surfactants described, for example, in Dutch Patents 7,807,255 and 10,403,381 and 7,406,306.

It is preferred that the surfactant contained in the alkaline component be an alkyl ether sulfate. Alkyl ether sulfates have the advantage of helping to reduce incrustation. Preferably sodium tallow fatty alcohol ether sulfate is used. The alkaline component hardly dissolves until the temperature of the washing liquid reaches a value of 40 ° C and goes practically completely into solution before the temperature is 60 ° C.

The alkaline component should have this property in order, on the one hand, to be able to maintain the weakly acidic conditions for a sufficiently long time and in order, on the other hand, to be able to bring the pH of the washing liquid to 9.0-10.5 before a washing temperature of 60 ° C is reached.

The acidic and alkaline constituents may be in powder or agglomerated form. By agglomeration is meant, among other things, pelleting, tableting, granulation, extrusion, marumerization (breaking up of extruded products and formation of essentially spherical particles by dropping on a rotated disk, which throws the particles towards a stationary web), briquetting, rolling followed by cutting.

The supply units according to the present invention should be shaped in such a way that the bag has two compartments, the acidic component being in one compartment and the alkaline component in the other compartment.

The bags should be designed so that the alkaline component exhibits delayed dissolution as a result of the construction of the bag.

The use of such bags has the advantage that the alkaline component can be enclosed in the bag in the form of powder. For this purpose, a bag can be prepared in which the space containing the alkaline component (the "alkaline" space) consists wholly or partly of a material which becomes water-permeable or decomposes at a temperature between 40 and 60 ° C. By disintegration is meant here dissolution, dispersion and tearing of the bag. A bag can in principle consist of, for example, three layers of material, the outer wall of the "acidic" space being permeable to water, the outer wall of the alkaline component being impermeable to water and the partition wall, for example, consisting of a mixture of poly (meth) acrylic acid (Eudragit L D) and hydroxypropyl methylcellulose. A partition thus assembled is torn apart at a temperature between 40 and 60 ° C, after which the alkaline component can be freely dissolved in the washing liquid.

The water-permeable outer wall preferably consists of a non-woven material.

Different materials can be used for the water-impermeable wall. Preferably, however, polyethylene, polypropylene, polyvinyl chloride or a nonwoven material provided with a water-insoluble coating is used. Alternatively, the "alkaline" space may be closed with a strip which is water permeable or decomposes at a temperature between 40 and 60 ° C. Such a strip may be a connecting strip between an impermeable partition and an outer wall. Such a strip may, for example, consist wholly or partly of polyvinyl alcohol or a mixture of poly- (meth) acrylic acid (Eudragit L 30 D) and hydroxypropylmethylcellulose.

However, it is preferred that the alkaline space be provided with one or more seams, which are opened in water at a temperature between 40 and 60 ° C. A bag of this type can be created by arranging in the seams a material which disintegrates between 40 and 60 ° C. The seams can then be formed in whole or in part from a mixture of polyethylene glycol and one or more thermoplastic acrylic resins. Polyethylene glycol having a molecular weight of 1500 melts at a washing liquid temperature of 42 ° C, after which the seams are opened.

The following examples serve to further describe the present invention. EXAMPLE 1 (Comparative) The following experiments were performed in a Zanker washing machine (EA SA). The volume of the washing liquid was 16 liters. The water had a hardness of 15 ° (German degrees), and the bicarbonate content was 200 mg / liter. To the washing liquid was added 216 g of the integrated detergent composition described in Example VIII of U.S. Pat. No. 3,761,415. The composition consisted of 35% by weight. citric acid, 63.5% by weight of sodium carbonate and 1.5% by weight of synthetic detergent. The relationship between time, temperature and the acidity of the washing liquid was determined.

After 2 minutes at a temperature of 20 ° C, the washing liquid had already reached a pH value of 8.7. After 10 minutes at 37 ° C the pH was 8.9 and after 40 minutes at 8700 the pH was 9.25. As a result of the relatively high citrate ion concentration and the low pH value, there was hardly any precipitation of calcium carbonate or magnesium carbonate.

The above values show that this detergent composition differs both in principle and design from the composition of the present invention.

While the object of the above patent is to prevent precipitation of calcium carbonate and magnesium carbonate, the present invention precisely involves the formation of such a precipitate. Accordingly, the detergent composition of the present invention contains a significantly lesser proportion of acid. The feature that citrate ions go into solution before the sodium carbonate, as described in U.S. Pat. Although in the present invention it is also desired that the acidic constituent should go into solution before the alkaline constituent, this characteristic is in itself insufficient. EXAMPLE 2 The following experiments were performed in an Miele automatic washing machine (No. 416). To determine the degree of incrustation, special sample fabrics were washed. The water had a hardness of 15 ° (German degrees), and the hydrogen carbonate content was 200 mg / liter. A supply unit according to the invention consisted of a bag with 2 chambers and the dimensions 14 x 16 cm which bag had an outer wall of a laminated non-woven material for the "alkaline" space and an outer wall of a non-woven material for the "acidic" space and a On one side of the bag, a connecting strip was arranged between the outer wall of the "alkaline" space and the partition, which strip was about 0.05 mm thick and broke at a temperature of 45-60 ° C. The strip consisted of a mixture of 15 parts of Eudragit L 30 D (30% by weight) and 2 parts of Methocel HG 4000 (hydroxypropylmethylcellulose).

The seams of the bag were sealed with glue. The acidic component consisted of: 25 g of fumaric acid 4 g of tallow fatty toxilate, 25 ethylene oxide.

The alkaline component consisted of: 52.7 g of anhydrous sodium carbonate 42.4 g of sodium perborate 11.9 g of sodium disilicate 4.0 g of sodium palmitate 9.0 g of lauryl ether sulphate 1.0 g of carboxymethylcellulose 0.5 g of optical brightener 0.6 g of sodium salt of ethylenediamine -tetra-acetic acid 0.5 g of silicone oil.

After 15 wash cycles, during which the same sample fabrics were washed at all times, it was found that the primary cleaning effect of the detergent composition of the invention was not inferior to that of phosphate-containing detergent compositions. After 4, 7 and 15 wash cycles, the incrustation values were 0.21, 0.25 and 0.49%, respectively. These values show that the present invention also in this respect is not inferior to the conventional phosphate-containing detergent compositions in quality.

EXAMPLE 3 The following wash attempts the Erres brand (AEH 341). In goods 3.5 A supply unit according to the bag was carried out in a washing machine in all cases, the amount was washing kg. the water reached a hardness of 15 ° (German degrees). the invention consisted of two spaces and the dimensions 13 x 15 cm, which bag had an outer wall of a polyethylene laminated, nonwoven material for the "alkaline" space, an outer wall of a non-woven material powdered with polyethylene for the "acidic" space and a polyethylene partition.

The four seams between the water-permeable outer wall and the partition wall were permanently sealed.

Of the four seams between the outer wall and the "alkaline" space and the partition, two were permanently sealed.

The other two seams were filled with a material which decomposed in water at 40-50 ° C. This material consisted of a mixture of 10% by weight of polyethylene glycol with a molecular weight of 1500 and 90% by weight of a mixture of thermoplastic acrylic resins.

The seams were sealed using pressure at elevated temperature. The polyethylene glycol melted at 42 ° C. When the seams were opened, the alkaline component of the washing liquid was released. The acidic component was in the form of extruded pieces about 0.8 mm in diameter and 1-3 mm in length. The alkaline component consisted of a powder.

The acidic component was composed of: 6.9 g 6.9 g 9.2 g 2.7 g The 8.0 g 5.7 g 2.0 g adipic acid succinic acid glutaric acid tallow alcohol alcohol ethylene oxide. The alkaline component consisted of: tallow fatty ether sulphate sodium dodecyl benzenesulfonate sodium salt of hardened rapeseed oil n: g ... i-på * P e. I .nL-Ifïï: J tlÜOåa 10 7807255-0 13 10.0 g sodium disilicate 48.0 g sodium peroxide .0 g of anhydrous sodium carbonate 1.0 g of carboxymethylcellulose In one experiment, a cotton material was washed 17 times with the above detergent composition at a temperature of 90 ° C. The relationship between the temperature of the washing liquid and the pH value at the 17 wash cycle is shown in Fig. 1. The primary cleaning effect is comparable to that of conventional phosphate-containing detergent compositions. After the material was washed 5, 11 and 17 times, the incrustation value was 0.30, 0.42 and 0.59%, respectively. These results clearly show the effect and the favorable results that can be obtained with the detergent composition according to the invention.

Claims (4)

7807255-0 10 15 20 25 30 14 PATENT REQUIREMENTS Delivery unit, consisting of a detergent composition enclosed in a bag, characterized in that the bag has two compartments, and that the detergent contains: a) 5-30% by weight of one or more solid acids, which form water-soluble calcium salts and magnesium salts and / or calcium complexes and magnesium complexes, wherein at least one acid has a pK1 value in the range 2.8-4.8, b) at least 5% by weight of alkali carbonate, and c) common detergent constituents, the total amount of alkali being present in the stoichiome excess relative to the total amount of acid, in which the acid or acids are entrapped in one space and the alkaline substance or substances in the other space, and that the content of the space containing the acid or acids, when using a household washing machine in which the usual washing procedure is carried out starting from cold water is released at such a rate in the washing liquid, which gradually increases in temperature, that the pH of the washing liquid is in a ration has reached a temperature those of 25 ° C and that the second range 2.0-5.0 before the temperature space consists wholly or partly of a material which becomes permeable to the washing liquid or decomposes therein after the weakly acidic conditions have been maintained long enough for to substantially completely dissolve the precipitated carbonates, and that the contents of this second space are practically completely dissolved before the washing liquid has reached a temperature of 60 DEG C. and imparts to the washing liquid a pH in the range 9.0-10.5. 2. A supply unit according to claim 1, characterized in that the space containing the alkaline substances is provided with one or more seams, which are opened in the washing liquid at a temperature in the range 40-6o ° c. h 'v, de i; _ 10 7807255-0 15 3. A supply unit according to claim 2, characterized in that at least one seam of the bag is wholly or partly constituted by a mixture of polyethylene glycol and one or more thermoplastic acrylic resins. l Bag for the manufacture of a supply unit according to any one of the preceding claims, characterized in that the bag has two spaces, and that the part of the bag which forms one space consists wholly or partly of a material , which is or becomes permeable or decomposes in washing liquid at a temperature below 25 ° C, while the part of the bag which forms the second space consists wholly or partly of a material which becomes permeable or decomposes in the washing liquid at a temperature of 40-60 ° C .