DE2158056A1 - laundry detergent - Google Patents

Description

DAI - 1

DAINICHISBIKA COLOR & CHEMICALS MFG. CO. LTD., Tokyo, Japan

laundry detergent

The invention relates to a detergent with anionic and / or non-ionic and / or cationic and / or amphoteric surfactants and / or alkaline agents and / or acidic agents as washing-active substances.

Detergents for fibers, textiles, clothing, metal, machine parts, Ceramics and other household items usually contain fatty acid soaps, synthetic surfactants Medium, alkaline and acidic agents, depending on the application. Usually a detergent solution is prepared by Dissolve an arbitrary amount of detergent in a solvent, depending on the operator's experience Often more detergent is then added or the detergent solution is changed, depending on the degree of soiling the detergent solution. Therefore, the concentration of detergent in the detergent solution can vary come even if the operator tries to follow the instructions carefully. So it is difficult to precisely select the concentration of the detergent solution and, in particular, to adjust the pH value of the detergent solution This is particularly critical when the laundry or other items to be washed are at a particular location pH value can be destroyed or damaged.

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Generally, it is a major component or an essential one An electrolyte or the effectiveness of the main components or additives is determined by the additive Affected hydrogen ion concentration. Accordingly is it is possible to adjust the detergent concentration based on the pH of the detergent solution, whereby a easy adjustability of the detergent solution achieved and an economical use of the detergent is guaranteed is «If the laundry or other items to be washed are at a certain pH value of the detergent solution corrode or be damaged, the washing process can be controlled with the help of the pH indicator and the laundry or the other items to be washed can be effectively protected. Bs is required to have a To choose an indicator which does not discolour the laundry or other items to be washed, thereby the purpose of the What would be ruined "

It is therefore an object of the present invention to provide a detergent to create an indication of the pH of the detergent solution without discolouring the items to be washed allowed.

This object is achieved according to the invention by a detergent which has a content of one in a solution of the Detergent with soluble or dispersible polymers pH indicator properties, in an amount from 0.1 to 50 Percentage by weight, based on the washing-active substances, has «

When using the detergent according to the invention, a certain pH value is exceeded by a Color change of the Wasohm! Tel solution displayed «The. Polymers with pH indicator properties will not be in the wash or adsorbed on other items to be washed and can be completely removed with the detergent solution and rinsed out «Ea will not leave any stains.

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By. Use of the ash agent according to the invention can can easily be avoided that the pH of the detergent solution assumes a value at which the objects to be washed corrode or become damaged.

According to the invention, the detergent can use all washing raw materials which are suitable for removing dirt from objects to be washed in water or in an aqueous medium. The detergent according to the invention is suitable as a household detergent for clothes, dishes, furniture and the like or as an industrial detergent for washing fibers, in particular wool, for finishing, for cleaning of metal parts and machine parts, for cleaning of laundry, also for pulp and in the paper industry, for washing cars and ships, for washing of Glass and ceramics, from cans and bottles or the like.

The detergent according to the invention can in particular contain anionic surface-active agents, such as. B * Salts of higher fatty acids, salts of higher alcohol sulfates, salts of liquid fatty oil sulfates, salts of higher alcohol phosphates, salts of alkyl aryl sulfonates, salts of naphthalene sulfonate formaldehyde condensates. In addition, nonionic surfactants, such as. B. polyoxyethylene-alkyl-ethers, polyoxyethylene-alkyl-phenol-fcther, polyoxyethylene-alkyl-ester, polyoxyethylene-anhydrosorbitol-alkyl-ester and polyoxyethylene-polyoxypropylene block copolymers in question, as well as cationic surface-active agents such. B. quaternary ammonium salts and alkylpyridinium salts, and amphoteric surfactants, such as. B. nonionic-anionic, nonionic-cationic and anionic-cationic surface-active agents «Alkaline agents are also suitable, such as. B. Sodium hydroxide, sodium sesquisilicate, sodium metasilicate, sodium orthophosphate, water glass (Na ₂ O * 1.6 SiO ";Na" 0 * 2 SiO-; Na ₂ O * 3 »2 SiO ₂ ), sodium carbonate, sodium pyrophosphate and sodium borate, as well as acidic agents such as B. sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfamic acid

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acid, oxalic acid or citric acid or mixtures all of these means,

In addition, additives or "builders" can be added to the detergent be admixed, such as B. sodium sulfate, sodium metasilicate, Sodium sesquisilicate, sodium orthosilicate, sodium carbonate, Sodium bicarbonate, sodium orthophosphate, sodium tripolyphosphate, Sodium hexamethaphosphate, sodium chloride, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, Ethylenediamine tetraacetic acid and fluorescent optical brighteners.

The polymer with pH indicator properties used for the detergent according to the invention has a structure at which the pH indicator is linked to a polymer group. This polymer indicator has a sharp color change in a specific pH range and can be produced by one of the following processes:

(A) A pH indicator with a group that is condensable or addition condensable is condensed with a polymer or a polymerizable monomer, which has a condensable or addition condensable group.

(b) A pH indicator with a diazonium group is used

mixed with an OCP-a * ¹¹ ^ ¹ © ¹¹ ^ ¹⁵⁰¹ ! -unsaturated monomers and polymerized, the pH indicator with the diazonium group being used as the polymerization initiator.

(c) A pH indicator with an δ (, ß-ethylenically unsaturated Group is marked with a ((, ß-ethylenically unsaturated Monomers mixed and copolymerized.

These methods can be combined or applied sequentially. Instead of the pH indicator you can a preproduct of the pH indicator occur, after which

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Condensation reaction or addition reaction or polymerization reaction the intermediate component is converted to a pH indicator, the pH indicator polymer arises. To achieve a sharp color change at pH change or to shift the pH range at which If the color change takes place during washing, it is possible to use conventional dyes, pigments or polymer material add bound dyes. It is also possible to use the pH indicator polymer with a dye, a pigment or a dye-bound polymer or derivative thereof which interacts with the pH indicator polymer is actionable to respond. Further, such a reaction can be carried out with the raw material or with an intermediary will. This further conversion of the pH indicator polymer can take place before the reaction, during the reaction or take place after the reaction to form the pH indicator polymer. If an intermediate stage for manufacture of the pH indicator polymer is used, a development treatment follows. For the production of the invention pH indicator polymers used pH indicators can be weak acids or weak Bases whose visible absorption spectrum in the dissociated state is different from that in the normal Molecular state.

The pH indicators include:

(a) Phthalein indicators such as B. phenolphthalein, o-Kreβol-phthalein, thymol-phthalein, p-xylenol-phthalein, ρς-naphthol-phthalein, dibromophenol-phthalein, phenol-4-carboxy-phthalein, Thymol - ^ - carboxy-phthalein, p-xylenol-4-carboxy-phthalein, Phenol-3, ^, 5 »(> - tetrachlorophthalein, etc .;

(b) sulfonophthalein indicators, such as. B. phenol red, Cresol red, a-cresol purple, p-xylenol blue, thymol blue, Xylenol orange, bromophenol red, bromocresol purple, bromocresol green, Bromothymol blue and bromophenol blue or the like;

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(ο) Azo indicators, such as B. Congo Red, Metlxyl Orange, p-Äthoxycrysoizin, ιί-naphthyl red, tropaolin 000, alizarin yellow R, methyl red and azo blue;

(d) Other indicators such as B. methyl violet 6b, crystal violet, pentamethoxy red, litmus, quinoline blue, nile blue and indigo carmine.

The production of the pH indicator polymer according to process (A) is to be explained below. The condensable or addition condensable group may be an amino group, a hydroxyl group, a carboxy group, a carbamide group, a sulfamide group, an ester group of a lower alcohol, a lower pettester group, a group with an aromatic ring, which has substituted hydrogen, an N-methyl group, an N-halomethyl group, a C-methylol group, a C-halomethyl group, a Bpoxy group, a halohydrin group, an aldehyde group, an isocyanate group, an acid chloride group, a halotriazine group and a diazonium group be ·

The pH indicator may have such a reactive group per se, or a suitable pH indicator may be prepared by introducing one of the reactive groups mentioned into the pH indicator molecule or its precursor «

The polymers or polymerizable monomers which can be reacted with the pH indicator having a condensable or addition condensable group include conventional reactive polymers and polymerizable monomers such as e.g. B. the following compounds}

(1) Polymer "and monomers for the preparation of a pH indicator ePolyeeren with a methylol group, an oxymethyl Alk group, a halomethyl group or the like al" condensable group ·

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(a) condensates of formaldehyde with melamine, urea, phenol, dimethylaniline, p-toluenesulfamide and naphthalenesulfonic acid; Co-condensates of the same, their alkoxymethyl deriscates or halomethyl derivatives; Components for the production of these condensates.

(b) Compounds which are obtained by reacting formaldehyde with polyamide, with glue, with polyacrylamide or with acrylamide copolymers and components for the preparation of these compounds.

(c) homopolymers of unsaturated methylol amides, such as B. of N-methylolacrylamide and copolymers thereof with other monomers "

(2) Polymers and monomers for making the pH indicator polymer with a Bpoxy group or a halohydrin group as a condensation group.

(a) condensates of polyvalent amines, of polyvalent phenols or of polyvalent amides with bpihalohydrin, Dihalohydrin or polyepoxy compounds and co-condensates as well as the components for the production of these condensates,

(b) Homopolymers of the unsaturated epoxy compounds or chlorohydrin compounds such as. B. glycidyl methacrylate, G-chloro-β-hydroxy-n-propyl methacrylate and copolymers thereof with other monomers *

(c) ethylene oxide, ethylene hydrochloride, propylene oxide.

(3) Polymers and monomers for the manufacture of pH indicator polymers with carboxyl groups, acid chloride groups, acid anhydride groups, ester groups lower Alcohols, lower fatty ester groups as condensation groups. 209824/1070

(a) reaction products of polyhydric alcohol, such as ethylene glycol, propylene glycol, neopentyl glycol, glycerine, Sorbitan anhydride, polyethylene glycol, polypropylene glycol, diethanolamine, triethanolamine, methyl cellulose, hydroxyethyl cellulose with polybasic carboxylic acids, such as maleic anhydrides, fumaric acid, phthalic anhydride, 4-sulfophthalic acid, Adipic acid, citric acid, tartaric acid as well as components for the manufacture of these products,

(B) reaction products of ethylene diamine, hexamethylene diamine, ethanolamine, mono- (polyethylene glycol) amine with the called polybasic carboxylic acids and the components for the production of these products.

The pH indicator polymer is known through the implementation of the pH indicator be made with a polymer if a polymer is used as the starting material and a pH indicator, which has a group which can react with the polymer or in which the reactive group is introduced became. The condensation reaction of the reactive pH indicator and the reactive polymer or a component thereof depending on the kinds of the reactive groups and the chemical Properties of the starting compounds carried out.

If the polymer used is a curable plastic, it is possible to use a water-soluble pH indicator polymer or a pH indicator polymer soluble in organic solvents s by stopping the condensation reaction at an initial stage. It is further possible to obtain a pH indicator polymer which is insoluble in water or organic solvents, which in Particulate form is used when the condensation reaction is allowed to proceed to completion.

The following describes the production of the pH indicator * »Polymers (b) explained. In this production (b) the

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Diazonium group in the form of diazonium chloride, heavy metal complex salt, Alkyl sulfonate salt, alkyl sulfate salt, Aryl sulfonate salt, alkyl aryl sulfonate salt and fluoborate salt or in the form of a diazoamino group.

The Ddazonium compound can through. Diazotize a Amino group of the pH indicator are made. If required., a stabilizer can be added to the diazonium compound. Those added to the diazonium compound ^, ß-Ethylenically unsaturated monomers can be conventional be radically polymerizable monomers, e.g. unsaturated carboxylic acids such as acrylic acid, methacrylic acid or alkyl esters, Hydroxyalkyl esters, polyalkylene glycol esters and dialkylaminoethyl esters the same as well as acid amides, N-alkoxymethyl acid amides and glycidyl esters thereof, and acrylonitrile, vinyl acetate and styrene.

It is assumed that the polymerization of the | (, ß-ethylenically unsaturated monomers in the presence of the diazonium compound of the pH indicator is brought about by the diazonium group being poor or by the influence of light or by a change in pH or by the influence a diazo-decomposing agent such as titanium trichloride, copper chloride or copper powder is decomposed and forms free radicals of the pH indicator and nitrogen gas, whereupon the polymerization of the ft ( _t ß-ethylenically unsaturated monomers in the presence of these free radicals as starters takes place , at the same time the polymer obtained enters a conjugated compound with the pH indicator.

The following is the preparation of the pH indicator polymer (c) described · The (X, ß-ethylenically unsaturated group can be an aorylamide group, a methacrylamide group, a Methacryloyl-oxy-ß-hydroxy-n-propyl-amino group, a methacryloyl-oxy-ß-hydroxy-n-propyl-ether group, an aorylamide

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methylene group or a vinyl group or the like be. This b (»p-ethylenically unsaturated group becomes either introduced into a preliminary stage of the pH indicator or into the finished pH indicator. The κί, ß-Ethylenic Unsaturated monomers which are mixed with the pH indicator can be one of the monomers mentioned under (b) be. The pH indicator is in a conjugated bond with the polymer by copolymerization of the pH indicator with the flljJJ-ethylenically unsaturated group and the <W »ß-ethylenically unsaturated monomer in the presence a conventional polymerization initiator, such as. B. potassium persulfate, ammonium persulfate, azobisisobutyronitrile or brought benzoyl peroxide.

In preparation (b) and (c) the pH indicator polymers be prepared by solution polymerization in aqueous solution or in an organic solvent or by emulsion polymerisation, by suspension polymerisation in water or by block polymerisation. That which can be produced in this way pH indicator polymers can be soluble in water or in alcohol, depending on the properties of the polymer or in organic solvents or it can also be insoluble due to complete crosslinking.

If the pH indicator polymer obtained has reactive groups these reactive groups can be substituted by anionic, nonionic or cationic hydrophilic groups by mixing the polymer with chloroacetic acid, sodium bisulfite, sulfamic acid, sulfuric acid, Ethylene oxide, lower amine, pyridinium hydrochloride or Ethylenimine converts. The reactive group can also be substituted by hydrophobic groups by adding the polymer with higher aliphatic or aromatic amines or alcohols or with carbamide, methylolcarbamide, acid chloride or isocyanate or the like.

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The pH indicator polymers obtained change their color in a certain pH range, although some are soluble in an aqueous medium and others are dispersible in an aqueous medium. A slight change in the area of the color change and a change in the color tone are found when the polymer is connected to the pH indicator at a point at which the pH range and the color tone are influenced when the color change of the pH indicator «As an example a pH indicator polymer should be considered, which was made from phenolphthalein as indicator and melamine-formaldehyde condensate as polymer. This polymer is colorless in the acid form and reddish purple in the base form and the area of the color change of the water-soluble pH indicator polymer is at pH values from 7.9 to 9V5 and the range of color change of the water-insoluble pH indicator polymer is at pH values from 6.5 to 12.0. Sharp color changes are found, while the phenolphthalein itself is colorless in the acid form and turns red in the base form and at a pH range from 8.0 to 9> 6 »

Since the sensitivity of the water-insoluble pH indicator polymer particles to change in pH depends on the particle size and physical properties, e.g. Depending on the wettability with water, it is preferred to choose the particles as fine as possible. The ratio of the pH indicator polymer to the washing raw materials in the detergent according to the invention should be large enough so that the change in color of the detergent solution can be recognized. The amount of pH indicator in the pH indicator polymers can be selected depending on the type of reaction and the combination of starting materials, as well as the molecular weight of the polymer and the manufacturing conditions. It is usually $ 50 to $ 0.1, preferably $ 30 to $ 1. The amount of the pH indicator polymer to the detergent in the detergent according to the invention is not limited, but it is usually $ 50 to $ 0.1 > and preferably 10 # to

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$ 1 in the case of a powdery insoluble in water pH indicator polymers and preferably $ 5 to $ 0.1 in the case of a water-soluble pH indicator polymer.

The pH indicator polymer can be combined with the neutral builder, with surface-active agents, with wetting agents, snit moisture-proof agents and also with detergents in a suitable Foapn, such as. B. In aqueous solution, in aqueous dispersion, in paste form, in the form of a fine powder or in the form of granules or capsules depending on who Type of detergent to be mixed »

To produce a granulate, the pH indicator poly " , mere mixed with a small amount of water, with a volatile organic solvent and if necessary with a surfactant or a builder, followed by granulation in an agitator. If a Drying is carried out, an aqueous solution or a solution in an organic solvent Spray drying can be dried. A wetting paste or wet paste can also be used for granulation.

In the following, the functionality of the inventive Detergent with the detergent substances and the pH indicator polymer explained.

Household detergents are mainly used for washing clothes, dishes and furniture. A typical example of such a weakly basic detergent includes 15-30 # surfactants, such as. B. Sodium alkylbenzene sulfonate, sodium - ^ (- olefin-sulfοnafc and the sodium salt of a higher alcohol sulfate, 1 - 2 $ sodium benzenesulfonate, 10 - 30 $ tripoly-phosphate as a builder, 2 - 6 # sodium silicate, 20 - 50 ¹ Jd sodium sulfate and a small amount of carboxymethyl cellulose and a fluorescent optical brightener

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obtain.

To carry out the washing operation, about 50 g of the Add detergent in about 30 liters of water in a washing machine dissolved in a detergent solution. The pH range for a good one The washing effect is usually in the weakly alkaline range and should especially be achieved during the washing operation pH range of 9 »5 - 10.0 must be maintained. During the washing operation, the pH of the washing liquor is gradual decreasing due to decomposition and contamination. At the same time, the washing activity is reduced.

By the addition of a pH indicator polymer having a pH range from 10.0 to 9.5 _t ^be the * occurs, the alkaline color, and with a pH range from 9.0 to 8.5, wherein the acidic decolorization takes place, one can control the concentration of the detergent in the washing liquor easily and economically with the help of the indicator with such a detergent. Furthermore, the removal of the dirt and the inactivation of the washing liquor by decomposition of the detergent can be followed by observing the change in color, so that new detergent can be added at the right time or the washing liquor can be changed. In this way, the washing process is made effective and economical.

Bs is a major advantage of the detergent according to the invention, that the pH indicator polymer has a polymer structure, so that the pH indicator polymer in the form of finer Particles or microfine particles are dispersed, causing staining or discoloration of the surface the laundry or other items to be washed advantageously will be avoided · In the metal industry Metals often corroded or damaged in the washing bath at an unfavorable pH value. Such corrosion can

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ζ. B. take place at a pH of 10, G and higher, when the metal is zinc, or at a pH greater than 10.0 in the case of aluminum, or at a pH greater than 11.0 for tin and greater than 11.5 for bronze.

Thus, with the help of the detergent according to the invention The harmful corrosion of metal to be washed can be avoided by using a pH indicator polymer with a Applying color change in a suitable pH range together with the detergent for metal washing, the Addition of a further amount of detergent or the dilution with water can be made immediately to the process to be effective and to achieve good product quality. In the fiber industry it is necessary Avoid working conditions in which the fiber is damaged, namely during finishing processes, during washing and when bleaching and loosening encrusted dirt from various fibers. Wool is z. B. partially at a pH of more than 9 decomposes and silk should be at a pH of less than 10.5 and preferably less than 10.0 are treated. Rayon should also be treated at a pH below 10.0 » The control of the process and the product quality can be carried out easily and precisely by using the inventive Applies detergent with the pH indicator polymer with a suitable pH range of the color change.

When removing encrusted soiling, an enzyme and a non-ionic surfactant are used in the detergent. A suitable pH for removing encrusted dirt depends on the temperature, length of time and type of enzyme and is usually in the range of 6.3 - 6 _? 5, if the bath with 7-12 g / l commercial amylass and one with 0 _t 0h #

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non-ionic surfactant produced and is used at 6o - 70C. Here too is it is possible to remove encrusted Carry out dirt under optimal conditions a pH indicator polymer with a corresponding transition area is present. Thus, when using the detergent according to the invention, one can more easily and clearly Way on the basis of the color change in the various applications control the pH, so that the detergent can be used in the most effective way and operate in a hazardous pH range, in which the laundry or other items to be washed can be damaged can be avoided.

The laundry or other items to be washed can be washed without discoloration due to the pH indicator, so that the detergent applied economically and effectively can be easily and precisely controlled, the washing process and the quality of the washed. Products can be increased.

In the following the invention is illustrated by means of embodiments explained in more detail. All parts and percentages are parts by weight or percentages by weight.

0.32 part of powdered thymolphthalein-4-oarbamidpolyäthylengIycol (pH indicator polymer having a molecular weight of about 4,000, made according to Procedure (a), which is colorless in the acidic range and bright blue in the alkaline range and at a pH range of 8,9 - 9f5 turns) with 100 parts of the following Mixture mixed, resulting in the detergent according to the invention.

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Sodium alkylbenzene sulfonate 25 parts

Sodium tripolyphosphate 30 parts

Sodium metasilicate 10 parts

anhydrous sodium sulfate 3k parts

Carboxymethyl cellulose 1 part

100 parts in total

About 50 g of the obtained. Laundry detergents will be available in 30 Water in an electric washing machine and stirred for about 10 seconds) with a detergent solution with a The result is a pH of 9 »8 and a strong blue color.

A stained and soiled cloth gets in the bathroom given and washed. After a few minutes, the blue color of the bath suddenly turns gray reddish-brown coloring, which corresponds to the coloring of a dirty washing solution. At this point in time the pH of the bath is 9.0. If another 50 g of the detergent are then added, the color fails of the bath turns blue again and the pH value of 9 »7 is established. The cloth is now washed further in the same bath and then dried. Bs is checked for discoloration due to the pH indicator polymer. There will be no discoloration established.

Example 2

A G6> condensate of p-xylenol-4-carboxy-phthaleinnaphthalene-sulfonic acid-formaldehyde-rhodamine B (15 «7 * H ^Ί1 x0.1) is used (pH indicator polymer, prepared according to process (A), which is red in the acidic range and turns blue in the alkaline range and at a pH of 8.8 - 9 »5). From this substance k0 parts are used. In addition, 5 parts of polyethylene glycol with an average molecular weight of about 8,000 are used, as well as 55 parts of anhydrous sodium sulfate *

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The pH indicator polymer, the polyethylene glycol and the anhydrous sodium sulfate are in a high speed Mixer mixed and the mixture is processed in a granulator to a granulate in which more than 80 $ of the 'grains have a particle size of 20 meshes each 2.5 cm.

In addition, the following granular type detergent is produced:

Sodium alkylbenzene sulfonate 25 parts

Sodium tripolyphosphate 30 parts

Sodium metasilicate 10 parts

anhydrous sodium sulfate 33.9 parts

Carboxymethyl cellulose 1 part

fluorescent brightener 0.1 part

Total quantity 100 parts

100 parts of the granular type detergent are uniformly mixed with 0.6 parts of the pH indicator polymer, whereby a detergent having a plurality of red particles is obtained.

According to Example 1, about 50 g of the detergent are used in 30 Given water and stirred in an electric washing machine for about 10 seconds · This creates a washing bath with a strong blue color and a pH value of 9 | 8. A stained one s and soiled cloth is placed in the bath and washed. After a few minutes the blue one disappears Sudden coloration and a reddish-gray to brown coloration appears. At this time the bath has a pH value of 9.0. If another 50 g of the detergent has been poured into the Bath are given, the color of the bath changes to blue and the pH is now 9ι7 · the washed Cloth shows no discoloration from the indicator polymer.

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Beisg ± el_3

Dibromothyraolphthalein bound to a co-polymer from Acrylic acid hydroxyethyl methacrylate type (1: 2x2) (pH indicator Po lymeres, made by. Method (b), which is colorless in the acidic range and strong blue in the alkaline range and which has a color change in the pH range from 8.5 to 9.5)

30 parts

Poly (sodium methylene naphthalene

sulfate) 30 parts

Polyethylene glycol (average Molecular weight about 8,000) 5 parts

anhydrous sodium sulfate ^ 35 parts

Total quantity 500 parts

The pH indicator polymer, the poly (sodium methyl naphthalene sulfonate), the polyethylene glycol and the anhydrous sodium sulfate are mixed uniformly, 3 parts of this mixture are also gleüiförmig 100 parts of a basic detergent according to Example 1 mixed, resulting in the detergent according to the invention The washing test according to Example 1 is carried out and similar results are observed.

Example ^

Dibromothymol-4 copolymer of methporyl acid amide phthalein acrylamide hydroxyethyl methacrylate (Ιχ2ι2) (pH indicator polymers β, prepared by method (c), which in the acidic area is colorless and in alkaline area strong blue and welob.es a color change in one has a pH range of 8.5 - 9.5)

30 parts

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Poly (sodium methylene naphthalene sulfate) 30 parts polyethylene glycol (durchsclinittlich.es

Molecular weight about 8,000) 5 parts

anhydrous sodium sulfate 35 parts

Total quantity 100 parts

The pH indicator, the poly (sodium methylene naphthalene sulfonate), the polyethylene glycol and the anhydrous Sodium sulfate is mixed uniformly and 0.8 part of this mixture is mixed with 100 parts of the basic detergent uniformly mixed according to Example 1, the detergent according to the invention being formed. Of the Washing test according to Example 1 is carried out, with similar results being obtained.

Example 5

Fully hardened or cross-linked powder of a co-condensate of dibromophenol-3 »^» 5f6-tetrachlorophthaleinmelamine-formaldehyde-rhodamine B (8t * t7: 45: 0.12) (pH indicator polymer, produced according to process (A), which is red in the acidic range and blue in the alkaline range and which changes at a pH range of 10.5 - 9 »5)

50 parts of poly (sodium methylene naphthalene sulfonate) 50 parts

Total quantity 100 parts

The pH indicator and the poly (sodium methylene naphthalene sulfonate) are mixed uniformly and the mixture is granulated in a granulator, resulting in granules in which more than 80 % of the particles have a particle size of 20 meshes per 2.5 cm . 4 parts of this granulated pH indicator polymer are made uniform with 100 parts of the basic detergent according to Example 2

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mixed, the detergent according to the invention with a plurality of red particles is obtained. The washing test according to Example 2 is repeated with this product, similar results are obtained,

Example_6

Co-condensate of p-xylenol-4-carboxyphthalein-napb.thalenesulfonic acid-formaldehyde (I5i? 4x1i) (pH indicator polymer, produced according to process (A), which is colorless in the acidic range and blue in the alkaline range and which is colorless a pH range from 8.8 to 9.5 changes)

KO parts

2-methoxy-4-anilinocarbonyl-benzene-azo-3-hydroxy-2 ¹ -naphthoic anilide (- ** "-), bound to a copolymer of the acrylic acid hydroxymethyl methacrylate (1j4: 5) type (polymer-bound red dye material ) 0.5 part of poly (sodium methylene napthalene sulfonate) 10 parts of polyethylene glycol (average molecular weight about 8,000) 5 parts of anhydrous sodium sulfate hk _t 5 parts

Total quantity 100 parts

These components are mixed in a high-speed mixer and the mixture is granulated, whereby a Granulate is obtained in which more than 80 $ of the particles have a particle size of 20 meshes per 2.5 cm. 0.8 part of this granulated pH indicator polymer becomes uniform with 100 parts of the basic detergent according to Example 2 mixed, wherein a detergent according to the invention, with a multitude of red particles is obtained. The washing test according to Example 2 is carried out, similar results are obtained.

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Claims (10)

2158058 PATENT CLAIMS . Detergents with anionic. © η and / or non-ionic and / or cationic and / or amphoteric surfactants and / or alkaline and / or acidic Agents as washing-active substances, characterized by a content that is soluble in a solution of the washing agent or dispersible polymers with pH indicator properties in an amount of Q, 1 - 50 percent by weight, based on the active washing substances. 2. Detergent according to claim 1, characterized in that the polymer with pH indicator properties in colloidal Form is dispersible in the detergent solution. 3 x detergent according to any one of claims ₍₁ or 2, daduroh in that the polymers with pH-indicator properties in admixture with the detergent-active substances and with builders present. k. Detergent according to one of Claims 1 to 3, characterized in that the polymer with pH indicator properties is in granulated form with granulation additives. 5. Detergent according to one of claims 1 to k _t, characterized in that the polymer with pH indicator properties consists of a polymer backbone with indicator-dye groups. 6. Detergent according to claim 5 _f, characterized in that the indicator dye is a phthalein indicator, a sulfonphthalein indicator or an azo indicator. 209824/1070 7 »Detergent according to one of claims 1 to 6, characterized characterized in that the pH indicator is about 50 to 0.1 Percentage by weight of the polymer with pH indicator properties matters « 8. Detergent according to one of claims 1 to 7 »characterized characterized in that the polymer with pH indicator properties contains the indicator dye in fused-on form having. 9. Detergent according to one of claims 1 to 3, characterized in that the polymer with pHrlndikator properties has the indicator dye as end groups. 10. Detergent according to one of claims 1 to 9, characterized characterized in that the polymer with pH indicator properties is polymerized into the indicator dye Has shape « 209824/1070