DE2158056C3 - laundry detergent - Google Patents

Description

The invention relates to a detergent for fibers and textile material with anionic and / or nonionic and / or cationic and / or amphoteric surfactants and / or alkaline agents and / or acidic agents as washing-active substances and with a pH indicator.

Detergents for fibers, textiles and clothing usually contain fatty acid soaps, synthetic ones surfactants, alkaline agents and acidic agents, depending on the application. Usually one becomes Detergent solution is prepared by placing an arbitrary amount of detergent in a solvent dissolves, depending on the operator's experience. Often more detergent is then added, or the detergent solution is changed depending on how dirty the detergent solution is. Hence it can different concentrations of the detergent in the detergent solution come, even if the Operator to carefully read the operating instructions

ίο tries to obey Thus it is difficult to concentrate the detergent solution and in particular the pH of the detergent solution to adjust. This is particularly critical if the laundry is destroyed or at a certain pH value damaged.

In general, a major component or additive is an electrolyte, or the like Effectiveness of the main components or additives depends on the hydrogen ion concentration Accordingly, it is possible to adjust the detergent concentration to adjust based on the pH of the detergent solution, making an economical Application of the detergent is guaranteed when the laundry is at a certain pH If the detergent solution is damaged, the laundry can be effectively protected.

A convenient way to check the pH of a solution is to add a pH indicator dye. But if you have a detergent solution for washing fibers or textile material one of the If the usual pH indicator dyes are added, the laundry will be discolored by absorption of the Dye on the fibers. Therefore, up to now pH indicator dyes have only been added to cleaning agents, which are not intended for washing textile fibers and textile material. The US patents 25 02 881 and 29 94 664 describe cleaning agents for cleaning windows, painted surfaces, Floors, tiles, wood, glass or pipes or the like,

with lower molecular pH indicator dyes being added to monitor the pH value.

DE-OS 14 67 666 describes a detergent for fibers and textile material, which is in the solid state Contains particles of a low molecular weight dye for a mottled appearance. Since according to According to this publication, the absorption of the dyes on the fibers cannot be avoided, one therefore chooses Dyes which are colorless under the pH conditions of the detergent solution, so that the unavoidable Absorption of the low molecular weight dye on the fibers does not cause discoloration or staining the laundry leads.

It is therefore an object of the present invention to provide a To create detergents for fibers or textile material, which is a pH indicator for monitoring the Contains pH of the detergent solution, which is not substantially absorbed by the laundry and thus does not lead to discoloration of the laundry.

According to the invention, this object is achieved by a

^h0 detergent dissolved, which has 0.1 to 50 percent by weight, based on the washing-active substances, of a polymer which is soluble or dispersible in a solution of the detergent and has pH indicator properties, which when a certain pH value is exceeded

^M tes of the detergent solution changes.

When using the detergent according to the invention, a certain value is exceeded pH value due to a change in the color of the detergent

solution displayed. The polymer with pH indicator properties is not adsorbed in the laundry and can be completely removed with the detergent solution and rinsed out. It will not leave any stains.

By using the detergent according to the invention can easily be avoided that the pH of the Detergent solution assumes a value at which the objects to be washed are damaged.

According to the invention, the detergent can use all washing raw materials contain, which are suitable for objects to be washed, dirt in water or in to remove aqueous medium. The detergent according to the invention is suitable as a household detergent for Clothing or as an industrial detergent for washing fibers, in particular wool, for finishing the cleaning of laundry, also for pulp and in the paper industry.

The detergent according to the invention can, in particular, contain anionic surface-active agents! included, 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. Furthermore, nonionic surfactants, such as. B. polyoxyethylene-alkyl-ether, polyoxyethylene-alkyl-phenol-ether, polyoxyethylene-alkyl-ester, polyoxyethylene-anhydrosorbitol-alkyl-ester and polyoxyethylene-polyoxypropylene block copolymers in question, as well as cationic surfactants such. B. quaternary ammonium salts and alkyloyridinium salts, as well as amphoteric surfactants, such as. B. nonionic-anionic, nonionic-cationic and anionic-cationic surfactants. Alkaline agents are also possible, such as B. Sodium Hydroxide, Sodium Sesquisilicate, Sodium Metasilicate. Sodium orthophosphate. Water glass (Na ₂ O · 1.6 SiO _2; Na ₂ O · 2 SiO _2; Na ₂ O ■ 3.2 SiO _2), sodium carbonate, sodium pyrophosphate and sodium borate, as well as acidic agents such. B. sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfamic acid, oxalic acid or citric acid or mixtures of all of these agents.

Furthermore, additives or "builders" can be added to the detergent, such as. B. sodium sulfate, Sodium metasilicate, sodium sesquisilicate, sodium or- · * 5 thosilicate, sodium carbonate, sodium bicarbonate, sodium hexamethaphosphate, Sodium tripoly-phosphate, sodium hexamethaphosphate, sodium chloride, carboxymethyl cellulose, Methyl cellulose, hydroxyethyl cellulose, Ethylenediamine-tetraacetic acid and fluorescent Ό optical brighteners.

The polymer used for the detergent according to the invention has pH indicator properties has a structure in 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 according to one of the following processes can be produced:

(A) A pH indicator with a group which mi is condensable or addition condensable. becomes with a polymer or a polymerizable Monomers condensed, which is a condensable or addition condensable Group. f> '>

(B) A pH indicator with a diazonium group is mixed with a Λ, / I-ethylenically unsaturated monomer and polymerized, the pH indicator with the diazonium group being used as a polymerization initiator.
(C) A pH indicator having an α-ethylenically unsaturated group is mixed with an α-ethylenically unsaturated monomer and copolymerized.

These methods can be combined or applied sequentially. Instead of pH indicator can be a Vorprodukat of the pH indicator, after the condensation reaction or Addition reaction or polymerization reaction the intermediate component to a pH indicator is converted to form the pH indicator polymer. To achieve a sharp color change in the event of a change in pH or to shift the pH range at which the color changes during washing takes place, it is possible to use conventional dyes, pigments or dyes bound to polymer material to add. It is also possible to use the pH indicator polymer with a dye, pigment or polymer with bound dye or a derivative thereof which can be reacted with the pH indicator polymer to react. Can be finer such a reaction can be carried out with the raw material or with an intermediary. These Further implementation of the pH indicator polymer can take place before the reaction, during the reaction or after the Reaction to form the pH indicator polymer take place. If an intermediate stage for manufacture of the pH indicator polymer is used, a development treatment follows. The for Production of the pH indicator polymer used according to the invention The pH indicators used can be weak acids or weak bases, the visible absorption spectrum of which is dissociated State is different from that in the normal molecular state.

The pH indicators include:

a) Phthalein indicators such as B. phenolphthalein, o-cresol-phthalein, thymoi-phthalein, p-xylenoI-phthalein. α-naphthol-phthalein, dibromophenolphthalein, Phenol-4-carboxy-phthalein, thymol-4-carboxy-phthalein, p-xylenol-4-carboxy-phthalein, PhenolOAS.ö-tetrachlorophthalein, etc .;

b) sulfon-phthalein indicators, such as. B. phenol red, cresol red, m-cresol purple, p-xylenol blue, thymol blue, Xylenol orange, bromophenol red. Bromocresol purple, bromocresol green, bromothymol blue and Bromophenol blue or the like;

c) Azo indicators, such as B. Congo red, methyl orange, p-ethoxycrysoizine, Λ-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 following describes the production of the pH indicator polymer according to method (A) are explained. The condensable or addition condensable group can be an amino group, a hydroxyl group, a carboxy group, a carbamide group. a suIfamid group, an ester group of a lower alcohol, a lower ester group, a group with an aromatic ring which has substituted hydrogen, an N-methylol group, an N-halomethyl group, a C-methylol group, a

C-halomethyl group, an epoxy group, a Halohydrin group, an aldehyde group, an isocyanate group, an acid chloride group, a Halotriazine group and a diazonium group.

The pH indicator may have such a reactive group per se, or a suitable one pH indicator can be produced by adding one of the mentioned reactive groups to the molecule of the Introduces pH indicator or its precursor

The polymers or the polymerizable monomers, which with the pH indicator that has a condensable or addition condensable group, can be implemented include conventional reactive polymers and polymerizable monomers, such as B. the following connections:

1. Polymers and monomers for the production of a pH indicator polymer with a methylol group, an alkoxymethyl group, a halomethyl group or the like as a condensable group.

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

b) Compounds made by reacting formaldehyde with polyamide, with glue, with Polyacrylamide or with acrylamide copolymers and components for production of these connections.

c) homopolymers of unsaturated methylolamides, such as. B. of N-methylolacrylamide and Copolymers of the same with other monomers.

2. Polymers and monomers for the production of the pH indicator polymer with an epoxy group or a halohydrin group as a condensation group.

a) Condensates of polyvalent amines, of polyvalent phenols or of polyvalent ones Amides with epihalohydrin, 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 ;> the chlorohydrin compounds such as B. glycidyl methacrylate, γ-chloro-jS-hydroxyn-propyl methacrylate and copolymers of the same with other monomers.

c) ethylene oxide, ethylene chlorohydrin, propylene oxide.

3. Polymers and monomers for the production of pH indicator polymers with carboxyl groups, Acid chloride groups, acid anhydride groups, ester groups of lower alcohols, lower fatty ester groups as condensation groups.

a) reaction products of polyhydric alcohol, such as. B. of ethylene glycol, propylene glycol, Neopentyl glycol, glycerine, sorbitol anhydride, polyethylene glycol, polypropylene glycol, diethano'amine, Triethanolamine, methyl cellulose, hydroxyethyl cellulose with polybasic carboxylic acids, ivie z. B. maleic anhydrides, fumaric acid, phthalic anhydride, 4-sulfophthalic acid.

Adipic acid, citric acid, tartaric acid and components for the manufacture of these products, b) Reaction products of ethylenediamine, hexamethylenediamine, ethanolamine, mono- (polyethylene glycol) amine with the polybasic carboxylic acids mentioned and the components for the manufacture of these products.

The pH indicator polymer can by reaction

ίο the pH indicator made with a polymer are, if you used a polymer as a starting material and a pH indicator, which a Has 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 one Component of the same will depend on the type of reactive groups and chemical properties of the starting compounds carried out.

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

The following describes the production of the pH indicator polymer (B) will be explained. In this preparation (B) the diazonium group can be 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 diazonium compound can be made by diazotizing an amino group of the pH indicator will. If necessary, a stabilizer can be added to the diazonium compound. The the Diazonium compound added «, 0-ethylenically unsaturated Monomers can be conventional radically polymerizable monomers, ζ Β. unsaturated Carboxylic acids, such as acrylic acid, methacrylic acid or alkyl esters, hydroxyalkyl esters, polyalkylene glycol esters and dialkylaminoethyl esters thereof and acid amides, N-alkoxymethyl acid amides and glycidate esters thereof as well as acrylonitrile, vinyl acetate and styrene.

It is believed that the polymerization of the

so Λ, ^ - ethylenically unsaturated monomers in the presence of the diazonium compound of the pH indicator caused by the fact that the diazonium group by heat or by the influence of light or by pH change or by the influence of a diazo decomposition agent, like £ .. B. 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 ", /! - ethylenically unsaturated monomers takes place in the presence of these free radicals as starters, with the resultant at the same time Polymer enters a conjugate bond with the pH indicator.

The following describes the production of the pH indicator polymer (C). The Λ, / J-ethylenically unsaturated Group can be an acrylamide group, a methacrylamide group, a methacryloyl-oxy - ^ - hydroxy-n-propyl-amino group, a methacryloyl-oxy-0-hydroxy-n-propyl ether group, an acrylamide

ethylene group or a vinyl group or the like. Be. This t.ß- ethylenically unsaturated group is introduced either into a preliminary stage of the pH indicator or into the finished pH indicator. The *. /} - ethylenically unsaturated monomer, which is mixed with the pH indicator, can be one of the monomers mentioned under (B). The pH indicator is conjugated with the polymer by copolymerization of the pH indicator with the ■ x. / J-ethylene: s (.h unsaturated group and the \ .; i-ethylenically unsaturated monomers in the presence of a conventional polymcnsationsstarers such as / .. B. potassium perersulfai, ammonium per sulfate, azobisisobutyl sulphuronitrile or benzoyl peroxide.

In the preparation (B) and (C) the pH indicator polymers by solution polymerization in aqueous solution or in an organic solvent be prepared or by emulsion polymerization, by suspension polymerization in water or through block polymerization. The pH indicator polymer that can be prepared in this way can be soluble in water or in alcohol or, depending on the properties of the polymer 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 using the PoIvmere with chloroacetic acid. Sodium bisulfite. Sulfamic acid. Sulfuric acid. Ethylene oxide, lower amine, Reacts pyridinium hydrochloride or ethyleneimine. 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. Methyloicarbamide. Acid chloride or isocyanate or the like. Reacts.

The pH indicator polymers obtained change their color in a certain pH range, though some are soluble in aqueous medium and others in are dispersible in an aqueous medium. A minor one

.-_ j ι .. η: -u ~ - Λ ~~ tr - -U

Changes in hue are found when the polymer is bonded to the pH indicator at one point. at which the pH range and the hue in color of the pH indicator affect ^ ⁴ are influ-. As an example, consider a pH indicator polymer made from phenolphthalein as indicator and meiamine-formaldehyde condensates as polymers water-soluble pH indicator polymer lies at pH values from 7.9 to 9.5. and the range of the color change of the water-insoluble pH indicator polymer lies at pH values from 6.5 to 12.0. Sharp color changes are found, while the phenol phthalene itself is in the The acid form is colorless and in the base form turns red and at a pH range of 8.0 to 9.6.

Since the sensitivity of the water-insoluble & o pH indicator polymer particles against pH change on particle size and physical properties, such as B. depending on the wettability with water, it is preferred to have the particles as fine as possible to choose. The ratio of the pH indicator polymer to the laundry raw materials in the inventive Detergent should be large enough so that the envelope can be seen in the color of the detergent solution is. The amount of pH indicator in the pH indicator polymers can vary depending on the type and type of reaction Combination of the starting materials as well as the molecular weight of the polymer and the manufacturing conditions to be selected. It is usually 50 to 0.1%. preferably 30 to 1%. the Amount of the pH indicator polymer to the detergent substances in the detergent according to the invention not restricted; however, it is usually 50 to 0.1, and preferably 10 to 1% in the case of one powdered water-insoluble pH indicator polymers and preferably 5 to 0.1% in the case of a water soluble pH indicator polymers. That pH indicator polymers can be used with the neutral builder, with surface-active agents, with wetting agents, with moisture-proof agents and also with detergents in a suitable form, such as. Am aqueous solution, in aqueous dispersion, in Pasietiform. in the form of a fine powder or in the form of granules or capsules depending on the type of detergent be mixed.

To produce granules, the pH indicator polymer is mixed with a small amount of water mixed with a volatile organic solvent and if necessary with a surfactant or builder all rolled into one Agitator is granulated. If drying is carried out, an aqueous solution or a solution in an organic solvent can be dried by spray drying. Door granulating a wetting paste or wet paste can also be used.

The following is the mode of operation of the invention Detergent with the detergent substances and the pFI indicator polymer are explained.

Household detergents are mainly used to wash clothes. A typical one Example of such a weakly basic detergent comprises 15 to 30% surfactants such as z. B. sodium alkylbenzenesulfonate. Sodium volefin sulfonate iinri rtas sodium salt pinps higher alcohol sulfate.

1 to 2% sodium benzene sulfonate. 10 to 30% tripolyphosphate as builder, 2 to 6% sodium silicate. 20 to 50% sodium sulfate and a small amount of carboxymethyl cellulose and a fluorescent optical Brightener. Such a detergent is made by spray drying a slurry of the components obtained in the form of granules with internal cavities.

To carry out the washing operation, t.% Va 50 g of the detergent in about 30 l of water in one Washing machine dissolved into a detergent solution. The pH range for a good washing effect is usually in the weakly alkaline range and should especially during the washing operation in one pH range from 9.5 to 10.0 must be maintained. During the washing operation is the pH of the washing liquor gradually decreasing due to decomposition and contamination. At the same time will the washing activity is reduced.

By adding a pH indicator polymer with a pH range from 10.0 to 9.5, at which the alkaline Coloring occurs and one can have a pH range of 9.0 to 8.5 at which the acidic decolorization takes place With such a detergent, the concentration of the detergent in the washing liquor is slightly and control economically with the help of the indicator. You can also remove the dirt and the

Inactivation of the washing liquor by decomposition of the detergent by observing the color change track so that new detergent can be added at the right time or the detergent solution can be changed. In this way, the washing process is made efficient and economical.

t! s is a major advantage of the invention Detergent that the pH indicator polymer has a polymer structure, so that the pH indicator polymer is dispersed in the form of fine particles or microfine particles, causing staining or discoloration of the surface of the laundry advantageously is avoided.

In the fiber industry it is necessary to have working conditions avoid, in which the fiber is damaged, namely in finishing processes, with Washing, bleaching and removing encrusted dirt from various fibers, woiie is z. 13. Partially decomposes at a pH greater than 9, and silk should be at a pH of less than 10.5 and preferably less than 10.0 are treated. Rayon should also be with one pH less than 10.0 to be treated. The control of the process and the product quality can can be easily and accurately carried out by combining the detergent of the invention with the pH indicator polymer applies with a suitable pH range of color change.

When removing encrusted soiling, the detergent contains an enzyme and a nonionic surfactant applied. A suitable pH for removing encrusted dirt depends on the temperature, the length of time and the type of enzyme and lies usually in the range from 6.3 to 6.5, if the bath contains 7 to 12 g / l of commercial amylase and 0.04% of a nonionic surfactant and used at 60 to 70 ° C. Even Here it is possible to use the procedure for removing encrusted dirt under optimal conditions riiirrhviifiihppn wpnn pin nH.lnHiliotnr.Pnlumprpc with

a corresponding transhipment area is present. Thus, when using the inventive Den Detergent in a simple and clear way due to the color change in the different Applications control the pH so that the detergent is applied in the most effective manner can be and a mode of operation in a dangerous pH range, in which the laundry or others objects to be washed can be damaged, can be avoided.

The laundry can be washed without discoloration by the pH indicator, so that the detergent can be used economically and effectively; the washing process can be controlled simply and precisely and the quality of the washed products can be increased.

In the following, the invention is explained in more detail on the basis of exemplary embodiments. All partial information and percentages are parts by weight or percentages by weight.

example 1

032 parts of powdered thymolphthalein-4-carbamide polyethylene glycol (pH indicator polymer with a molecular weight of about 4,000 according to method A, which is colorless in the acidic range and strong blue in the alkaline range and in one pH range from 8.9 to 9.5 changes) are mixed with 100 parts of the mixture below, wherein the detergent according to the invention is produced.

Sodium alkylbenzenesulfonate 25 parts Sodium tripolyphosphate 30 parts Sodium metasilicate 10 parts anhydrous sodium sulfate 34 pieces Carboxymethyl cellulose I part 11 in total 100 parts

Approximately 50 g of the detergent * obtained are used in 30 1 Put water in an electric washing machine and stir for about 10 seconds, using a detergent solution

ii with a ph who! of 9.8 and a strong blue Color arises.

A stained and dirty cloth is placed in the had and washed. After a few minutes suddenly changes the blue color of the bath to a gray to reddish-brown color, which is the The color corresponds to that of dirty detergent solution. At this point the pH of the bath is 9.0. if then another 50 g of the detergent are added, so the color of the bath looks up again

2) Blue around and the pH value of 9.7 is established. That Cloth is then washed further in the same bath and then dried. It will look at discoloration Checked reason of pH indicator polymer. No discoloration is found.

Example 2

It becomes a co-condensation of p-xylenol-4-carboxyphoid thalein-na ph thalin-si! I fonsäure - formaldehyde-rhodamine B (I 5: 74: 11: 0.1) used (pH indicator polymer. produced according to process A. which is red in the acidic range and blue in the alkaline range and at a pH value of 8.3 to 9.5 changes). 40 parts of this ·· substance are used. Furthermore, 5 Tr> ilp Pnlväthvlpn-tjlvrnl with pinpm (liirrhqchniltlirhpn Molecular weight of about 8000 used and 55 parts of anhydrous sodium sulfate.

The pH indicator polymer, polyethylene glycol and the anhydrous sodium sulfate are mixed in a high speed mixer and the mixture is mixed processed in a granulator to a granulate in which more than 80% of the grains have a particle size of Have 20 stitches per 2.5 cm.

The following granular type detergent is also produced:

Sodium alkylbenzenesulfonate 25 parts Sodium tripolyphosphate 30 parts Sodium metasilicate 10 parts anhydrous sodium sulfate 33.9 parts Carboxymethyl cellulose Part 1 fluorescent brightener 0.1 part

Total of lOO parts

100 parts of the granular type detergent will be used uniformly mixed with 0.6 parts of the pH indicator polymer, being a detergent with a variety of red particles is obtained.

According to Example 1, about 50 g of the detergent are placed in 301 water and in an electric Washer stirred for about 10 seconds. This creates a wash bath with a strong blue color and a pH of 9.8. A stained and

It

soiled cloth is put in the bath and washed. After a few minutes it disappears suddenly blue in color and a reddish-gray to brown color appears. At that time the bathroom did a pH of 9.0. If again about 50 g of the detergent are added to the bath, the beats The bath changes color to blue and the pH is now 9.7. The washed cloth shows none Discoloration due to the indicator polymer.

H e i s ρ i e I J

Dibromothymolphthalein bound to a
Co-polymer of the acrylic acid-hydroxyethyl methacrylate type (1: 2: 2) (pH indicator polymer. Manufactured according to process B. which is colorless in the acidic range
and strong in the alkaline range
and which has a color change in the
has a pH range of 8.5 to 9.5)
PoIy (N at rhi m-met hy len-naph thai insu I fat)
Polyethylene glycol (average
Molecular weight about 8000)
anhydrous sodium sulfate

30 parts
30 parts

5 parts
4 3τ parts
500 parts

total quantity

The pH indicator polymer, the poly (sodium methylcn-naphthalene sulfonate), the polyethylene glycol and the anhydrous sodium sulfate are mixed uniformly. 3 parts of this mixture are also used uniformly mixed with 1000 parts of a basic detergent according to Example 1, the inventive Detergent is produced. The washing test of Example I is carried out and similar results are obtained observed.

Example 4

Dibromothymol-4 copolymer from
Methacrylic acid amide phthaleinacrylamide hydroxyethyl methacrylate
'! · 2 ■ 2 ^ '"H!" D ^; l · ⁰ '" ¹ ' .ρ«! ·. '»» ·· "!

produced by process C, which

is colorless in the acidic range and in the

alkaline area strong blue and

which is a color change in one

pH range from 8.5 to 9.5) 30 parts

Poly (sodium methylene naphthalene sulfate) 30 parts

Polyethylene Glycol (average

Molecular weight about 8000) 5 parts

anhydrous sodium sulfate 35 parts

Total 100 parts

The pH indicator, the poly (sodium methyl naphthalene sulfonate), the polyethylene glycol and the anhydrous sodium sulfate are mixed uniformly, and 0.8 parts of this mixture are mixed with 100 parts of the basic detergent according to Example 1 mixed uniformly to form the detergent according to the invention. The washing test according to example 1 is carried out with similar results.

Example 5

Fully hardened or crosslinked

Powder of a co-condensate of dibromo-

phenol-SAS.e-tetrachlorphthalein-mel-

amine-formaldehyde-rhodamine B

(8: 47: 45: 0.12) (pH indicator-poly-

meres, produced according to method A,

which is red in the acidic area and

in the alkaline range blue and which

at a pH range of 10.5 to 9.5

enveloped) 50 parts

Poly (N a tr ium- me thy len-naph thai in-

Milfonat) 50 parts

Total 100 parts

The pH indicator and the poly (sodium methylene naphthalene sulfonate) are mixed evenly.

UdU Ulf mixture wii'u granulated in a Cjr <inüuiUir.

whereby a granulate is obtained in which more than 80% of the particles have a particle size of 20 meshes per 2.5 cm exhibit. 4 parts of this granulated pH indicator polymer are uniformly mixed with 100 parts of the basic detergent according to Example 2, wherein the detergent according to the invention is obtained with a plurality of red particles. Of the The washing test according to Example 2 is repeated with this product, with similar results being achieved.

Example 6

Co-condensate of p-xylenol-4-carboxyphthalein-naphthalene-n-sulfonic acid-formaldehyde (15: 74: 1 l) (pH indicator polymer, prepared according to process A. which is colorless in the acidic range
is and in the alkaline range blue and
which at a pH range of
8.8 to 9.5 turns) 40 parts

2-methoxy-4-anilinocarbonyl-benzene-azo-3-hydroxy-2'-naphthoic anilide (-4 "-),
to a co-polymer of the acrylic acid hydromethyl methacrylate type ( 1: 4: 5)
bound (polymer-bound red
Dye material)
Poly (sodium methylene naphthalene sulfonate)

Polyethylene glycol (average
Molecular weight about 8000)
anhydrous sodium sulfate

0.5 parts 10 parts

5 parts
44.5 parts

100 parts

total quantity

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 mesh per 2.5 cm. 0.8 parts of this granulated pH indicator polymer are uniformly mixed with 100 parts of the basic detergent according to Example 2, whereby a detergent according to the invention having a large number of red particles is obtained. It will be the Washing test carried out according to Example 2, with similar results being achieved.

Claims (10)

Patent claims: 1. Detergents for fibers and textile material with anionic and / or nonionic and / or cationic and / or amphoteric surfactants and / or alkaline and / or acidic Agents as washing-active substances and with a pH indicator, characterized by 0.1 to 50 percent by weight, based on the washing-active substances, one in a solution of the detergent soluble or dispersible polymers with pH indicator properties that when exceeded a certain pH value of the detergent solution changes 2. Detergent according to claim 1, characterized in that the polymer with pH indicator properties is dispersible in colloidal form in the detergent solution 3. Detergent according to one of claims 1 or 2, characterized in that the polymer with pH indicator properties are present in a mixture with the washing-active substances and with builders 4. Detergent according to one of claims 1 to 3, characterized in that the polymer with pH indicator properties in granulated form with granulation additives. 5. Detergent according to one of claims I to 4, characterized in that the polymer with pH indicator properties consists of a polymer backbone with indicator-dye groups. 6. Detergent according to claim 5, characterized in that the indicator dye is a Phthalein indicator, a sulfonphthalein indicator or is an azo indicator. 7. Detergent according to one of claims 1 to 6, characterized in that the pH indicator is about 50 to 0.1 percent by weight of the polymer with pH indicator properties. 8. Detergent according to one of claims 1 to 7, characterized in that the polymer with pH indicator properties has the indicator dye in condensed form. 9. Detergent according to one of claims I to 8, characterized in that the polymer with The indicator dye has pH indicator properties as end groups. 10. Detergent according to one of claims 1 to 9, characterized in that the polymer with The indicator color has pH indicator properties in polymerized form.