DK146781B - PROCEDURE FOR WASHING TEXTILES - Google Patents

Description

(19) DENMARK (J)

ug SUBMISSION WRITING oo 146781 B

DIRECTORATE OF

THE PATENT AND TRADEMARKET SYSTEM

(21) Patent Application No. 4517776 (51) Int.CI.3: D06L 1/12 (22) Filing Date: 07 Oct 1976 C 11 D 3/12 (41) Alm. available: 09 Apr 1977 (44) Submitted: 02 Jan 1984 (86) International Application No: - (30) Priority: 08 Oct 1975 DE 2544949 (71) Applicant: 'HOECHST AKTIENGESELLSCHAFT; 6230 Frankfurt / Main 80, DE.

(72) Inventor: Klaus' Henning; DE, Joachim 'Kandler; THE.

(74) Plenipotentiary: Budde, Schou & Co Engineering Company (54) Textile washing process

The present invention relates to a method for washing fabrics with an aqueous detergent-containing raft containing as a detergent substantially an organic anionic, nonionic, ampholytic or zwitterionic surfactant, a technical al-Q 2 potassium tripolyphosphate as a water-soluble builder, a finely divided al. - potassium aluminum silicate as water-insoluble builder and, optionally, ® additional detergent auxiliaries.

JO It is known that the washing and cleaning power of soaps and synthetic surfactants can be increased by the addition of certain compounds.

Such connections are referred to as builders.

^ The mechanism and details of the effect of builders have not yet been fully elucidated, so that it is not possible to predict in principle which types of connection could be suitable for this purpose.

Due to the many different single effects that together contribute to the enhancement of tenside washing power, the following requirements must be set for a builder based on the knowledge available today. The builder should be suitable for: 1. forming water-soluble complexes with water hardness agents such as calcium and magnesium ions; 2. dispersing pigment dirt particles as a major component of laundry dirt in the wash raft; 3. stabilizing released dirt in the washing raft to prevent the dirt particles from rubbing pulls on the fiber, 4. to inactivate mineral components present in the wash raft, and 5. to reduce the surfactant adsorption on the fiber.

In order to obtain information on the performance and suitability of individual products as builders, it is appropriate to determine their behavior and efficiency in a washing and cleaning process. This ensures that all factors involved in the builder effect are taken into account qualitatively and quantitatively.

Known builders are the water soluble alkali metal salts of mineral acids such as alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.

Among the known builders, the alkali metal polyphosphates occupy a preferred position because all of the above conditions are fulfilled by these, in combination with interface active compounds, produce synergistic effects as to the washing effect. As a result, they are today the most important builder in all detergents for fine washing, rough washing and variegated washing. In these, the pentane sodium triphosphate is used primarily. The detergents content of this builder ranges from 25 to 65¾ and in detergents the content is up to 90% for some.

As a result of the significant increase in the consumption of phosphate-containing detergents, both in the household and in the industry, the natural water content of these phosphates has increased. In discussing the causes of the increasing watercourse eutrophication, the water-soluble nitrate and phosphate salts have been recently attributed to the fact that they promote the growth of certain algae species under certain conditions and thus contribute to the eutrophication of the watercourses, the oxygen budget of the streams is disturbed. Although unambiguous clarification of the phosphate-containing detergent-containing detergent's share in stream runout is not yet feasible at present, it still seems desirable to develop potential nitrogen and phosphate-free substitutes for the builders used heretofore in detergent compositions or to obtain a detergent composition reduction total phosphorus content by combining alkali metal polyphosphates with other suitable detergent components.

Therefore, various organic compounds have been proposed as builders, e.g. nitrilotriacetic acid, ethylenediaminetetraacetic acid, citric acid, oxydacetic acid, oxydiruccinic acid, cyclocarboxylic acids or polymeric carboxylic acids such as polymaleic acid and polyacrylic acid and copolymers thereof with unsaturated carboxylic acids, olefins or short chain aliphatic or unsaturated, unsaturated or short chain

However, the above compounds have not been found to be satisfactory in every respect because they show either a strong complex formation with heavy metals and transition metals, whereby through direct sequestration or later remobilization of the river sediment, enrichment of heavy metals in the surface watercourses can occur. can enter the drinking water or because they do not have sufficient build-up properties initially mentioned and thereby do not give satisfactory washing results or are not sufficiently biodegradable.

More recently, it has been recognized that the water-insoluble alkali metal aluminum silicates, due to their ion exchange ability, are also suitable to replace a portion of the sodium tripolyphosphate in detergent compositions and thus reduce the total phosphate content of the detergent. Upon completion of the washing process, such water-insoluble builders can be easily separated from the washing float. However, although they remain in the wash float's wastewater, unlike the known organic builders, they do not cause a biological strain on the surface watercourses.

A method of washing e.g. textiles in the presence of water-insoluble alkali metal aluminum silicates in addition to traditional detergent components are disclosed in German Publication No. 2,412,837. In these detergent compositions, the proportion of 4,66781 meta and polyphosphates is limited such that the maximum phosphate content in the washing float is 0.6 g of phosphorus per day. liters of washing floats. According to the embodiments, 2.5 - 29.2 parts by weight of penta-sodium triphosphate and 45 - 11.3 parts by weight of sodium aluminum silicate with a calcium binding capacity of 150 mg CaO / g silicate per 100 parts by weight of detergent.

The advantages described in German Patent Specification No. 2,412,837 to said builder combination of sodium tripolyphosphate and sodium aluminum or sodium borosilicate in detergent compositions relate only to the so-called primary washing action, which is merely a measure of the clarification of an artificial smear material obtained. However, it has been found in practice that the secondary detergent effect of the known detergent composition - defined by the extent of the intrusion of the woven material - is unsatisfactory. However, in assessing a washing method, the secondary washing effect has the same meaning as the primary washing effect. Highly encrusted laundry loses in utility value because its suction capacity is reduced, wear is accelerated and wear is reduced as a result of a hard and rough grip. Finally, a further disadvantage of the known detergent composition is the result of the induction of the heater elements in the household washing machine induced by the washing process. Incorporated heater elements increase the energy cost of the washing process and lead to premature wear of the washing machine.

It has now surprisingly been found that the disadvantages of the detergent compositions according to German publication no.

2,412,837 is overcome when it is ensured that the content of alkali metal rayon or alkali metal diphosphate in the washing float - conditional on the process of preparing the alkali metal tripolyphosphate or washing powder - is not more than 0.1 g per liter. liters of washing floats.

In this case, contents of 0.5 - 2 g of alkali metal tripolyphosphate and 0.5-4 g of alkali metal aluminum silicate per liters of washing float sufficient to achieve a satisfactory primary and secondary washing effect.

Depending on the preparation, commercially available alkaline metal tripolyphosphates contain up to 20% by weight of alkali metal mono or alkali metal diphosphate, depending on the manufacturing process used. In addition, if the washing powder preparation is carried out by the heat-spray drying process, as is the case to a large extent, the content of alkali-metal mono- or alkali-metal diphosphate is increased as a result of the hydrolysis which takes place during the slurry preparation, and the pyrolysis of the tripolyphosphate feed, further to a considerable extent, so that the finished washing powder can contain significant proportions of these phosphates.

With the calcium and magnesium ions of the wash water, alkali metal mono and alkali metal diphosphates form insoluble precipitates unless the effect of these hardness forms is eliminated by appropriate measures. Despite the proportions of alkali metal mono- and alkali metal diphosphate, traditional washing powders that are confiscated on a sodium tripolyphosphate basis according to the prior art nevertheless provide satisfactory washing results because the content of the commercial sodium tripolyphosphate in the detergent is selected so that after the complexation of the calcium and sodium tripolyphosphate is available during the washing process so that precipitation of alkaline earth metal mono and alkaline earth metal diphosphates is avoided even at washing temperatures of up to 90 ° C. The use of detergent compositions corresponding to German publication specification No. 2,412,837 with reduced alkali metal tripolyphosphate content apparently cannot prevent the precipitation of salts which act as an inducing agent.

Accordingly, the invention relates to a method for washing fabrics by treating the fabrics with an aqueous detergent-containing float at a temperature of from ca. 20 to 95 ° C, wherein the detergent contains an organic, anionic, non-ionic, ampholytic or zwitterionic surfactant, an alkali metal mono or alkali metal diphosphate contaminated with water-soluble builder, a finely divided alkali metal aluminum silicate with a minimum of 5 100 g of dewatered silicate as a water-insoluble builder and optionally additional washing aids, which is characterized in that the washing float at a content of 0.5 - 2 g of alkali metal tripolyphosphate and 0.5 - 4 g of alkali metal aluminum silicate per at the same time does not contain more than 0.1 g of alkali metal mono or alkali metal diphosphate per liter. liter.

In a preferred embodiment of the process of the present invention, the detergent fleet may contain organic surfactants in amounts of from approx. 0.3 to approx. 1 g / liter.

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Furthermore, it has been found advantageous to use an alkali metal aluminum silicate having a particle size of no more than 40 µ ++ and a calcium bonding capacity of from approx. 10 to approx. 14 g Ca per 100 g of silicate as water insoluble builder. The alkali metal aluminum silicate may e.g. be a crystalline zeolite composed in the unactivated form of 18.2% Na 2 O, 30.8% Al 2, and 34.1%

SiO2 and 16.7% ^ O.

Finally, the present washing float preferably contains washing aids such as sodium silicate and / or magnesium silicate and / or carboxymethyl cellulose and / or sodium perborate tetrahydrate and / or ethylene diamine tetraacetic acid and / or sodium sulfate.

The present use of surfactants includes anionic, cationic, zwitterionic, ampholytic or nonionic surfactants.

Anionic surfactants are understood to mean the water-soluble salts of higher fatty or resin acids, such as sodium or potassium soaps of cured or uncured coconut palm or rapeseed oil, and of tallow and similar mixtures thereof. In the sense of the invention, anionic compounds are further understood to mean higher alkyl-substituted, single-core, aromatic sulfonates, such as alkyl benzene sulfonates having 9-14 carbon atoms in the alkyl group, alkylnaphthalene sulfonates, alkyltoluenesulfonates, alkylxylene sulfonates or alkylphenol sulfonates, - or hexa-decyl sulfate, triethanolamine lauryl sulfate, sodium or potassium oleyl sulfate, and sodium or potassium salts of lauryl sulfate ethoxylated with ca. 2-6 moles of ethylene oxide. Further suitable anionic surfactants are secondary linear alkanesulfonates as well as α-olefin sulfonates having a chain length of 12-20 carbon atoms.

The nonionic surfactants within the scope of the invention are understood to include such compounds which contain an organic, hydrophobic group and a hydrophilic group. Examples of nonionic surfactants are the condensation products of alkyl phenols with ethylene oxide or of higher fatty alcohols with ethylene oxide, furthermore the condensation products of polypropylene glycol with ethylene oxide or propylene oxide and the condensation products of ethylene oxide with the reaction product from ethylene diamine and propylene oxide. Also long-chain tertiary amine oxides belong to the group of the above compounds.

Finally, in the series of products of ampholytic or zwitterionic nature useful as surfactant constituents of the present process, the following compounds must be incorporated: Derivatives of aliphatic, secondary and tertiary amines or quaternary ammonium compounds having 8-18 carbon atoms and a hydrophilic group in the aliphatic group such as sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate, 3- (N, N-dimethyl-N - hexadecylamino) propane-1-sulfonate or fatty acid aminoalkyl-N, N-dimethylacetobethane wherein the fatty acid contains 8-18 carbon atoms and the alkyl group 3 carbon atoms.

Excipients and additives include products such as alkali metal or ammonium salts of sulfuric acid, silicic acid, carboxylic acid, boric acid, alkylene, hydroxyalkylene or aminoalkylene phosphonic acid, as well as bleaches, stabilizers for peroxide compounds and water-soluble organic complexing agents.

To the latter group belong specified natriumperboratmono- or tetrahydrate, or alkali metal salts of peroxymono--disvovlsyre, alkali metal salts of perpyrophosphor acid, water-insoluble, precipitated magnesium silicate and the alkali metal salts of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, methylenediphosphonic acid, hydroxyethandiphosphon acid and nitrilotrismethylene phosphonic acid.

Substances that increase the dirt-carrying capacity of washing floats, such as carboxymethyl cellulose, polyvinyl alcohol and polyvinylpyrrolidone, or foam regulators such as mono- and dialkylphosphoric acid esters having 16-20 carbon atoms in the alkyl group, as well as optical brighteners, disinfectants and the enzyme ligands thereof, and / or proteolytic enzymes method used detergent and detergent.

Laundry aids or additives which, in connection with the other components of the detergent, contribute to an improvement in the washing effect, in particular magnesium silicate, sodium silicate, sodium perborate tetrahydrate, sodium sulfate or carboxymethyl cellulose.

The preparation of the alkali metal mono- and alkali metal diphosphate-poor washing powders suitable for the present washing process can be e.g. be made by using either sodium tripolyphosphate which is purified by recrystallization or prepared from thermal phosphoric acid by the one-stage heat atomization process and having an active compound content of at least 95% peritanium sodium triphosphate, for 8 minutes. for the preparation of the washing powder or that sodium tripolyphosphate of at least 90% is used in the detergent confection according to the dry mixing process. In the latter case, no loss of sodium tripolyphosphate due to hydrolysis and pyrolysis occurs in the confection of the detergent.

The present process is illustrated in more detail by the following example.

Example

To determine the influence of tetrasodium di-phosphate on the secondary washing effect of combinations of sodium tripolyphosphate and sodium aluminum silicate, washing experiments are carried out in a Miele 416 S domestic washing machine with natural industrial water of 18 ° dH. As detergent components are used a) constant amounts of a detergent primer and b) variable amounts of sodium tripolyphosphate, tetrasodium diphosphate and sodium aluminum silicate.

The detergent primer has the following composition: 7% by weight dodecylbenzenesulfonate 3% by weight tallow fatty alcohol ethoxylate with 11 moles of ethylene oxide per liter. mole of tallow fatty alcohol, 3 wt.% cured tallow soap, 4 wt.% magnesium silicate, 3 wt.% sodium silicate, 1 wt.% carboxymethyl cellulose, 25 wt.% sodium perborate tetrahydrate, 0.2 wt.% ethylene diamine tetraacetic acid, 8 wt.% water and ad 100 wt.

The sodium tripolyphosphate used in the wash experiments is prepared by recrystallization of technical sodium tripolyphosphate, whose purity is 94.2%, corresponding to the indications of O.T. Quimby in J. Phys. Chem. 58 (1954), page 603. The purified sodium tripolyphosphate contains an additional 0.1% by weight of sodium hydrogen phosphate and 0.2% by weight of tetrasodium diphosphate.

The tetrasodium diphosphate used in the wash experiments is a commercial product and it contains an additional 1% by weight di-sodium hydrogen phosphate and 0.5% by weight sodium tripolyphosphate.

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As sodium aluminum silicate, a finely divided crystalline zeolite of the type "molecular sieve A" is used. The exchange capacity of this product-> | ·· | · · | · The Ca-ion content is 14 g Ca per liter. 100 g of compound at 90 ° C. Molecular sieve A has the following composition: 18.2 wt% Na 2 O, 30.8 wt% A 2 And, 34.1 wt% S 10 O 2 and 16.7 wt% H 2 O. The molar ratio is 0.97 Na 2 O 2 Al 2 O 3, 9 SiO 2 * 3, 1.0. The particle size of the molecular sieve A is a maximum of 40 μ.

The dosage of the detergent primer in the wash float is 5 g / liter wash float. washing test. The quantities of the other detergent components vary, as can be seen from the table below. The washing tests are carried out in accordance with the washing program for pre-wash and ready-wash. Here the maximum temperature at the pre-wash is 40 ° C and at the clear wash approx. 85-90 ° C. In addition to the clear wash, the laundry is rinsed 5 times and brought to a new washing cycle without intermediate drying, because in the pre-test no difference in the washing result appears when the laundry has already been dried in a drying cabinet.

In accordance with the method proposed by the Schweizerische Gesellschaft fur analytische und angewandte Chemie in "Seifen und Waschmittel", Bern, 1955, page 116, woven test material and ballast are used as contaminated Renforcé woven cotton material from Eidgenossische Materialprufungsanstalt, St. Gallen, Switzerland, in 40 x 80 cm stitched strips. The amount of woven material is 1.2 kg, resulting in a nice ratio of 1: 12.5. After 50 wash cycles, the woven material is pre-washed at 900 ° C and the increment of the woven material is ascertained as a percentage of the glow man. After 50 wash cycles, the heater elements are also evaluated with respect to the purpose for which they are taken out of the washing machine. The results obtained for each test series, each containing 50 wash cycles, are given in the table.

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Table

Test series Dosage of detergent components (g / liter)

no .___ I II III_IV_V_VI

1 52 0 0 7.6 strong 2 5110 3.4 rings 3 5 1 1 0.05 3.8 rings 4 5 1 1 0.1 4.6 rings 5 511 0.15 6.7 means 6 5 1 1 0 , 3 7.8 strong 7 5210 2.2 rings 8 5 2 1 0.1 2.4 rings 9 5 2 1 0.3 3.8 strong 10 5 4 1 0 1.4 rings 11 5 4 1 0.1 1.6 rings 12 5 4 1 0.3 2.2 means 13 5120 0.8 none 14 5 1 2 0.1 0.9 none 15 5 1 2 0.4 1.9 means 16 5 0 1 0 10, 8 strong In the table, column I means the amount of detergent primer in g / liter wash float, column II: the amount of sodium aluminum silicate (molecular sieve A) in g / liter wash float, column III: the amount of sodium tripolyphosphate in g / liter wash float, column IV: the amount of tetrasodium diphosphate / liter wash nice, column V: increment of the woven material after 50 wash cycles in%.

column VI: increment of the heaters after 50 wash cycles.

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Experiments rows 2-4, 7, 8, 10, 11 and 14 correspond to the method of the present invention, while the other rows serve comparison. It can be seen from the table that the washing experiments carried out under washing conditions according to the invention cause a significantly poorer increment of the laundry and heater elements in the washing machine than in the comparative tests. Thus, the process at issue here must be regarded as a technical advance over the procedure in German Publication No. 2,412,837.