DE4029297A1 - AMINODICARBONIC ACIDS AND THEIR DERIVATIVES AS STABILIZERS FOR THE OXYGEN BLEACH IN TEXTILE LAUNDRY - Google Patents

Description

The invention relates to chemical compounds or mixtures of substances the property, the bleaching effect of bleaching active oxygen Bleaching agents containing oxidation level -1 in textile washing / Increase textile bleaching in the presence of traces of heavy metal ions.

As a bleaching agent for textile bleaching during washing are used in Western Europe almost exclusively sodium perborate or hydrogen peroxide used, which in addition to the surfactants and other active substances during the Washing process contribute to dirt removal and tissue lightening should. For typical stains that are hardly possible without bleach remove, count z. B. red and blue anthocyanin dyes Fruits, turmeric dyes from curry and mustard, brown tannins from Teas, humic acids from coffee, tea, cocoa and carotenoid dyes from carrots and tomatoes.

The principle of action of the bleaching agents includes the chemical one Saturation of delocalized double bond systems of colored soiling by hydroxylation and its subsequent oxidative Fragmentation into water-soluble products.

A high effectiveness of bleaching sets you as selective as possible oxidative attack on the double bonds of the colored contaminants ahead. At the same time, those in large surplus Textile fibers protected from oxidative damage. The chemical reaction mechanisms of effective bleaching and fiber damaging Side reactions differ considerably. Open here possibilities in the mode of action of the bleach to intervene to control. From dealing with such problems So-called bleaching systems can result as a solution to the problem.  

Sodium perborate or hydrogen peroxide form in the alkaline Wash liquor peroxide anions (I) at higher washing temperatures have a bleaching effect above about 70 ° C.

NaBO₃ · 4 H₂O → Na⁺ + BO ^- ₂ + 3 H₂O + H₂O₂

OH ^- + H₂O₂ ⇆ HOO ^- + H₂O (I)

Nowadays, lower washing temperatures of 30 ° C-60 ° C are common. The perborate must therefore be "activated". You bet Detergents, for example tetraacetylethylenediamine (TAED) or sodium p-isononanoylbenzenesulfonate (ISO-NOBS) too, with that from sodium perborate resulting hydrogen peroxide with formation of peracids, namely peroxyacetic acid (II) from TAED or peroxiisononanoic acid (III) react from iso-NOBS. The peracids already work bleaching at low washing temperatures.

CH₃-COOOH (II)

C₈H₁₇COOOH (III)

The peroxide anions I attack double bonds from colored contaminants nucleophilic, while they are from the percarboxylic acids II and III be attacked electrophilically. The textile fibers are practical ionic not oxidizable as it either has none or is chemically deactivated Double bonds included.

Although the homolytic decay of the intermediate or Hydrogen peroxide used directly as bleach in pure A high activation energy barrier of 48 kcal / mol, this reaction must be given special attention.

The homolysis of hydrogen peroxide becomes inevitable in the washing process Traces of heavy metal ions catalyzed and can thus Main reaction will be. Hydroxyl and perhydroxyl radicals are non-selective, saturated substances are also effective, i.e. H. Textile fibers, on and therefore bleach badly.  

For example, according to W. Trieselt, Melliand Textilberichte 1970, 1094 play the following reaction:

Fe ²⁺ + H₂O₂ → Fe ³⁺ + OH˙ + OH ^-

OH˙ + H₂O₂ → HOO˙ + H₂O

HOO˙ + CU ²⁺ → Cu⁺ + O₂ + H⁺

Fe ³⁺ + Cu⁺ → Fe ²⁺ + Cu ²⁺

The molecular oxygen produced in this example does not work bleaching and leaving the wash liquor as a gas. The intermediate Radicals can attack the fibers. That on iron and copper ions existing catalyst system regenerates itself continuously.

J. Dannacher and W. Schlenken, Textilveredlung 25, 205 (1990) say however, that the mechanism of textile bleaching has not yet been elucidated is.

The formation of radicals from hydrogen peroxide can be masked the heavy metal ions z. B. suppressed with complexing agents will. DE-OS 7 03 604 describes a method for stabilization of per compounds during textile washing by magnesium silicate. For stabilization and fiber protection, 0.2% to 1.5% Magnesium silicate recommended in detergents.

Magnesium silicate is also used in detergents today. Its effect is due to the combination with ethylenediaminetetraacetate (EDTA) or phosphonates e.g. B. 1-Hydroxyethane-1,1-diphosphonic acid still increased. The basic formulations for powder detergents contained according to G. Jakobi and A. Löhr, Detergents and Textile Washing, VCH publishing company, Weinheim 1987, p. 106, 0.2% -0.5% EDTA or phosphonates as stabilizers. G. Jakobi and M. Schwuger, Chemiker-Zeitung 99, 182 (1975) describe that the biological Degradability of EDTA and also 1-hydroxiethan-1,1-diphosphonic acid under the conditions of the "closed bottle test" as low  must be classified. Recently, Ch. Gousetis et al., Tenside Surf. Det. 27, 41 (1990) Isoserine diacetic acid as a new, biological degradable complexing agent for detergents and cleaning agents presented. The production of isoserine diacetic acid is very technical complex. DE-OS 23 39 888 describes the production and application of N, N-biscarboxymethyl-L-glutamic acid as a complexing agent for Laundry detergent. In the manufacture of this product, a big one Excess chloroacetic acid needed.

The object of the present invention was therefore to create new environmentally friendly To provide bleach stabilizers that are technically are easy to manufacture.

The task was solved by using natural or biotechnological easily produced amino acids.

The invention therefore relates to the use of natural Material or biotechnologically produced amino acids and / or their succinic acid amides and / or their maleic acid amides and / or their monocarboxymethylates in acid form or in the form of their Alkali metal salts as bleach stabilizers.

Typical representatives are the substances listed in the formula L-glutamic acid IV, L-glutamic acid succinic acid amide V and L-glutamic acid, N-carboxymethyl-L-glutamic acid VI or its sodium salts:

It has surprisingly been found that the non-toxic natural products L-glutamic acid or L-aspartic acid and its succinic acid or Maleic acid amides or monocarboxymethylate derivatives have a high effect as bleach stabilizers for hydrogen peroxide or hydrogen peroxide generating bleaching agents, especially for sodium perborate, in the presence of traces of heavy metal ions in textile washing have. The compounds used according to the invention are lower Concentration of 5-30 mg / l, preferably 10-20 mg / l, in the wash liquor effective. Another beneficial property of L-glutamic acid or L-aspartic acid is their by means of biotechnical processes industrial availability, which is a light and environmentally friendly Manufacturing guaranteed.  

After Römpp, Chemistry Lexicon 9th Edition, Vol. 2, p. 1606 (Thieme Verlag, 1990) can L-glutamic acid or sodium L-glutamate from protein hydrolyzates isolated or on an industrial scale by fermentation of D-glucose and ammonia can be obtained.

According to Römpp, Chemistry Lexicon 9th edition, Vol. 1, p. 267 (Thieme Verlag, 1989) L-aspartic acid is technically chemical or biotechnological Addition of ammonia to maleic or fumaric acid accessible.

The derivatization of aminodicarboxylic acids to aminotricarboxylic acids can, for example, by reacting L-glutamic acid with chloroacetic acid analogous to Example 12. The production of succinic acid or maleic acid amides of L-glutamic acid is in the examples 13-14. Mixtures of substances fall as reaction products which have been specified analytically and which are without further Workup was used directly as a complexing agent. Advantageous it should be noted that the reactions take place in water, which serves as a solvent for the products after the reaction.

The following examples 1-11 illustrate the mode of operation of the claimed compounds based on washing tests. For comparison are examples in the test series without stabilizer and one with EDTA as a stabilizer.

Examples 1-6

WFK cotton test fabrics are placed in a Linitest laboratory washing machine with red wine soiling (11 × 18 cm) for 30 minutes at 60 ° C in Washed 250 ml of washing solution and then rinsed and dried. The reflectance difference DR is spectrophotometric at λ = 560 nm with a photometer (Datacolor 3890) versus one unwashed test fabric determined (Table 1).

The washing solutions had the following composition:

438 mg Zeolite A (Wessalith P) / Cobuilder (Sokalan CP5) 9: 1
81 mg alkylbenzenesulfonate (Marlon A)
32 mg fatty alcohol oxyethylate (Marlipal 013/100)
38 mg coconut soap
213 mg sodium sulfate
74 mg soda water glass
171 mg sodium perborate tetrahydrate
24 mg tetraacetylethylenediamine (TAED)
9 mg magnesium silicate
2.3 mg stabilizer according to Table 1 (except in Examples 1 and 6), tap water 3 ° dH ad 250 ml
5 ppm copper (II) ions (except in example 6).

Table 1

Examples 7-11

In a household washing machine (Bosch V 630), 4 kg of white Cotton ballast fabric together with WFK cotton test fabric with tea soiling washed at 60 ° washing temperature (45 min main wash and 35 min rinse cycles). After loading the washing machine with the Laundry was added 10 ml of a 2.7% copper (II) - chloride dihydrate solution and the detergent with the following Composition in the incoming tap hydrogen (13 ° dH):

22.5 g Marlon A350 (= 11.25 g alkylbenzenesulfonate)
6.0 g Marlipal 24/70 (coconut fatty alcohol oxyethylate)
4.2 g Edenor W35 (powder soap)
37.5 g Wessalith P (zeolite A)
6.0 g Sokalan CP5 (acrylic acid / maleic acid copolymer)
15.0 g of soda
4.5 g sodium metasilicate pentahydrate
1.5 g carboxymethyl cellulose
30.0 g sodium sulfate decahydrate
0.7 g savinase (enzyme)
30.0 g sodium perborate tetrahydrate
4.5 g tetraacetylethylenediamine (TAED)
0.3 g stabilizer according to Table 2 (except in Example 7)
Water to 500 ml

After the wash program has ended, the test fabric is dried and the Remission difference DR spectrophotometric at λ = 560 nm with a Photometer (Datacolor 3890) determined against unwashed test fabric. The values are in Table 2.

Table 2

Example 12 N-carboxymethyl-L-glutamic acid disodium salt

84.55 g of monosodium are added to a stirred flask with an internal thermometer. L-glutamate dissolved in 76.2 g water and 60 g 40% sodium hydroxide solution. The The batch is heated to 70 ° C. A solution of 47.25 g of chloroacetic acid added dropwise in 80 g of water. Finally be  40 g of 40% sodium hydroxide solution were added and the mixture was stirred at 70 ° C. for 3 hours.

Yield: 388 g of clear aqueous solution, pH = 6.7.
Active substance content: 32%, NaCl 7.5%.

Example 13 L-glutamic acid succinic acid trisodium salt

In a stirred flask with an internal thermometer and reflux condenser 352 g of water are introduced, 160 g of 50% sodium hydroxide solution are added and therein 169 g monosodium L-glutamate dissolved. The approach is at 60 ° C heated. 100 g of succinic anhydride are added in portions within 3 minutes added. The temperature rises during the addition to 80 ° C. Finally, the mixture is stirred at 60 ° C. for 1 h.

Yield: 781 g of clear aqueous solution.

After 1 H NMR spectroscopic analysis 8 (50 MHz, D₂O) results in Composition of the solution from the evaluation of the integrals of the 2-H glutamic acid (dd, δ = 3.7 ppm) or amide (dd, δ = 4.1 ppm). In this case, an L-glutamate: amide ratio of 7.9: 13.0 obtained. This corresponds to the following product distribution in the solution: 195 g L-glutamic acid succinic acid trisodium salt, 72 g disodium L-glutamate and 61 g disodium succinate.

Example 14 L-glutamic acid maleic acid trisodium salt

The procedure is as in Example 13 with the following amounts of substance: 360 g Water, 160 g 50% sodium hydroxide solution, 169 g monosodium L-glutamate and 98 g maleic anhydride.

Yield: 787 g of clear aqueous solution.

The following product distribution results from the signal ratio of 12:21 in the solution: 198 g L-glutamic acid maleinamide trisodium salt, 70 g L-glutamic acid disodium salt and 58 g disodium maleate.

Claims (5)

1. Use of isolated from natural material or biotechnological produced amino acids and / or their succinic acid and / or their maleic acid amides and / or their monocarboxymethylates in acid form or in the form of their alkali metal salts as Bleach stabilizers. 2. Use of naturally or biotechnologically produced Amino acids according to claim 1, characterized, that as amino acids L-glutamic and / or L-aspartic acid be used. 3. Use of naturally or biotechnologically produced Amino acids according to claims 1 or 2, characterized, that the compounds in detergents, the sodium perborate included, used. 4. Use of naturally or biotechnologically produced Amino acids according to claims 1 to 3, characterized, that the concentration in the wash liquor 5-30 mg / l is. 5. Process for commercial textile washing, characterized, that compounds according to claims 1 or 2 of the wash liquor are added and this during a bleaching process Sodium perborate and / or hydrogen peroxide are present.