EP0693117B1 - Use of carboxyl-group-containing reaction products of proteins or hydrolysed proteins in washing and cleaning agents - Google Patents

Description

The invention relates to the use of carboxyl-containing Reaction products of proteins or protein hydrolyzates, which are hydrolyzed up to a maximum of dipeptides, as an additive in detergents and cleaning agents.

From Z. Chem. Volume 25, 18-19 (1985) is the conversion of amino acids or peptides with maleic anhydride in acetic acid.

From JP-A-56/012 351 are reaction products from amino acids and maleic anhydride or succinic anhydride known be produced in organic solvents. The implementation products are used for example in shampoos or cleaners.

Detergent formulations are known from EP-A 0 455 468, the chemically modified vegetable proteins as a graying inhibitor contain. The proteins are preferably converted with phthalic anhydride in an aqueous medium at pH modified by at least 8. The degree of modification of the proteins is however relatively small, so that the reaction products have practically no dispersing effect and also with Use in detergents the primary washing effect of the detergents do not increase.

DE-A-4 033 209 describes the conversion of protein hydrolyzates a molecular weight of 200 to 20,000 with ether carboxylic acid chlorides described in aqueous medium. The implementation products are used as surfactants in washing and cleaning agents.

From EP-A-0457205 the use of water-soluble or water-dispersible grafted proteins as an additive to washing and cleaning agents in amounts of 0.1 to 20 wt .-%, based on the respective formulations. The grafted proteins are obtained by free radical copolymerization of monoethylenically unsaturated monomers in the presence of proteins produced.

The present invention is based on the object of dispersing effective additives for use in reduced phosphate and phosphate-free detergents and cleaning agents are available too put.

a) Maleinsäureanhydrid, Maleinsäure und/oder Fumarsäure und

b) natürlichen Proteinen und/oder deren Hydrolysaten, die nicht weiter als bis zu Dipeptiden hydrolysiert sind,

bei Temperaturen von 120 bis 300°C unter Druck in Abwesenheit Radikale bildender Initiatoren, eines wäßrigen Mediums und eines organischen Lösemittels zu Umsetzungsprodukten mit einer Säurezahl von mindestens 1,5 mmol NaOH/g Umsetzungsprodukt erhältlich sind, als Zusatz zu phosphatreduzierten und phosphatfreien Wasch- und Reinigungsmitteln.The object is achieved according to the invention by using reaction products containing carboxyl groups, which are obtained by reacting

a) maleic anhydride, maleic acid and / or fumaric acid and

b) natural proteins and / or their hydrolyzates which are hydrolyzed no further than up to dipeptides,

at temperatures of 120 to 300 ° C under pressure in the absence of free radical initiators, an aqueous medium and an organic solvent to give reaction products with an acid number of at least 1.5 mmol NaOH / g of reaction product, as an additive to phosphate-reduced and phosphate-free washing and Detergents.

The component used to produce the reaction products a) Maleic anhydride, maleic acid, fumaric acid or Mixtures of the compounds mentioned. Preferably you bet Maleic anhydride.

Proteins or protein hydrolyzates come as compounds of component b) considered to be no further than up to dipeptides are hydrolyzed. All natural proteins can be considered as proteins be used. The proteins can be vegetable or animal Be of origin. The proteins can be in purified form or used unpurified to produce the reaction products will. Examples of a purified protein are soy protein isolate, while whey protein is an example of an unpurified Is protein. Examples of animal proteins are casein, Whey, gelatin and bone glue. Examples of vegetable proteins are the proteins from potatoes, sugar beets, marker peas, Soy, wheat and corn.

The protein hydrolyzates are obtained by hydrolysis of the proteins acidic, neutral, basic or fermentative conditions. The hydrolysis of the proteins can vary widely be carried out, but no further than up to dipeptides. The hydrolysis products can still have proportions of low molecular weight Contain peptides. Mixtures can also be used as component b) from proteins and protein hydrolyzates. examples for Acid, neutral or basic hydrolyzed proteins are bone glue, Soy hydrolyzate and wheat hydrolyzate. The proteins can however, they can also be treated reductively or oxidatively to get them into to convert a more water soluble form. For example wheat gluten or soy proteins can be caused by alkali sulfite, alkali thiosulfate, Mercaptoethanol, thioglycolic acid, thiolactic acid or Alkali sulfide can be reductively pretreated. You can also use Oxidizing agents, e.g. with hydrogen peroxide, peracetic acid, Peroxides, sodium or potassium peroxodisulfate, oxygen or Nitric acid are treated.

Due to their origin, the natural proteins can also contain other components such as carbohydrates, fiber components, cellulose and hemicellulose, oils or fats. For example, in addition to small amounts of fat and oil in milk, whey proteins contain large amounts of lactose and other carbohydrates. In addition to the soy proteins, soy milk can also contain oil and fat from the soy plant. Cellulose fractions can also be contained in the soy protein. The molecular weight of the proteins can be reduced or hydrolyzed to such an extent that di- and tripeptides are also present in addition to higher molecular weight protein hydrolyzates. Examples of dipeptides are:

Examples of tripeptides are:

The abbreviations used above mean:

Examples of synthetic proteins are polyaspartic acids that for example by polycondensation of L- or DL-aspartic acid or by thermal polycondensation of acidic ammonium salts of fumaric acid, maleic acid or malic acid are. Polycondensates of glutamic acid, which are polymerized of N-carboxylic anhydrides of glutamic acid and its esters are producible. All synthetic are suitable as component b) Peptides generated by the polymerization of N-carboxylic acid anhydrides are available in the manner of an anionic polymerization. Such synthetic peptides are also suitable as component b), by the mixed polymerization of various N-carboxylic acid anhydrides different amino acids are available.

Soy proteins are preferably used as component b), Wheat, potatoes, whey, casein and gelatin.

The acid number is obtained by reacting components a) with b) of proteins increases. The acid number is the amount required Sodium hydroxide solution to neutralize 1 g of the reaction product is needed. It is included, for example, by titration Determined with the help of 0.1 N sodium hydroxide solution. The acid numbers of the proteins are between 0 and 1, while the acid numbers of the reaction products at least 1.5 mmol sodium hydroxide solution / g reaction product be. The acid numbers of the hydrolyzed proteins can up to 1.3 mmol sodium hydroxide solution / g. You will be through the implementation the protein hydrolyzates with the compounds of the component a) further increased. The acid numbers of the reaction products are preferably 1.8-10 mmol of sodium hydroxide solution / g of reaction product.

The compounds of components a) and b) are at temperatures implemented in the range of 90 - 300. The implementation will in particular at temperatures from 120 to 300 ° C., preferably 150 up to 270 ° C under pressure, e.g. up to 30 bar. The connections Component a) can be used as a solvent for the Proteins or protein hydrolyzates can be used. The implementation of components a) and b) is preferably in the absence of Water carried through. A method of operation in which the implementation is particularly preferred in molten maleic anhydride. The components a) and b) can be in any weight ratio implemented with each other, e.g. in a weight ratio of 99: 1 to 1:99. Components a) are preferably used in excess, e.g. their proportion in the reaction mixture is 55-90% by weight. The excess components a) can after completion of the implementation can be easily removed from the reaction mixture. If for example, maleic anhydride used as component a) , you can easily do it by sublimation, distillation or Extract with solvents such as acetone or ethyl acetate remove from the reaction mixture.

The reaction products from components a) and b) have K values (determined according to Fikentscher in 1% aqueous solution on Sodium salt at pH 7 and 25 ° C) from 10 to 100.

The reaction products can be in the form of the free acids or in Form of salts with alkali metal, alkaline earth metal and ammonium bases be used. Usually one adds to the production of the salts to an aqueous solution of the reaction products or a slurry of the reaction products in water a base or a mixture of several bases, for example suitable Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, Potassium hydrogen carbonate, calcium hydroxide, calcium oxide, Barium hydroxide, magnesium hydroxide or magnesium oxide and ammonia and amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, ethanolamine, diethanolamine, Triethanolamine, morpholine and cyclohexylamine.

The reaction products from components a) and b) are biological degradable according to OECD Guidelines for Testing of Chemicals, Paris 1981, 302 B (modified Zahn-Wellens test). You are too degradable according to the decrease in dissolved oxygen in the closed Bottle test and according to the modified SCAS test, cf. R. Wagner, Methods for Testing the Biochemical Degradability chemical substances, Verlag Chemie, Weinheim 1988, page 62.

The reaction products described above or their alkali, ammonium and alkaline earth metal salts are added to phosphate-reduced or phosphate-free detergents and cleaning agents. In most cases the amount applied is Reaction products 0.1 - 30 wt .-%, based on the washing and Cleaning supplies. Under reduced phosphate detergents such terms are understood as no more than 25% by weight of phosphate, calculated as sodium triphosphate. Most phosphate-free detergents contain sodium aluminum silicate (Zeolite A). The implementation products from the components a) and b) or their salts are preferably used in amounts from 1 to 20% by weight, based on the detergent or cleaning agent formulation, used. Under detergent formulations all cleaners for hard surfaces should be understood, e.g. Dishwashing detergent, industrial bottle washer cleaner, Cleaner for dairies and floor cleaning agents.

The reaction products are preferably in textile detergents used. They have good dispersibility in the detergent fleet for particle dirt, especially for clay minerals (Clay). This property is important because it is clay-like Soiling of textile goods is widespread. The implementation products also act as a builder for detergents and cause a reduction in the incrustation during the washing process and the graying on the washed textile. they are thus also suitable as incrustation and graying inhibitors.

The composition of the washing and cleaning formulations can be very different. Detergents and cleaning agents included usually 2 to 50 wt .-% surfactants and optionally builders. This information applies to both liquid and powdery Detergents and cleaning agents. Examples of the composition of detergent formulations used in Europe, the United States and are common in Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) tabulated. Further information on the composition of detergents and cleaning agents can WO-A-90/13581 and Ullmanns Encyklopadie Technical Chemistry, Verlag Chemie, Weinhein 1983, 4th edition, Pages 63-160 are taken. Such detergent formulations are also of interest, up to 60 wt .-% of an alkali silicate and up to 10% by weight of a polycondensate according to the invention contain. The alkali silicates include, for example amorphous sodium disilicates into consideration, which are described in EP-A-0 444 415 are described, as well as crystalline layered silicates, which according to EP-A-0 337 219 contained in detergent formulations as a builder are and according to EP-B-0 164 514 for softening water used, and sodium silicates by draining from sodium silicate solutions and drying up to water contents of 15 to 23, preferably 18 to 20 wt .-% are available. Sodium aluminum silicates (Zeolite A) can be used in amounts up to 50% can be contained in detergents.

The detergents can optionally also contain a bleach, e.g. Sodium perborate, which if used in Amounts up to 30 wt .-% in the detergent formulation can be. The detergents and cleaning agents can, if necessary contain other common additives, e.g. Complexing agents, citrates, Opacifiers, optical brighteners, enzymes, perfume oils, color transfer inhibitors, Graying inhibitors and / or bleach activators.

The reaction products are also used as water treatment agents suitable. They are usually in amounts from 1 to 1000 ppm of water in cooling circuits, evaporators or sea water desalination plants added. They also act as a deposit inhibitor in the evaporation of sugar juice. They will Thin sugar added in amounts of 0.1 to 1000 ppm.

The K values of the neutralized reaction products were H. Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932) in aqueous solution at a temperature of 25 ° C and one Concentration of 1 wt .-% at pH 7 on the sodium salt of the polymers certainly.

Examples General manufacturing instructions for the implementation products

The quantities of maleic anhydride and protein given in Table 1 are introduced into a 500 ml pressure-tightly sealable reactor which is equipped with a stirrer and heated to a temperature of 140 ° C. under pressure for 4 h with exclusion of moisture. A solution or a slurry of the reaction product is then obtained in molten maleic anhydride. In order to purify the reaction mixture, 1 l of anhydrous acetone is added after the reaction mixture has cooled, the mixture is stirred for 3 h and filtered. The filter residue is then extracted with acetone in an extractor for 4 h and then dried in vacuo. The reaction products listed in Table 1 are obtained, which are characterized by means of the K value and the acid number.

The implementation products were used for the technical tests 1 to 10 converted into the sodium salts in which 10 g of Stir powdery products in 100 ml of water and add neutralized by 10% aqueous sodium hydroxide solution until no more sodium hydroxide solution was used and an aqueous solution or slurry of the reaction products with a pH was between 7 and 8.

Application engineering examples

The clay dispersion was carried out as described below Clay dispersion test (CD test) assessed.

CD test

Finely ground china clay is used as a model for particulate dirt SPS 151 used. 1 g of clay is added with the addition of 1 ml 0.1% sodium salt solution of the polyelectrolyte in 98 ml of water Intensely dispersed for 10 minutes in a standing cylinder (100 ml). Immediately after stirring, take from the center of the standing cylinder a 2.5 ml sample and determined after dilution to 25 ml the turbidity of the dispersion with a turbidimeter. After 30 or Samples are taken again for 60 minutes of the dispersion and how the turbidity determines above. The turbidity of the dispersion is specified in NTU (nephelometric turbidity units). The less the higher the dispersion settles during storage are the measured turbidity values and the more stable the dispersion. The dispersion constant becomes the second physical quantity which determines the temporal behavior of the sedimentation process describes. Because the sedimentation process is almost can be described by a mono-potential time setting, specifies τ the time in which the turbidity is 1 / e-th of the initial state falls at time t = O.

The higher a value for τ, the slower the dispersion settles.

Primary washing ability test

The clay detachability (TAV test) of textile fabrics was special examined on the basis of washing tests. The one described below TAV test shows the basic sound release ability of a Additives in the presence of one surfactant, but excluding others, usual detergent ingredients and is therefore independent of the chosen detergent formulation. Are clay minerals dyed and give this to a deposit on the tissue a color veil. To the primary washing action of clay on the To capture fabric, cotton / polyester fabric was mixed with a clay consisting of 33.3% each from varieties 178 / R (ocher), 262 (brown) and 84 / rf (red-brown) from Carl Jäger, Hilgert, evenly coated. The types of clay are different "fat"; i.e. they differ in the content of aluminum, iron and manganese oxide. The clay mixture was in the form of a 20% Suspension in deionized water with vigorous pumping around the Suspension brought homogeneously onto the tissue. This was done with a Jigger from Küsters, Krefeld, at 10 meters / minute using of body goods made of 33% cotton and 67% polyester (BW / PES fabric) from Winkler, Waldshut. After 3 Runs were then completely desalted with 600 l Rinsed water once. After that, the wet tissue was in one Stenter dried at 50 ° C and 2 meters / minute drying speed. The clay fabric produced in this way contains 1.76% clay, determined by ashing at 700 ° C, 2.5 h.

The tissue thus obtained is pre-measured via color strength and in Classes divided. Be as a color strength range for a class 10 units set arbitrarily. The color strength range of everyone The blended fabrics used are between 260 and 340 color strength units. A washing series consisting of 6 washing attempts, is made of only one class with soiled fabric carried out.

The washing tests (TAV test) were carried out under the following conditions: Washing machine Launder-o-meter Number of wash cycles 1 Number of rinsing cycles 1 Number of wash attempts 6 Washing temperature 20 - 24 ° C Washing time 15 minutes Fleet quantity 500 g PU -Water + 80 ppm ethoxylated oxo alcohol (C ₁₃ / C ₁₅ -oxo alcohol + 8 EO) Water hardness (Ca ²⁺ + Mg ²⁺ ) 1 mmol / l Molar ratio ca ²⁺ : Mg ²⁺ : HCO ₃ 3: 1: 6 pH 10 + 0.1 Test concentration of the polymer 80 ppm Dirty tissue 5 g clay fabric (∼ 30.5 cm x 8 cm) White tissue or clean tissue 5 g PES / BW fabric (∼ 30 cm x 8 cm)

After rinsing with 500 g of water (hardness 1 mmol / l Ca ²⁺ and Mg ²⁺ ), 20 ° C, 1 min in a launder-o-meter, the fabrics are spun and then hung up to dry individually. The fabric is measured with an Elrepho 2000 from Data Color, Heidenheim, namely 6 measuring points per piece of fabric. The wavelength range used for the evaluation is 400 - 700 nm. The reflectance is measured as a function of the wavelength. Barium sulfate serves as a reference. According to W. Baumann, R. Broßmann, BT Gröbel, N. Kleinemeier, M. Kraver, At Leaver and H.-P. Oesch; Melliand Textile Reports Volume 67, 562 ff. (1986), the color strength calculated with weighting of the eye irritation function. The weighting factors for eye irritation ( X ₁₀ (λ) + Y ₁₀ (λ) + Z. ₁₀ (λ)) are shown in the table below: λ (nm) Weighting factors ( X ₁₀ (λ) + Y ₁₀ (λ) + Z. ₁₀ (λ)) 400 0.1071 420 1.1984 440 2.4131 460 2.1759 480 1.1062 500 0.6831 520 0.9402 540 1.3525 560 1.7025 580 1.8831 600 1.7823 620 1.2544 640 0.6114 660 0.2129 680 0.0568 700 0.0133

The weighting with the eye irritation function of humans should be Weight slight yellowing of the fabric more. The exact Derivation of the mathematical evaluation was carried out by A. Kud in Tenside, Surfactants, Detergents, Vol. 28, 497 ff (1991).

f_s,b =

Farbstärke des angeschmutzten Gewebes (Tongewebe) vor dem Waschen

f_s,a =

Farbstärke des angeschmutzten Gewebes nach dem Waschen

f_s,o =

Farbstärke des sauberen Gewebes vor der Anschmutzung (Schmutzgewebe vor der Anschmutzung).

The primary wash efficiency in% is calculated using the following equation: P = (f s, b - f s, a ) / (f s, b - f so ) · 100

f _{s, b} =

Color strength of the soiled fabric (clay fabric) before washing

f _{s, a} =

Color strength of the soiled fabric after washing

f _{s, o} =

Color strength of the clean fabric before soiling (dirty fabric before soiling).

The use of color strength to calculate the primary wash effect compared to remission at a wavelength or the K / S values used in the literature (K = absorption coefficient and S = scattering coefficient) at one wavelength the advantage that the visible range of the spectrum is covered and Dirt particles of all colors are taken into account.

The polymers to be used according to the invention were after TAV test described above, cf. Examples 10 to 18. The results obtained are together with the results Comparative Examples 3 and 4 in the table described below 3 specified. As can be seen from this occurs by adding the polymers to be used according to the invention to the aqueous Solution of the nonionic surfactant an increase in the primary washing effect on.

Comparative Example 3

Instead of the reaction products used in Examples 10 to 18 the same amount was used, i.e. 80 ppm, citric acid in the form of the monosodium salt.

Comparative Example 4

Example 10 was repeated with the only exception that the test was carried out in the absence of reaction product 1, ie the effect of a surfactant solution containing 80 ppm of the surfactant used in Examples 10 to 18 was tested. Example No. Implementation product no. Effect [%] on test Sound transfer assets 10th 1 62.0 11 2nd 62.7 12th 3rd 64.5 13 4th 61.1 14 5 65.0 15 6 60.0 16 7 59.2 17th 8th 56.4 18th 10th 58.1 Comparative example 3rd - 55.3 4th - 55.3

Claims (3)

1. The use of carboxyl-containing reaction products obtainable by reacting

   (a) maleic anhydride, maleic acid and/or fumaric acid, and

   (b) natural proteins and/or natural-protein hydrolyzates not hydrolyzed further than the dipeptide stage,

   at temperatures from 120 to 300°C under superatmospheric pressure in the absence of free-radical initiators, in the absence of an aqueous medium and in the absence of an organic solvent to form reaction products having an acid number of at least 1.5 mmol of NaOH/g of reaction product, in reduced-phosphate and phosphate-free detergents and cleaners.
2. A use as claimed in claim 1, characterized in that component (a) is maleic anhydride.
3. The use as claimed in claim 1 or 2, characterized in that proteins from soybean, wheat, potatoes, whey, cusein or gelatin are used.