EP0693117A1

EP0693117A1 - Use of carboxyl-group-containing reaction products of proteins or hydrolysed proteins in washing and cleaning agents

Info

Publication number: EP0693117A1
Application number: EP94912550A
Authority: EP
Inventors: Matthias Kroner; Gunnar Schornick; Richard Baur; Alexander Kud; Volker Schwendemann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1993-04-10
Filing date: 1994-03-29
Publication date: 1996-01-24
Anticipated expiration: 2014-03-29
Also published as: EP0693117B1; DE59406092D1; US5665693A; DE4311854A1; WO1994024254A1

Abstract

Described is the use, as an additive to phosphate-reduced and phosphate-free washing and cleaning agents, of carboxyl-group-containing reaction products of (a) maleic acid anhydride, maleic acid and/or fumaric acid and (b) proteins or hydrolysed proteins, the reaction products having an acid number of at least 1.5 mmol of NaOH per gram of reaction product.

Description

Use of reaction products of proteins or protein hydrolyzates containing carboxyl groups in detergents and cleaning agents

description

The invention relates to the use of reaction products of proteins or protein hydrolyzates containing carboxyl groups, which are at most hydrolyzed to dipeptides, as additives in detergents and cleaning agents.

The reaction of amino acids or peptides with maleic anhydride in acetic acid is known from Z. Chem. Volume 25, 18-19 (1985).

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

Detergent formulations are known from EP-A 0 455 468 which contain chemically modified vegetable proteins as graying inhibitors. The proteins are preferably modified by reaction with phthalic anhydride in an aqueous medium at a pH of at least 8. However, the degree of modification of the proteins is relatively low, so that the reaction products have practically no dispersing action and do not increase the primary washing action of the detergents even when used in detergents.

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

The object of the present invention is to provide additives with a dispersing action for use in phosphate-reduced and phosphate-free washing and cleaning agents.

The object is achieved according to the invention by using reaction products containing carboxyl groups

a) maleic anhydride, maleic acid and / or fumaric acid and b) proteins or protein hydrolyzates which are hydrolyzed no further than dipeptides,

with an acid number of at least 1.5 mmol sodium hydroxide / g of reaction product as an additive to phosphate-reduced and phosphate-free detergents and cleaning agents.

To produce the reaction products, component a) is maleic anhydride, maleic acid, fumaric acid or mixtures of the compounds mentioned. Maleic anhydride is preferably used.

Suitable compounds of component b) are proteins or protein hydrolysates which are hydrolyzed no further than up to dipeptides. All synthetic or natural proteins and mixtures of synthetic and natural proteins can be used as proteins. The proteins can be of vegetable or animal origin. The proteins can be used in purified form or unpurified for the production of the reaction products. Examples of a purified protein are soy protein isolate, while whey protein is an example of an unpurified protein. Examples of animal proteins are casein, whey, gelatin and bone glue. Examples of vegetable proteins are the proteins from potatoes, sugar beets, peas, soybeans, wheat and corn.

The protein hydrolyzates are produced by hydrolysis of the proteins under acidic, neutral, basic or fermentative conditions. The hydrolysis of the proteins can be carried out to different extents, but no further than up to dipeptides. The hydrolysis products can also contain fractions of low molecular weight peptides. Mixtures of proteins and protein hydrolyzates can also be used as component b). Examples of acidic, neutral or basic hydrolyzed proteins are bone glue, soy hydrolyzates and wheat hydrolyzates. However, the proteins can also be treated reductively or oxidatively in order to convert them into a more water-soluble form. For example, wheat gluten or soy proteins can be reductively pretreated by alkali sulfite, alkali thiosulfate, mercaptoethanol, thioglycolic acid, thiolactic acid or alkali sulfide. You can also with oxidizing agents, e.g. be treated with hydrogen peroxide, peracetic acid, peroxides, sodium or potassium peroxodisulfate, oxygen or nitric acid.

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 included In addition to small amounts of fat and oil in milk, whey proteins also contain large amounts of lactose and other carbohydrates. In addition to the soy proteins, soy milk can also contain oil and fat components 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, in addition to higher molecular weight protein hydrolyzates, di- and tripeptides are also present. Examples of dipeptides are:

Asp-Glu Asp-Asp Asp-Gly

Examples of tripeptides are:

Asp-Asp-Asp Asp-Glu-Asp Asn-Gln-Ser Glu-Ser-Pro Asp-Ser-Pro Asp-Glu-Gly Asp-Lys-Asn

Examples of synthetic proteins are polyaspartic acids which can be obtained, 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. Polycondensates of glutamic acid, which can be prepared by polymerizing N-carboxylic anhydrides of glutamic acid and its esters. All synthetic peptides which can be obtained by polymerizing N-carboxylic acid anhydrides in the manner of an anionic polymerization are suitable as component b). Also suitable as component b) are those synthetic peptides which are obtainable by copolymerization of different N-carboxylic acid anhydrides of different amino acids. Proteins from soy, wheat, potatoes, whey, casein and gelatin are preferably used as component b).

The acid number of the proteins is increased by the reaction of components a) with b). The acid number is the amount of sodium hydroxide solution required to neutralize 1 g of the reaction product. It is determined, for example, by titration using 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 are at least 1.5 mmol of sodium hydroxide solution / g of reaction product. The acid numbers of the hydrolyzed proteins can be up to 1.3 mmol sodium hydroxide solution / g. They are further increased by the reaction of the protein hydrolyzates with the compounds of component a). 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 reacted at temperatures in the range from 90 to 300. The reaction is carried out in particular at temperatures from 120 to 300 ° C., preferably 150 to 270 ° C. under pressure, for example up to 30 bar. The compounds of component a) can be used as solvents for the proteins or protein hydrolyzates. The reaction of components a) and b) is preferably carried out in the absence of water. However, the reaction can also be started in the presence of water, for example at temperatures in the range from 50 to 99 ° C. and as the reaction progresses, the temperature of the reaction mixture is increased to such an extent that the water is virtually completely removed from the reaction mixture. Maleic anhydride can initially form from maleic acid, which then reacts with the proteins or protein hydrolyzates. A procedure in which the reaction is carried out in molten maleic anhydride is particularly preferred. Components a) and b) can be reacted with one another in any weight ratio, for example in the weight ratio 99: 1 to 1:99. Components a) are preferably used in excess, for example their proportion in the reaction mixture is 55-90% by weight. The excess components a) can be easily removed from the reaction mixture after the reaction has ended. If, for example, maleic anhydride was used as component a), it can easily be removed from the reaction mixture by sublimation, distillation or extraction with solvents such as acetone or ethyl acetate. The reaction products from components a) and b) have K values (determined according to Fikentscher in 1% aqueous solution on the sodium salt at pH 7 and 25 ° C.) from 10 to 100.

The reaction products can be used in the form of the free acids or in the form of the salts with alkali metal, alkaline earth metal and ammonium bases. To prepare the salts, a base or a mixture of several bases is usually added to an aqueous solution of the reaction products or to a slurry of the reaction products in water. Suitable are, for example, 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 biodegradable according to the OECD Guidelines for Testing of Chemicals, Paris 1981, 302 B (modified Zahn-Wellens test). They are also 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 of Chemical Substances, Verlag Chemie, Weinheim 1988, page 62.

The reaction products described above or their alkali, ammonium and alkaline earth metal salts are used as an additive to phosphate-reduced or phosphate-free washing and cleaning agents. In most cases, the amount of reaction products used is 0.1-30% by weight, based on the washing and cleaning agents. Phosphate-reduced detergents are to be understood as meaning those formulations which contain no more than 25% by weight of phosphate, calculated as sodium triphosphate. Most of the phosphate-free detergents contain sodium aluminum silicate (Zeolite A). The reaction products from components a) and b) or their salts are preferably used in amounts of 1 to 20% by weight, based on the detergent or cleaning agent formulation. Detergent formulations are to be understood to mean all cleaners for hard surfaces, e.g. Dishwashers, cleaners for industrial bottle washing, cleaners for dairies and floor cleaning agents.

The reaction products are preferably used in laundry detergents. They have a good dispersibility in the detergent fleet for particle dirt, especially for clay minerals (clay). This property is important because lehmar- soiling of textile goods are widespread. The reaction products also act as builders for detergents and bring about a reduction in incrustation and graying on the washed textile goods during the washing process. They are therefore also suitable as incrustation and graying inhibitors.

The composition of the washing and cleaning formulations can be very different. Detergents and cleaning agents usually contain 2 to 50% by weight of surfactants and optionally builders. This information applies to both liquid and powder detergents. Examples of the composition of detergent formulations which are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) tabulated. Further information on the composition of detergents and cleaners can be found in WO-A-90/13581 and Ullmanns Encyklopadie der Technische Chemie, Verlag Chemie, Weinhein 1983, 4th edition, pages 63-160. Also of interest are detergent formulations which contain up to 60% by weight of an alkali silicate and up to 10% by weight of a polycondensate according to the invention. Examples of suitable alkali silicates are the amorphous sodium disilicates, which are described in EP-A-0 444 415, and crystalline sheet silicates, which, according to EP-A-0 337 219, are contained in detergent formulations as builders and according to EP-A B-0 164 514 are used for softening water, and sodium silicates, which can be obtained by dewatering sodium silicate solutions and drying to water contents of 15 to 23, preferably 18 to 20% by weight. Sodium aluminum silicates (zeolite A) can be contained in detergents in amounts of up to 50%.

The detergents can optionally also contain a bleaching agent, e.g. Sodium perborate, which, if used, can be present in the detergent formulation in amounts of up to 30% by weight. The detergents and cleaning agents can optionally contain other conventional 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 suitable as water treatment agents. They are usually added to the water in cooling circuits, evaporators or seawater desalination plants in quantities of 1 to 1000 ppm. They also act as covering Preventing the evaporation of sugar juice. They are added to the thin sugar juice in amounts of 0.1 to 1000 ppm.

The K values of the neutralized reaction products were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in aqueous solution at a temperature of 25 ° C. and a concentration of 1% by weight. % determined at pH 7 on the sodium salt of the polymers.

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 equipped with a stirrer and heated to a temperature of 140 ° C. under pressure for 4 h with exclusion of moisture. A solution or 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 for 4 h in an extractor with acetone 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.

Table 1

⁺⁾ The filter residue was extracted with ethyl acetate

For the application tests, the reaction products 1 to 10 were converted into the sodium salts by stirring 10 g of the powdery products in 100 ml of water and neutralizing them by adding 10% strength aqueous sodium hydroxide solution until no more sodium hydroxide solution was used and one aqueous solution or slurry of the reaction products with a pH between 7 and 8 was formed.

Application engineering examples

The clay dispersion was evaluated according to the clay dispersion test (CD test) described below.

CD test

Finely ground china clay SPS 151 is used as a model for particulate dirt. 1 g of clay is intensively dispersed in a standing cylinder (100 ml) for 10 minutes with the addition of 1 ml of a 0.1% sodium salt solution of the polyelectrolyte in 98 ml of water. Immediately after stirring, a 2.5 ml sample is taken from the center of the standing cylinder and, after dilution to 25 ml, the turbidity of the dispersion is determined using a turbidimeter. After the dispersion has stood for 30 or 60 minutes, samples are taken again and the turbidity determined as above. The turbidity of the dispersion is given in NTU (nephelometric turbidity units). The less the dispersion settles during storage, the higher the measured turbidity values and the more stable the dispersion. The dispersion constant, which describes the temporal behavior of the sedimentation process, is determined as the second physical measured variable. Since the sedimentation process can be described approximately by a mono-potential time, τ indicates the time in which the turbidity drops to 1 / e-th of the initial state at time t = 0.

The higher a value for τ, the slower the dispersion settles. Table 2

As follows from the dimensional values given in the table, the reaction products to be used according to the invention are good dispersants for clay.

Primary washing ability test

The clay detachability (TAV test) of textile fabrics was specifically investigated using washing tests. The TAV test described below shows the basic clay detachability of an additive in the presence of a surfactant, but with the exclusion of other, conventional detergent ingredients, and is therefore independent of the detergent formulation chosen. Clay minerals are colored and, when deposited on the fabric, give it a color veil. In order to determine the primary washing effect of clay on the fabric, cotton / polyester fabric with a clay mixture consisting of 33.3% each of the types 178 / R (ocher colors), 262 (brown) and 84 / rf (red-brown) from Carl Jäger, Hilbert, evenly coated. The types of clay are different "bold"; i.e. they differ in the content of aluminum, iron and manganese oxide. The clay mixture was homogeneously applied to the tissue in the form of a 20% suspension in deionized water with vigorous pumping around the suspension. This was carried out with a jigger from Küsters, Krefeld, at 10 meters / minute using body goods made from 33% cotton and 67% polyester (BW / PES fabric) from Winkler, Waldshut. After 3 runs, 600 1 of completely deionized water were then rinsed once. The wet tissue was then dried in a tenter at 50 ° C. and a drying speed of 2 meters / minute. The clay fabric produced in this way contains 1.76% clay, determined by ashing at 700 ° C. for 2.5 hours.

The tissue thus obtained is pre-measured via color strength and divided into classes. 10 units are arbitrarily specified as the color strength range for a class. The color strength range of all classes is between 260 and 340 color strength units for the blended fabric used. A washing series consisting of 6 washing tests is carried out with soiled tissue from only one class.

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 washing attempts: 6

Washing temperature: 20 - 24 ° C Washing time: 15 min Fleet quantity 500 g VE ¹⁾ water + 80 ppm ethoxylated oxo alcohol

(Cι ₃ / C ₁₅ -oxo alcohol + 8 EO)

Water hardness (Ca ^2_t + Mg ²⁺ ): 1 mmol / 1 5 molar ratio Ca ²⁺ : Mg ²⁺ : HC0 ₃ ^_ : 3: 1: 6 pH: 10 ± 0.1

Test concentration of the polymer: 80 ppm dirt tissue: 5 g clay tissue (~ 30.5 cm x 8 cm) white tissue or clean tissue: 5 g PES / BW tissue (~ 30 cm x 8 cm)

D VE = completely desalinated

After rinsing with 500 g water (hardness 1 mmol / 1 Ca ²⁺ and Mg ²⁺ ), 15 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 20 degree of reflection 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 Textilberichte Band 67, 562 ff. (1986), the color strength calculated with weighting of the eye irritation function. The 25 weighting factors for the eye irritation function (Xχo (λ) + Y ^ (λ) + Zχo (λ)) can be found in the following table:

The weighting with the human eye irritation function should weight even slight yellowing of the tissue more. The exact derivation of the mathematical evaluation was described by A. Kud in Tideside, Surfactants, Detergents, Volume 28, 497 ff (1991).

The primary washing effect in% is calculated according to the following equation:

P = (f _s , b "fs, a) / (fs, b ~ fs, o) ^• 100

^~ _S , _Ώ ⁼ color strength of the soiled fabric (clay fabric) before washing

f _Sra = color strength of the soiled fabric after washing

f _{S / 0} = color strength of the clean fabric before soiling (dirty fabric before soiling).

The use of the color strength for calculating the primary washing effect has the advantage in comparison to the reflectance at a wavelength or the K / S values (K = absorption coefficient and S = scattering coefficient) used in the literature that the visible range of the spectrum is recorded and dirt particles of all colors are taken into account.

The polymers to be used according to the invention were tested according to the TAV test described above, cf. Examples 10 to 18. The results obtained are given in Table 3 together with the results of Comparative Examples 3 and 4 described below. As can be seen from this, the primary effect is increased by adding the polymers to be used according to the invention to the aqueous solution of the nonionic surfactant.

Comparative Example 3

Instead of the reaction products used in Examples 10 to 18, the same amount, ie 80 ppm, of citric acid in the form of the monosodium salt was used. Comparative Example 4

Example 10 was repeated with the only exception that the test was carried out in the absence of reaction product 1, i.e. tested the effect of a surfactant solution containing 80 ppm of the surfactant used in Examples 10 to 18.

Table 3

Claims

1. Use of reaction products containing carboxyl groups

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

(b) proteins or protein hydrolyzates that are hydrolyzed no further than dipeptides,

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 cleaning agents.

2. Use according to claim 1, characterized in that the reaction products are obtainable by reaction of (a) and (b) at temperatures from 120 to 300 ° C under pressure.

3. Use according to claim 1 or 2, characterized in that maleic anhydride is used as component (a).