[go: up one dir, main page]

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

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

Info

Publication number
EP0693117A1
EP0693117A1 EP94912550A EP94912550A EP0693117A1 EP 0693117 A1 EP0693117 A1 EP 0693117A1 EP 94912550 A EP94912550 A EP 94912550A EP 94912550 A EP94912550 A EP 94912550A EP 0693117 A1 EP0693117 A1 EP 0693117A1
Authority
EP
European Patent Office
Prior art keywords
proteins
reaction products
washing
acid
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94912550A
Other languages
German (de)
French (fr)
Other versions
EP0693117B1 (en
Inventor
Matthias Kroner
Gunnar Schornick
Richard Baur
Alexander Kud
Volker Schwendemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0693117A1 publication Critical patent/EP0693117A1/en
Application granted granted Critical
Publication of EP0693117B1 publication Critical patent/EP0693117B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers

Definitions

  • reaction products of proteins or protein hydrolyzates containing carboxyl groups in detergents and cleaning agents
  • 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.
  • 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.
  • 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.
  • 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).
  • acidic, neutral or basic hydrolyzed proteins are bone glue, soy hydrolyzates and wheat hydrolyzates.
  • the proteins can also be treated reductively or oxidatively in order to convert them into a more water-soluble form.
  • wheat gluten or soy proteins can be reductively pretreated by alkali sulfite, alkali thiosulfate, mercaptoethanol, thioglycolic acid, thiolactic acid or alkali sulfide.
  • the natural proteins can also contain other components such as carbohydrates, fiber components, cellulose and hemicellulose, oils or fats.
  • whey proteins also contain large amounts of lactose and other carbohydrates.
  • 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:
  • tripeptides examples are:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • a bleaching agent e.g. Sodium perborate
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the clay dispersion was evaluated according to the clay dispersion test (CD test) described below.
  • 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.
  • 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.
  • reaction products to be used according to the invention are good dispersants for clay.
  • 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.
  • 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.
  • 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 Jardinrs, 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 were carried out under the following conditions:
  • Washing machine Launder-o-meter
  • Washing temperature 20 - 24 ° C Washing time: 15 min
  • 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)
  • the primary washing effect in% is calculated according to the following equation:
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

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

Verwendung von Carboxylgruppen enthaltenden Umsetzungsprodukten von Proteinen oder Proteinhydrolysaten in Wasch- und Reinigungs¬ mittelnUse of reaction products of proteins or protein hydrolyzates containing carboxyl groups in detergents and cleaning agents
Beschreibungdescription
Die Erfindung betrifft die Verwendung von Carboxylgruppen enthal¬ tenden Umsetzungsprodukten von Proteinen oder Proteinhydrolysa- ten, die höchstens bis zu Dipeptiden hydrolysiert sind, als Zu¬ satz in Wasch- und Reinigungsmitteln.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.
Aus Z. Chem. Band 25, 18-19 (1985) ist die Umsetzung von Amino¬ säuren oder Peptiden mit Maleinsäureanhydrid in Essigsäure be- kannt.The reaction of amino acids or peptides with maleic anhydride in acetic acid is known from Z. Chem. Volume 25, 18-19 (1985).
Aus der JP-A-56/012 351 sind Umsetzungsprodukte aus Aminosäuren und Maleinsäureanhydrid oder Bernsteinsäureanhydrid bekannt, die in organischen Lösemitteln hergestellt werden. Die Umsetzungspro- dukte werden beispielsweise in Shampoos oder Reinigern verwendet.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.
Aus der EP-A 0 455 468 sind Waschmittelformulierungen bekannt, die chemisch modifizierte pflanzliche Proteine als Vergrauungsin- hibitor enthalten. Die Proteine werden vorzugsweise durch Umset- zung mit Phthalsäureanhydrid in wäßrigem Medium bei einem pH-Wert von mindestens 8 modifiziert. Der Grad der Modifizierung der Pro¬ teine ist jedoch relativ gering, so daß die Umsetzungsprodukte praktisch keine dispergierende Wirkung aufweisen und auch beim Einsatz in Waschmitteln die Primärwaschwirkung der Waschmittel nicht erhöhen.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.
In der DE-A-4 033 209 wird die Umsetzung von Proteinhydrolysaten eines Molgewichts von 200 bis 20 000 mit Ethercarbonsäurechlori- den in wäßrigem Medium beschrieben. Die Umsetzungsprodukte werden als Tenside in Wasch- und Reinigungsmitteln verwendet.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.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, dispergie- rend wirkende Zusätze für den Einsatz in phosphatreduzierten und phosphatfreien Wasch- und Reinigungsmitteln zur Verfügung zu stellen.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.
Die Aufgabe wird erfindungsgemäß gelöst, durch Verwendung von Carboxylgruppen enthaltenden Umsetzungsprodukten ausThe object is achieved according to the invention by using reaction products containing carboxyl groups
a) Maleinsäureanhydrid, Maleinsäure und/oder Fumarsäure und b) Proteinen oder Proteinhydrolisaten, die nicht weiter als bis zu Dipeptiden hydrolisiert sind,a) maleic anhydride, maleic acid and / or fumaric acid and b) proteins or protein hydrolyzates which are hydrolyzed no further than dipeptides,
mit einer Säurezahl von mindestens 1,5 mmol Natriumhydroxid/g Um- Setzungsprodukt als Zusatz zu phosphatreduzierten und phosphat¬ freien Wasch- und Reinigungsmitteln.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.
Zur Herstellung der Umsetzungsprodukte verwendet man als Kompo¬ nente a) Maleinsäureanhydrid, Maleinsäure, Fumarsäure oder Mischungen der genannten Verbindungen. Vorzugsweise setzt man Maleinsäureanhydrid ein.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.
Als Verbindungen der Komponente b) kommen Proteine oder Protein- hydrolysate in Betracht, die nicht weiter als bis zu Dipeptiden hydrolysiert sind. Als Proteine können alle synthetischen oder natürlichen Proteine sowie Mischungen aus synthetischen und na¬ türlichen Proteinen eingesetzt werden. Die Proteine können pflanzlichen oder tierischen Ursprungs sein. Die Proteine können in gereinigter Form oder ungereinigt zur Herstellung der Umset- zungsprodukte eingesetzt werden. Beispiele für ein gereinigtes Protein ist Sojaproteinisolat, während Molkenprotein ein Beispiel für ein ungereinigtes Protein ist. Beispiele für tierische Pro¬ teine sind Casein, Molke, Gelatine und Knochenleim. Beispiele für pflanzliche Proteine sind die Proteine aus Kartoffeln, Zuckerrü- ben, Markerbsen, Soja, Weizen und Mais.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.
Die Proteinhydrolysate werden durch Hydrolyse der Proteine unter sauren, neutralen, basischen oder fermentativen Bedingungen her¬ gestellt. Die Hydrolyse der Proteine kann unterschiedlich weit durchgeführt werden, jedoch nicht weiter als bis zu Dipeptiden. Die Hydrolyseprodukte können noch Anteile an niedrigmolekularen Peptiden enthalten. Als Komponente b) kann man auch Mischungen aus Proteinen und Proteinhydrolysaten einsetzen. Beispiele für sauer, neutral oder basisch hydrolysierte Proteine sind Knochen- leim, Sojahydrolysate und Weizenhydrolysate. Die Proteine können jedoch auch reduktiv oder oxidativ behandelt werden, um sie in eine besser in Wasser lösliche Form zu überführen. Beispielsweise können Weizengluten oder Sojaproteine durch Alkalisulfit, Alkali- thiosulfat, Mercaptoethanol, Thioglykolsäure, Thiomilchsäure oder Alkalisulfid reduktiv vorbehandelt werden. Sie können auch mit Oxidationsmitteln, z.B. mit Wasserstoffperoxid, Peressigsäure, Peroxiden, Natrium- oder Kaliumperoxodisulfat, Sauerstoff oder Salpetersäure behandelt werden.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.
Die natürlichen Proteine können herkunftsbedingt auch andere Be¬ standteile wie Kohlenhydrate, Faserbestandteile, Cellulose und Hemicellulose, Öle oder Fette enthalten. Beispielsweise enthalten Molkeproteine neben geringen Mengen an Fett und Öl der Milch größere Mengen Laktose und andere Kohlenhydrate. Sojamilch kann neben den Sojaproteinen noch Öl- und Fettanteile aus der Soja¬ pflanze aufweisen. Auch Celluloseanteile können im Sojaprotein enthalten sein. Die Proteine können im Molekulargewicht so weit erniedrigt bzw. hydrolysiert werden, daß neben höhermolekularen Proteinhydrolysaten auch Di- und Tripeptide vorliegen. Beispiele für Dipeptide sind: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-GlyAsp-Glu Asp-Asp Asp-Gly
Beispiele für Tripeptide sind:Examples of tripeptides are:
Asp-Asp-Asp Asp-Glu-Asp Asn-Gln-Ser Glu-Ser-Pro Asp-Ser-Pro Asp-Glu-Gly Asp-Lys-AsnAsp-Asp-Asp Asp-Glu-Asp Asn-Gln-Ser Glu-Ser-Pro Asp-Ser-Pro Asp-Glu-Gly Asp-Lys-Asn
Beispiele für synthetische Proteine sind Polyasparaginsäuren, die beispielsweise durch Polykondensation von L- oder DL-Asparagin- säure oder durch thermische Polykondensation von sauren Ammonium¬ salzen der Fumarsäure, Maleinsäure oder Äpfelsäure erhältlich sind. Polykondensate der Glutaminsäure, die durch Polymerisieren von N-Carbonsäureanhydriden der Glutaminsäure und ihrer Ester herstellbar sind. Als Komponente b) eignen sich alle syntheti¬ schen Peptide, die durch Polymerisation von N-Carbonsäureanhydri¬ den nach Art einer anionischen Polymerisation erhältlich sind. Als Komponente b) eignen sich außerdem solche synthetischen Pep- tide, die durch Mischpolymerisation von verschiedenen N-Carbon¬ säureanhydriden unterschiedlicher Aminosäuren erhältlich sind. Als Komponente b) verwendet man vorzugsweise Proteine aus Soja, Weizen, Kartoffeln, Molke, Casein und Gelatine. 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).
Durch die Umsetzung der Komponenten a) mit b) wird die Säurezahl der Proteine erhöht. Die Säurezahl ist die erforderliche Menge an Natronlauge, die zur Neutralisation von 1 g des Umsetzungsproduk¬ tes benötigt wird. Sie wird beispielsweise durch Titration mit Hilfe von 0,1 N-Natronlauge ermittelt. Die Säurezahlen der Pro¬ teine betragen zwischen 0 und 1, während die Säurezahlen der Um- Setzungsprodukte mindestens 1,5 mmol Natronlauge/g Umsetzungspro¬ dukt betragen. Die Säurezahlen der hydrolysierten Proteine können bis zu 1,3 mmol Natronlaύge/g betragen. Sie .werden durch die Um¬ setzung der Proteinhydrolysate mit den Verbindungen der Kompo¬ nente a) weiter erhöht. Die Säurezahlen der Umsetzungsprodukte betragen vorzugsweise 1,8 - 10 mmol Natronlauge/g Umsetzungspro¬ dukt.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.
Die Verbindungen der Komponenten a) und b) werden bei Temperatu¬ ren in dem Bereich von 90 - 300 umgesetzt. Die Umsetzung wird insbesondere bei Temperaturen von 120 bis 300°C', vorzugsweise 150 bis 270°C unter Druck, z.B. bis zu 30 bar, durchgeführt. Die Ver¬ bindungen der Komponente a) können dabei als Lösemittel für die Proteine oder Proteinhydrolysate verwendet werden. Die Umsetzung der Komponenten a) und b) wird vorzugsweise in Abwesenheit von Wasser durchgeführt. Man kann die Umsetzung jedoch auch in Gegen¬ wart von Wasser beginnen, z.B. bei Temperaturen in dem Bereich von 50 - 99°C und mit Fortschreiten der Umsetzung die Temperatur des Reaktionsgemisches so weit erhöhen, daß das Wasser aus dem Reaktionsgemisch praktisch vollständig entfernt wird. Hierbei kann sich aus Maleinsäure zunächst Maleinsäureanhydrid bilden, das dann mit den Proteinen oder Proteinenhydrolysaten reagiert. Besonders bevorzugt ist eine Arbeitsweise, bei der man die Umset¬ zung in geschmolzenem Maleinsäureanhydrid durchführt. Die Kompo¬ nenten a) und b) können in jedem beliebigen Gewichtsverhältnis miteinander umgesetzt werden, z.B. im Gewichtsverhältnis 99:1 bis 1:99. Vorzugsweise setzt man die Komponenten a) im Überschuß ein, z.B. beträgt ihr Anteil in der Reaktionsmischung 55 - 90 Gew.-%. Die überschüssigen Komponenten a) können nach Beendigung der Um¬ setzung leicht aus dem Reaktionsgemisch entfernt werden. Wenn beispielsweise Maleinsäureanhydrid als Komponente a) eingesetzt wurde, kann man es leicht durch Sublimieren, Destillieren oder Extrahieren mit Lösemitteln, wie Aceton oder Essigsäureethylester aus der Reaktionsmischung entfernen. Die Umsetzungsprodukte aus den Komponenten a) und b) haben K- Werte (bestimmt nach Fikentscher in 1 %iger wäßriger Lösung am Natriumsalz bei pH 7 und 25°C) von 10 bis 100.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.
Die Umsetzungsprodukte können in Form der freien Säuren oder in Form der Salze mit Alkalimetall-, Erdalkalimetall- und Ammonium¬ basen eingesetzt werden. Zur Herstellung der Salze fügt man übli¬ cherweise zu einer wäßrigen Lösung der Umsetzungsprodukte bzw. zu einer Aufschlämmung der Umsetzungsprodukte in Wasser eine Base oder eine Mischung mehrerer Basen zu. Geeignet sind beispiels¬ weise Natronlauge, Kalilauge, Soda, Pottasche, Natriumhydrogen- carbonat, Kaliumhydrogencarbonat, Kalziumhydroxyd, Kalziumoxid, Bariumhydroxyd, Magnesiumhydroxyd oder Magnesiumoxid sowie Ammo¬ niak und Amine wie Methylamin, Ethylamin, n-Propylamin, Isopro- pylamin, n-Butylamin, Isobutylamin, Ethanolamin, Diethanolamin, Triethanolamin, Morpholin und Cyclohexylamin.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.
Die Umsetzungsprodukte aus den Komponenten a) und b) sind biolo¬ gisch abbaubar nach OECD Guidelines for Testing of Chemicals, Pa- ris 1981, 302 B (modifizierter Zahn-Wellens-Test) . Sie sind auch abbaubar gemäß der Abnahme des gelösten Sauerstoffs im geschlos¬ senen Flaschentest sowie gemäß dem modifizierten SCAS-Test, vgl. R. Wagner, Methoden zur Prüfung der biochemischen Abbaubarkeit chemischer Substanzen, Verlag Chemie, Weinheim 1988, Seite 62.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.
Die oben beschriebenen Umsetzungsprodukte bzw. ihre Alkali-, Am¬ monium- und Erdalkalimetallsalze werden als Zusatz zu phosphatre¬ duzierten oder phosphatfreien Wasch- und Reinigungsmitteln ver¬ wendet. In den meisten Fällen beträgt die angewendete Menge an Umsetzungsprodukten 0,1 - 30 Gew.-%, bezogen auf die Wasch- und Reinigungsmittel. Unter phosphatreduzierten Waschmitteln sollen solche Formulierungen verstanden werden, die nicht mehr als 25 Gew.-% Phosphat, berechnet als Natriumtriphosphat enthalten. Phosphatfreie Waschmittel enthalten größtenteils Natriumalumi- nium-silikat (Zeolith A) . Die Umsetzungsprodukte aus den Kompo¬ nenten a) und b) bzw. deren Salze werden vorzugsweise in Mengen von 1 bis 20 Gew.-%, bezogen auf die Wasch- oder Reinigungsmit¬ telformulierung, eingesetzt. Unter Reinigungsmittelformulierungen sollen sämtliche Reiniger für harte Oberflächen verstanden wer- den, z.B. Geschirreiniger, Reiniger für die industrielle Fla¬ schenwäsche, Reiniger für Molkereibetriebe und Fußbodenreini¬ gungsmittel.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.
Die Umsetzungsprodukte werden vorzugsweise in Textilwaschmitteln eingesetzt. Sie besitzen in der Waschmittelflotte ein gutes Dis- pergiervermögen für Partikelschmutz, insbesondere für Tonminera¬ lien (Clay) . Diese Eigenschaft ist deshalb wichtig, weil lehmar- tige Verschmutzungen von Textilgut weit verbreitet sind. Die Um¬ setzungsprodukte wirken außerdem als Builder für Waschmittel und bewirken während des Waschvorgangs eine Reduktion der Inkrustie¬ rung und der Vergrauung auf dem gewaschenen Textilgut. Sie sind somit auch als Inkrustations- und Vergrauungsinhibitoren geeig¬ net.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.
Die Zusammensetzung der Wasch- und Reinigungsformulierungen kann sehr unterschiedlich sein. Wasch- und Reinigungsmittel enthalten üblicherweise 2 bis 50 Gew.-% Tenside und gegebenenfalls Builder. Diese Angaben gelten sowohl für flüssige als auch für pulverför- ige Wasch- und Reinigungsmittel. Beispiele für die Zusammenset¬ zung von Waschmittelformulierungen, die in Europa, in den USA und in Japan gebräuchlich sind, findet man beispielsweise in Chemical and Engn. News, Band 67, 35 (1989) tabellarisch zusammengestellt. Weitere Angaben über die Zusammensetzung von Wasch- und Reini¬ gungsmitteln können der WO-A-90/13581 sowie Ullmanns Encyklopädie der technischen Chemie, Verlag Chemie, Weinhein 1983, 4. Auflage, Seiten 63-160 entnommen werden. Außerdem sind solche Waschmittel- formulierungen von Interesse, die bis zu 60 Gew.-% eines Alkali¬ silikats und bis zu 10 Gew.-% eines erfindungsgemäßen Polykonden- sats enthalten. Als Alkalisilikate kommen beispielsweise die amorphen Natriumdisilikate in Betracht, die in der EP-A-0 444 415 beschrieben werden, sowie kristalline Schichtsilikate, die gemäß der EP-A-0 337 219 in Waschmittelformulierungen als Builder ent¬ halten sind und gemäß der EP-B-0 164 514 zur Enthärtung von Was¬ ser verwendet werden, und Natriumsilikate, die durch Entwässern von Natriumsilikatlösungen und Trocknen bis zu Wassergehalten von 15 bis 23, vorzugsweise 18 bis 20 Gew.-% erhältlich sind. Natriumaluminium-silikate (Zeolith A) können in Mengen bis zu 50 % in Waschmitteln enthalten sein.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%.
Die Waschmittel können gegebenenfalls noch ein Bleichmittel ent¬ halten, z.B. Natriumperborat, das im Fall seines Einsatzes in Mengen bis zu 30 Gew.-% in der Waschmittelformulierung enthalten sein kann. Die Wasch- und Reinigungsmittel können gegebenenfalls weitere übliche Zusätze enthalten, z.B. Komplexbildner, Citrate, Trübungsmittel, optische Aufheller, Enzyme, Parfümöle, Farbüber- tragungsinhibitoren, Vergrauungsinhibitoren und/oder Bleichakti- vatoren.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.
Die Umsetzungsprodukte sind außerdem als Wasserbehandlungsmittel geeignet . Sie werden dabei üblicherweise in Mengen von 1 bis 1000 ppm dem Wasser in Kühlkreisläufen, Verdampfern oder Meerwas- serentsalzungsanlagen zugesetzt. Sie wirken außerdem als Belags- Verhinderer bei der Eindampfung von Zuckersaft. Sie werden dem Zuckerdünnsaft in Mengen von 0,1 bis 1000 ppm zugesetzt.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.
Die K-Werte der neutralisierten Umsetzungsprodukte wurden nach H. Fikentscher, Cellulose-Chemie, Band 13, 58 bis 64 und 71 bis 74 (1932) in wäßriger Lösung bei einer Temperatur von 25°C und ei¬ ner Konzentration von 1 Gew.-% bei pH 7 am Natriumsalz der Poly¬ meren bestimmt.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.
BeispieleExamples
Allgemeine Herstellvorschrift für die UmsetzungsprodukteGeneral manufacturing instructions for the implementation products
In einem 500 ml fassenden druckdicht verschließbaren Reaktor, der mit einem Rührer ausgestattet ist, werden die in Tabelle 1 ange¬ gebenen Mengen an Maleinsäureanhydrid und Protein eingefüllt und unter Feuchtigkeitsausschluß für 4 h auf eine Temperatur von 140°C unter Druck erhitzt. Man erhält dann eine Lösung bzw. eine Auf- schlämmung des Umsetzungsproduktes in geschmolzenem Malein- säureanhydrid. Um die Reaktionsmischung zu reinigen, fügt man nach dem Erkalten des Reaktionsgemisches 1 1 wasserfreies Aceton zu, rührt die Mischung 3 h und filtriert. Der Filterrückstand wird anschließend 4 h in einem Extrahierapparat mit Aceton extra¬ hiert und danach im Vakuum getrocknet. Man erhält dabei die in der Tabelle 1 angegebenen Umsetzungsprodukte, die mit Hilfe des K-Wertes und der Säurezahl charakterisiert sind. 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.
Tabelle 1Table 1
+) Der Filterrückstand wurde mit Essigsäureethylester extrahiert +) The filter residue was extracted with ethyl acetate
Für die anwendungstechnischen Prüfungen wurden die Umsetzungspro¬ dukte 1 bis 10 in die Natriumsalze überführt, in dem man 10 g der pulvrigen Produkte in 100 ml Wasser aufrührte und durch Zugabe von 10 %iger wäßriger Natronlauge solange neutralisierte, bis keine Natronlauge mehr verbraucht wurde und eine wäßrige Lösung oder Aufschlämmung der Umsetzungsprodukte mit einem pH-Wert zwischen 7 und 8 entstanden war.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.
Anwendungstechnische BeispieleApplication engineering examples
Die Clay-Dispergierung wurde nach dem im folgenden beschriebenen Clay-Dispergiertest (CD-Test) beurteilt.The clay dispersion was evaluated according to the clay dispersion test (CD test) described below.
CD-TestCD test
Als Modell für partikulären Schmutz wird feingemahlener China- Clay SPS 151 benutzt. 1 g Clay wird unter Zusatz von 1 ml einer 0,1 %igen Natriumsalzlösung des Polyelektrolyten in 98 ml Wasser 10 Minuten in einem Standzylinder (100 ml) intensiv dispergiert. Sofort nach dem Rühren nimmt man aus der Mitte des Standzylinders eine Probe von 2,5 ml und bestimmt nach dem Verdünnen auf 25 ml die Trübung der Dispersion mit einem Turbidimeter. Nach 30- bzw. 60-minütiger Standzeit der Dispersion werden erneut Proben genom- men und wie oben die Trübung bestimmt. Die Trübung der Dispersion wird in NTU (nephelometric turbidity units) angegeben. Je weniger sich die Dispersion während der Lagerung absetzt, desto höher sind die gemessenen Trübungswerte und um so stabiler ist die Dis¬ persion. Als zweite physikalische Meßgröße wird die Dispersions- konstante bestimmt, die das zeitliche Verhalten des Sedimentati¬ onsprozesses beschreibt. Da der Sedimentationsprozeß annähernd durch ein monoexpotentielles Zeitgesetzt beschrieben werden kann, gibt τ die Zeit an, in der die Trübung auf 1/e-tel des Ausgangszu¬ standes zum Zeitpunkt t=0 abfällt.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.
Je höher ein Wert für τ ist, um so langsamer setzt sich die Dis¬ persion ab. Tabelle 2The higher a value for τ, the slower the dispersion settles. Table 2
Wie aus den in der Tabelle angegebenen-Maßwerten folgt, sind die erfindungsgemäß zu verwendenden Um¬ setzungsprodukte gute Dispergatoren für Clay.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.
Test auf PrimärwaschvermögenPrimary washing ability test
Speziell wurde das Tonablösevermögen (TAV-Test) von Textilgewebe an Hand von Waschversuchen untersucht. Der im Folgenden beschrie¬ bene TAV-Test zeigt das prinzipielle Tonablösevermögen eines Additivs in Gegenwart eines Tensids, jedoch unter Ausschluß ande¬ rer, üblicher Waschmittelingredentien und ist demzufolge unabhän¬ gig von der gewählten Waschmittelformulierung. Tonmineralien sind gefärbt und geben bei einer Ablagerung auf dem Gewebe diesem einen Farbschleier. Um die Primärwaschwirkung von Ton auf dem Gewebe zu erfassen, wurde Baumwoll/Polyestergewebe mit einer Ton¬ mischung bestehend aus je 33,3 % aus den Sorten 178/R (ockerfar¬ ben) , 262 (braun) und 84/rf (rotbraun) der Fa. Carl Jäger, Hil- gert, gleichmäßig beschichtet. Die Tonsorten sind unterschiedlich "fett"; d.h. sie unterscheiden sich im Gehalt an Aluminium-, Ei¬ sen- und Manganoxid. Die Tonmischung wurde in Form einer 20 %igen Suspension in vollentsalztem Wasser unter kräftigem Umpumpen der Suspension homogen auf das Gewebe gebracht. Dies wurde mit einem Jigger der Fa. Küsters, Krefeld, bei 10 Meter/Minute unter Ver¬ wendung von Körperware aus 33 % Baumwolle und 67 % Polyester (BW/ PES-Gewebe) der Fa. Winkler, Waldshut, durchgeführt. Nach 3 Durchläufen wurde anschließend mit 600 1 vollständig entsalztem Wasser ein Mal gespült. Danach wurde das nasse Gewebe in einem Spannrahmen bei 50°C und 2 Meter/Minute Trockengeschwindigkeit ge¬ trocknet. Das auf diese Weise hergestellte Tongewebe enthält 1,76 % Ton, bestimmt durch Veraschung bei 700°C, 2,5 h.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.
Das so erhaltene Gewebe wird via Farbstärke vorgemessen und in Klassen eingeteilt. Als Farbstärkebereich für eine Klasse werden 10 Einheiten willkürlich vorgegeben. Der Farbstärkebereich aller Klassen liegt bei dem verwendeten Mischgewebe zwischen 260 und 340 Farbstärkeeinheiten. Eine Waschserie, bestehend aus 6 Wasch¬ versuchen, wird mit angeschmutztem Gewebe aus nur einer Klasse durchgeführt.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.
Die Waschversuche (TAV-Test) wurden unter folgenden Bedingungen durchgeführt:The washing tests (TAV test) were carried out under the following conditions:
Waschgerät: Launder-o-meterWashing machine: Launder-o-meter
Anzahl der Waschzyklen: 1Number of wash cycles: 1
Anzahl der Spülzyklen: 1Number of rinsing cycles: 1
Anzahl der Waschversuche: 6Number of washing attempts: 6
Waschtemperatur: 20 - 24°C Waschdauer: 15 min Flottenmenge 500 g VE1)-Wasser + 80 ppm ethoxilierter OxoalkoholWashing temperature: 20 - 24 ° C Washing time: 15 min Fleet quantity 500 g VE 1) water + 80 ppm ethoxylated oxo alcohol
(Cι3/C15-Oxoalkohol + 8 EO)(Cι 3 / C 15 -oxo alcohol + 8 EO)
Wasserhärte (Ca2_t + Mg2+) : 1 mmol/1 5 Molverhältnis Ca2+: Mg2+:HC03 _: 3:1:6 pH: 10 ± 0,1Water 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
Testkonzentration des Polymer: 80 ppm Schmutzgewebe: 5 g Tongewebe (~ 30,5 cm x 8 cm) Weißgewebe bzw. sauberes 10 Gewebe: 5 g PES/BW-Gewebe (~ 30 cm x 8 cm)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 = vollständig entsalztesD VE = completely desalinated
Nach dem Spülen mit 500 g Wasser (Härte 1 mmol/1 Ca2+ und Mg2+) , 15 20°C, 1 min im Launder-o-meter werden die Gewebe geschleudert und anschließend zum Trocknen einzeln aufgehängt. Vermessen wird das Gewebe mit einem Elrepho 2000 der Fa. Data Color, Heidenheim, und zwar 6 Meßpunkte pro Gewebestück. Der für die Auswertung verwen¬ dete Wellenlängenbereich beträgt 400 - 700 nm. Gemessen wird der 20 Reflexionsgrad als Funktion der Wellenlänge. Als Referenz dient Bariumsulfat. Aus den Remissionswerten wird nach W. Baumann, R. Broßmann, B.T. Gröbel, N. Kleinemeier, M. Kraver, A.t. Leaver und H.-P. Oesch; Melliand Textilberichte Band 67, 562 ff. (1986), die Farbstärke mit Wichtung der Augenreizfunktion berechnet. Die 25 Wichtungsfaktoren für die Augenreizfunktion (Xχo (λ) + Y^ (λ) + Zχo (λ) ) sind der nachfolgenden Tabelle zu entnehmen: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:
Die Wichtung mit der Augenreizfunktion des Menschen soll schon leichte Vergilbungen des Gewebes stärker gewichten. Die genaue Herleitung der mathematischen Auswertung wurde von A. Kud in Ten- side, Surfactants, Detergents, Band 28, 497 ff (1991) , beschrie- ben. 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).
Die Primärwaschwirkung in % wird nach der folgenden Gleichung be¬ rechnet:The primary washing effect in% is calculated according to the following equation:
P = (fs,b " fs,a)/(fs,b ~ fs,o) • 100P = (f s , b "fs, a) / (fs, b ~ fs, o) • 100
~ S , Ώ = Farbstärke des angeschmutzten Gewebes (Tongewebe) vor dem Waschen ~ S , Ώ = color strength of the soiled fabric (clay fabric) before washing
fSra = Farbstärke des angeschmutzten Gewebes nach dem Waschenf Sra = color strength of the soiled fabric after washing
fS/0 = Farbstärke des sauberen Gewebes vor der Anschmutzung (Schmutzgewebe vor der Anschmutzung) .f S / 0 = color strength of the clean fabric before soiling (dirty fabric before soiling).
Die Verwendung der Farbstärke zur Berechnung der Primärwaschwir¬ kung hat im Vergleich zur Remission bei einer Wellenlänge oder dem in der Literatur verwendeten K/S-Werten (K = Absorptionskoef¬ fizient und S = Streukoeffizient) bei einer Wellenlänge den Vor¬ teil, daß der sichtbare Bereich des Spektrums erfaßt wird und Schmutzpartikel aller Farben berücksichtigt werden.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.
Die erfindungsgemäßen zu verwendenden Polymeren wurden nach dem oben beschriebenen TAV-Test geprüft, vgl. Beispiele 10 bis 18. Die dabei erhaltenen Ergebnisse sind zusammen mit den Ergebnissen der im folgenden beschriebenen Vergleichsbeispiele 3 und 4 in Ta¬ belle 3 angegeben. Wie daraus ersichtlich ist, tritt durch Zugabe der erfindungsgemäß zu verwendenden Polymeren zu der wäßrigen Lösung des nichtionischen Tensids eine Erhöhung der Primärwa¬ schwirkung auf.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.
Vergleichsbeispiel 3Comparative Example 3
Anstelle der in den Beispielen 10 bis 18 eingesetzten Umsetzungs¬ produkte verwendete man dieselbe Menge, d.h. 80 ppm, Citronen- säure in Form des Mono-natriumsalzes. Vergleichsbeispiel 4Instead 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
Beispiel 10 wurde mit der einzigen Ausnahme wiederholt, daß man den Test in Abwesenheit des Umsetzungsprodukts 1 durchführte, d.h. die Wirkung einer Tensidlosung prüfte, die 80 ppm des in den Beispielen 10 bis 18 verwendeten Tensids enthielt.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.
Tabelle 3Table 3

Claims

Patentansprüche Claims
1. Verwendung von Carboxylgruppen enthaltenden Umsetzungsproduk- ten aus1. Use of reaction products containing carboxyl groups
(a) Maleinsäureanhydrid, Maleinsäure und/oder Fumarsäure und(a) Maleic anhydride, maleic acid and / or fumaric acid and
(b) Proteinen oder Proteinhydrolysaten, die nicht weiter als bis zu Dipeptiden hydrolysiert sind,(b) proteins or protein hydrolyzates that are hydrolyzed no further than dipeptides,
mit einer Säurezahl von mindestens 1,5 mmol NaOH/g Um¬ setzungsprodukt als Zusatz zu phosphatreduzierten und phos¬ phatfreien Wasch- und Reinigungsmitteln.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. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Umsetzungsprodukte durch Reaktion von (a) und (b) bei Tempe¬ raturen von 120 bis 300°C unter Druck erhältlich sind.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. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man als Komponente (a) Maleinsäureanhydrid einsetzt. 3. Use according to claim 1 or 2, characterized in that maleic anhydride is used as component (a).
EP94912550A 1993-04-10 1994-03-29 Use of carboxyl-group-containing reaction products of proteins or hydrolysed proteins in washing and cleaning agents Expired - Lifetime EP0693117B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4311854A DE4311854A1 (en) 1993-04-10 1993-04-10 Use of carboxyl-containing reaction products of proteins or protein hydrolysates in detergents and cleaners
DE4311854 1993-04-10
PCT/EP1994/000982 WO1994024254A1 (en) 1993-04-10 1994-03-29 Use of carboxyl-group-containing reaction products of proteins or hydrolysed proteins in washing and cleaning agents

Publications (2)

Publication Number Publication Date
EP0693117A1 true EP0693117A1 (en) 1996-01-24
EP0693117B1 EP0693117B1 (en) 1998-05-27

Family

ID=6485241

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94912550A Expired - Lifetime EP0693117B1 (en) 1993-04-10 1994-03-29 Use of carboxyl-group-containing reaction products of proteins or hydrolysed proteins in washing and cleaning agents

Country Status (4)

Country Link
US (1) US5665693A (en)
EP (1) EP0693117B1 (en)
DE (2) DE4311854A1 (en)
WO (1) WO1994024254A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4428638A1 (en) * 1994-08-12 1996-02-15 Basf Ag Process for the preparation of polycondensates of aspartic acid and use of the polycondensates
DE19511859A1 (en) * 1995-03-31 1996-10-02 Basf Ag Process for the preparation of mixtures of polyaspartic acids and acylated polyaspartic acids
CA2298580A1 (en) * 1997-08-08 1999-02-18 The Procter & Gamble Company Laundry detergent compositions with amino acid based polymers to provide appearance and integrity benefits to fabrics laundered therewith
US6407053B1 (en) 1997-08-08 2002-06-18 The Procter & Gamble Company Laundry detergent compositions with amino acid based polymers to provide appearance and integrity benefits to fabrics laundered therewith
US6214786B1 (en) 1997-08-08 2001-04-10 The Procter & Gamble Company Laundry detergent compositions with amino acid based polymers to provide appearance and integrity benefits to fabrics laundered therewith
US5952288A (en) * 1997-10-06 1999-09-14 Colgate-Palmolive Co. Protein containing cleaning compositions
NL1019878C1 (en) 2002-01-31 2003-08-04 Inv Promotion Foldable target for offside.
US20060005316A1 (en) * 2004-07-07 2006-01-12 Durrant Edward E Carbonated cleaning composition and method of use
CA2518298A1 (en) * 2005-09-06 2007-03-06 Chaimed Technologies Inc. Biodegradable polymers, their preparation and their use for the manufacture of bandages

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1470429A1 (en) * 1964-06-16 1969-06-12 Wella Ag Process for the preparation of modified resins based on protein
DE2056814C3 (en) * 1970-11-19 1973-09-27 Chemische Werke Huels Ag, 4370 Marl Detergent containing a structural substance
JPS5612351A (en) * 1979-07-13 1981-02-06 Tokyo Fine Chem Kk N-short-chain acylaminoacid and its preparation
JP2616960B2 (en) * 1988-05-26 1997-06-04 日本油脂株式会社 Aqueous gelling agent and aqueous gel
JP2803265B2 (en) * 1989-12-26 1998-09-24 日本油脂株式会社 Denatured polypeptide and use thereof
US5112520A (en) * 1990-04-30 1992-05-12 Protein Technologies International, Inc. Method for improving the soil anti-redeposition properties of washing detergents and product
DE4016002A1 (en) * 1990-05-18 1991-11-21 Basf Ag USE OF WATER-SOLUBLE OR WATER-DISPERSIBLE PEPPER PROTEINS AS ADDITION TO WASHING AND CLEANING AGENTS
DE4033209A1 (en) * 1990-10-19 1992-04-23 Henkel Kgaa SURFACE-ACTIVE ETHERCARBONIC ACID DERIVATIVES
DE4221875A1 (en) * 1992-07-03 1994-01-05 Basf Ag Modified polyaspartic acids, process for their preparation and their use
US5442038A (en) * 1993-10-06 1995-08-15 Srchem, Inc. Polymers of maleic acid with amines
US5408029A (en) * 1993-10-06 1995-04-18 Srchem, Inc. Amino acid copolymers of maleic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9424254A1 *

Also Published As

Publication number Publication date
US5665693A (en) 1997-09-09
DE4311854A1 (en) 1994-10-13
WO1994024254A1 (en) 1994-10-27
DE59406092D1 (en) 1998-07-02
EP0693117B1 (en) 1998-05-27

Similar Documents

Publication Publication Date Title
EP0740696B1 (en) Use of polyasparaginic acid in washing agents
EP0648241B1 (en) Modified polyaspartic acids, process for preparing the same and their use
DE69418403T2 (en) Process for the production of amino acid particles
DE69026908T2 (en) Biodegradable, water-soluble graft copolymers, compositions of such copolymers and processes for the use of such copolymers
DE19516957C2 (en) Water-soluble copolymers and process for their preparation and their use
DE69200380T2 (en) Detergent composition containing hydrolyzable polyimide biopolymer in the washing process.
DE69223819T2 (en) Biodegradable polymers, processes for producing such polymers and compositions containing such polymers
EP0693117B1 (en) Use of carboxyl-group-containing reaction products of proteins or hydrolysed proteins in washing and cleaning agents
WO1993011214A1 (en) Washing and cleaning agents
DE4344029A1 (en) Copolymers of unsaturated carboxylic acids, process for their preparation and their use
EP0689555B1 (en) Polycocondensates of aspartic acid, methods of producing them and their use
DE1915652C3 (en)
DE1915652A1 (en) Washing, bleaching and cleaning agents
DE2025238B2 (en) Powdered detergents and cleaning agents
DE68927290T2 (en) Textile fabric softener containing natural hector rides
DE4131807A1 (en) WASHING DETERGENS WITH IMPROVED ANTI-GRAYING PROPERTIES AND METHOD FOR THE PRODUCTION THEREOF
DE2544242B2 (en)
DE1960140A1 (en) Washing, bleaching and cleaning preparations
DE2057259C3 (en) Detergents and cleaning agents
DE69616085T2 (en) AMINONITRILE INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF 2-HYDROXYETHYLIMINODIACETIC ACID
DE2152141A1 (en) Liquid detergent
DE2539071A1 (en) Washing or bleaching compsns. for textiles - contg. calcium binding agent and additives delaying pptn. of calcium cpds.
EP0775169A1 (en) Method for producing condensation polymers of aspartic acid and their use in washing and cleaning products
DE69630067T2 (en) Polymers of aspartic acid with sequestering action, process for their preparation and their use
EP0777696B1 (en) Process for preparing polyaspartic acid salts

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950814

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17Q First examination report despatched

Effective date: 19960911

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 59406092

Country of ref document: DE

Date of ref document: 19980702

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980619

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19990316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990329

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST