WO1993011214A1

WO1993011214A1 - Washing and cleaning agents

Info

Publication number: WO1993011214A1
Application number: PCT/EP1992/002702
Authority: WO
Inventors: Alexander Kud; Wolfgang Trieselt; Paul Diessel; Walter Denzinger; Heinrich Hartmann; Johannes Perner; Volker Schwendemann
Original assignee: Basf Aktiengesellschaft
Priority date: 1991-12-03
Filing date: 1992-11-24
Publication date: 1993-06-10
Also published as: DE4139826A1

Abstract

Described are washing and cleaning agents containing at least one surfactant and, optionally, the usual additives plus a combination of builders (I and II). Used as builder I are graft copolymers obtained by the radical-initiated copolymerization of monomer mixtures containing a) monoethylenically unsaturated C4-C8 dicarboxylic acids or alkali-metal and/or ammonium salts of such acids, b) monoethylenically unsaturated C3-C10 carboxylic acids or alkali-metal and/or ammonium salts of such acids and, optionally, other monomers in the presence of monosaccharides, oligosaccharides, polysaccharides, oxidatively, hydrolytically or enzymatically decomposed polysaccharides, oxidized hydrolytically or oxidized enzymatically decomposed polysaccharides or chemically modified mono-, oligo- or polysaccharides, and builder II includes at least one alkali-metal silicate. Also described is the use of mixtures of such graft copolymers (I) and alkali-metal silicates (II), in the ratio (I:II) by weight of 1.5:1 to 1:100, as builders in washing and cleaning agents containing surfactants.

Description

Detergents and cleaning agents

description

The invention relates to detergents and cleaning agents which contain at least one surfactant and as builder (I) a graft copolymer of monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated monocarboxylic acids on mono-, OHgo- or polysaccharides or their derivatives and (II) at least one alkali silicate.

From EP-A-0441197 graft copolymers are known which can be obtained by free-radical copolymerization of

(A) Monomer statements

(a) monoethylenically unsaturated C ₄ - to C ₈ -dicarboxylic acids, their anhydrides or alkali and / or ammonium salts,

(b) monoethylenically unsaturated C ₃ to C ₁₀ carboxylic acids or their alkali and / or ammonium salts,

(c) optionally other monoethylenically unsaturated monomers which are copolymerizable with the monomers (a) and (b), and optionally (d) monomers having at least two ethylenically unsaturated non-conjugated double bonds in the molecule in the presence of

(B) monosaccharides, oligosaccharides, polysaccharides, oxidatively, hydrolytically or enzymatically degraded polysaccharides, oxidized hydrolytically or oxidized enzymatically degraded polysaccharides or chemically modified mono-, oligo- and polysaccharides in the weight ratio (A): (B) from 95 to 20): (5 to 80). The graft polymers are used as additives for washing and cleaning agents in amounts of 0.1 to 20% by weight. EP-B-0025551 discloses the use of copolymers of, for example, acrylic acid and maleic acid as an incrustation inhibitor in low-phosphate or phosphate-free detergents. EP-B-0164514 discloses the use of crystalline layered sodium silicates for softening water, which contains calcium and / or magnesium ions and the use of these layered sodium silicates as builders in detergents and cleaners containing surfactants.

From EP-A-0337219 is a storage-stabilized detergent with increased bleaching action with a content of 2 to

20% by weight of detergents and customary washing aids are known, and the builder contains 10 to 50% by weight of crystalline

Layered silicate and a bleach. According to the information in the examples, the detergent formulations contain polycarboxylates. The crystalline layered silicate preferably corresponds to the δ modification of Na ₂ Si ₂ O ₅ .

EP-A-0416366 discloses a dishwashing detergent which contains a crystalline, largely water-insoluble sodium sheet silicate with a SiO ₂ / Na ₂ O molar ratio of 1.9 to 3.5: 1 in combination with a proton donor. Proton donors include polycarboxylates, e.g. E. Copolymers of acrylic acid and maleic acid with a molecular weight of 70,000 are used.

EP-A-0444415 discloses detergents which contain 5 to 50% by weight of at least one surfactant, 0.5 to 60% by weight of an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight. and contain common washing aids. According to the information in the examples, the detergent formulations contain a copolymer of acrylic acid and maleic acid with a molecular weight of approximately 60,000. With the help of the copolymers or graft copolymers known from EP-B-0025551 and EP-A-0441197, it is possible to formulate phosphate-reduced or phosphate-free detergents which, in terms of detergency, contain detergents with a phosphate content of approximately 45% by weight .-% correspond.

The object of the present invention is to provide detergents and cleaning agents which are reduced in phosphate or free of phosphate and which have an increased detergency compared to the previously known polymer-containing detergent formulations.

The object is achieved according to the invention with detergents and cleaning agents which contain at least one surfactant and a builder and, if appropriate, customary additives, if, as builders (I), they contain 0.5 to 15% by weight of graft copolymers which are obtainable by free-radically initiated copolymerization from (A) monomer mixtures

(a) monoethylenically unsaturated C ₄ - to Cn-dicarboxylic acids, their anhydrides or alkali and / or ammonium salts,

(c) optionally other monoethylenically unsaturated monomers which are copolymerizable with the monomers (a) and (b), and optionally

(d) at least two ethylenically unsaturated non-conjugated double bonds in the molecule having monomers in the presence of

(B) monosaccharides, oligosaccharides, polysaccharides, oxidatively, hydrolytically or enzymatically degraded polysaccharides, oxidized hydrolytically or oxidized enzy matically degraded polysaccharides or chemically modified mono-, oligo- and polysaccharides in the weight ratio (A): (B) from (95 to 20): (5 to 80), and

(II) contain 10 to 50% by weight of at least one alkali silicate.

The washing and cleaning agent builder consists of the above-mentioned graft polymers (I) and alkali silicates (II), the weight ratio (I): (II) being from 1.5: 1 to 1: 100. The graft copolymers (I) and processes for their preparation are described in detail in EP-A-0441197. All graft copolymers mentioned in EP-A-0441197 come into consideration as component (T) of the builder system of the present washing and cleaning agents. Preference is given to graft copolymers which are obtainable by free-radically initiated copolymerization of (a) maleic acid and (b) acrylic acid and / or methacrylic acid in the presence of (B) acid, catalytically or enzymatically degraded starches, which are sold commercially under the name starch saccharification products, and chemically modified degraded starches, e.g. B. hydrogenation products of starch hydrolysates such as sorbitol and mannitol, maltose and especially hydrogenated glycose syrups. In the preparation of the graft copolymers, the monomers of group (a) are preferably contained in the monomer mixture (A) in an amount of 15 to 60% by weight and the monomers in group (b) preferably in an amount of 40 to 85% by weight. The graft copolymers have K values (determined according to H. Fikentscher) from 8 to 90, preferably 20 to 75. Component (I) of the builders is in the washing and cleaning agents in an amount of 0.5 to 15, preferably 1 to 10% by weight present.

Component (II) of the builder system of washing and cleaning agents consists of at least one alkali silicate, which is contained in the respective formulations in an amount of 10 to 50% by weight. The alkali silicates are preferably sodium silicates. Suitable products of this type are, for example, sodium disilicates, which are obtained by drying Water glass solutions are available. This usually results in water-containing sodium disilicates which have water contents of about 15 to 23% by weight. Products of this type are commercially available. As component (II) there are also low-water sodium disilicates with water contents, which are preferably produced by partial dewatering of commercially available powdered sodium disilicates with water contents of 15 to 23% by weight. The low-water sodium disilicates obtainable in this way have a water content of less than 15% by weight. The water content of the partially dewatered sodium disilicate is preferably 0.3 to 6% by weight. These products are referred to in EP-A-0444415 as amorphous sodium disilicate. Another group of sodium silicates that can be used as component (II) are crystalline, largely water-insoluble sodium silicates with a molar ratio of SiO ₂ / Na ₂ O of 5: 1 to 1: 1, preferably 3.5: 1 to 1.9: 1.

Crystalline layered sodium silicates as component (II) are known for example from EP-B-0164514. For example, they have the composition NaMeSi _x .O _2X-1 . YH ₂ O, where Me = Na or H, x is a number from 1.9 to 4 and y is a number from 0 to 20. Naturally occurring phyllosilicates of the general formula Me _2n [Si ₂ O ₅ ] _n can also be used; Me = Na, K prefers Na and n = 1 to infinity. From this class of crystalline layered sodium silicates, the commercially available Na-SKS-6, which is similar to the δ-Na ₂ Si ₂ O ₅ , is preferably used. In addition, a crystalline silicate having a weight ratio of SiO ₂ to Na ₂ O = 2: 1 to 2.1: 1, which is under the name Portil ^® A commercially and has water contents of 15 to 23, preferably 18 to 20, preferably as Component (II) used. Other suitable compounds of component (II) are cyclic silicates of the general formula Me _2n (Si _n O _3n ) with Me = Na, K and n = 3, 4 and 6, where Me is preferably Na. Chain-like silicates of the general formulas also come as alkali silicates Me _6n (Si ₄ O _{1 1} ) n or Me _2n (SiO ₃ ) _n , in which Me = Na, K and n = 1 to infinity and Me is preferably Na.

Compounds of component (II) which are preferably used in detergents and cleaning agents are crystalline slide-shaped sodium silicates or crystalline sodium disilicate. The average particle diameter of the alkali silicates used in the washing and cleaning agents is approximately 0.01 to 1000 μm.

Components (I) and (II) can be added to the other constituents of the formulation either individually or as a mixture in the preparation of the washing and cleaning agents. For example, in the formulation of the washing and cleaning agents, it is possible to use mixtures of (I) and (II) in the weight ratio (I): (II) 1.5: 1 to 1: 100, preferably from 1: 3 to 1:25 to be incorporated as a builder in detergents and cleaning agents containing surfactants.

Although the addition of components (I) or (II) to detergent formulations already brings about an improvement in the primary and secondary washing action, the combined use of components (I) and (II) in detergents and cleaning agents leads to an unexpected improvement in the primary and Secondary washing effect of these agents.

Low-phosphate detergents and cleaning agents should be understood to mean such formulations that are less than

25% by weight of phosphate, calculated as pentasodium triphosphate, contain. The composition of detergents and cleaning agents can vary widely. Examples of the composition of washing formulations described in

Europe, the USA and Japan are common, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) in tabular form and in üllmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160. Further information on the composition of detergents and cleaning agents can be obtained from

WO-A-90/13581 can be taken. Detergents and cleaning agents usually contain tensides in amounts of 1 to

50% by weight. The detergents and cleaning agents can either be in Form of a powder or as a liquid. Detergents can in particular also contain a bleaching agent, for example peroxo compounds, such as sodium percrate, peroxocarboxylic acids or polymers with groups containing peroxo. However, sodium perborate is preferred. The bleaches are; in the case of their use in detergents and cleaning agents: contained in amounts of 2 to 30% by weight. The detergents and cleaning agents may optionally contain other conventional additives, e.g. B. complexing agents, citrates, opacifiers, optical brighteners, enzymes, perfume oils, color transfer inhibitors, graying inhibitors and / or Bieich activators. The graft polymers can also be used together with the silicate in liquid detergent formulations. In this case, aqueous solutions of alkali silicates can also be used.

The mixture of components (I) and (II) can also advantageously be used in conventional dishwashing detergents. The amounts to be used essentially correspond to the amounts used as additives for the formulation of textile detergents.

The K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932). K means =

x 10 ³ . The measurements were taken on 1

aqueous solutions of the sodium salts of the copolymers at 25 ° C and a pH of 7 carried out. Unless stated otherwise, the figures mean percentages by weight.

The DE values of the starches or their derivatives mean dextrose equivalents. They were determined using the LufrSchoorl method, cf. G. Tegge, Starch and Starch Derivatives, Behr's Verlag, Hambur 1984, page 305.

Graft copolymer 1

According to the procedure given in Example 1 of EP-A-0441197, a copolymer of 30% maleic acid and 70% acrylic acid was produced with the exception that instead of dextrin, the same amount of maltodextrin was used with a DE value according to (Luff-Schoorl) from 17 to 20. A graft copolymer was obtained: with a K value of 42.

Copolymer A: Commercial copolymer of 30% maleic acid and 70% acrylic acid with a K value of 60.

In order to demonstrate the effectiveness of the combination of components (I) and (II) in phosphate-free detergent formulations, the primary washing action, the graying-inhibiting action and the incrustation-inhibiting action of the detergent formulations described below were tested.

The primary washing effect and the graying-inhibiting effect were tested as follows:

Cotton fabric was subjected to a series of 3 washes together with standard dirt fabric. The dirty fabric is renewed after each wash, the test fabric becoming more soiled after each wash. The whiteness of the test fabric after the 3rd wash is used to assess the degree of soiling, the values are secured by repeated repetition and averaging. Percent remission was measured with an Elrepho (Zeiss) filter 8 at 480 nm. Test conditions:

Tester Launder-O-meter

Water hardness: 3.0 mol / l (Ca + Mg)

Molar ratio Ca: Mg: HCO ₃ = 4: 1: 8 liquor quantity: 250 g

Test temperature: 60 ° C

Test duration per cycle: 30 minutes (with heating up time)

Detergent concentration: 4.5 g / l

Prewash cycles

(without dirt tissue): 1

Washing cycles: 3

Clean fabric: cotton nettle fabric, 10 g

Washing trials were carried out with two combinations of dirty fabric. Dirt tissue combination A:

5 g WFK10D (WFK-Testgewebe GmbH, Krefeld)

5 g EMPA101 (from the Federal Materials Testing and Testing Institute, St. Gallen, Switzerland)

Dirt tissue combination B:

5 g WFK20D

5 g EMPA104 The detergent formulations used are given in Table 1.

The primary washing effect was determined with detergents 1 and 2. The results are shown in Table 2.

Table 2

Primary washing effect of detergents 1 and 2

(Fabric combination A)

As can be seen from Table 2, the graft copolymer 1 to be used according to the invention in combination with both a crystalline layered silicate and with a crystalline silicate exhibits a significantly higher remission and thus better primary washing action than when the commercially available copolymer A is combined with the same crystalline one Layered silicate or the crystalline silicate.

As can be seen from the following Table 3, the graying inhibition of the combination of graft copolymer 1 and crystalline to be used according to the invention is also

Layered silicate is better than a combination of commercially available copolymer A and the same layered silicate in a phosphate-free detergent formulation. Table 3

Graying inhibition

(Fabric combination B)

The secondary washing effect was determined using the incrustation. When washing in hard water, the incrustation-inhibiting effect of a detergent is of great importance. The one with the water hardness and

Insoluble salts formed from detergent ingredients (carbonates, silicates, calcium soaps) can deposit on the tissues and thus encrust them. The result is increased wear on the fabrics and poorer wearing properties of the textiles.

The following test conditions were selected to determine the incrustation effect: secondary washing effect incrustation

Test conditions:

Tester Launder-O-meter

Water hardness 4mmol Ca ⁺⁺ Mg ^- per 1

Molar ratio Ca: Mg 4: 1

Amount of liquor 250 g

Wash temperature 60 ° C

Test duration per cycle 30 minutes (with heating up time)

Detergent concentration 4.5 g / l

Wash cycles 15

Fabric 20 g cotton nettle fabric Determination method Ash content Burning the tissue in the

Muffle furnace at 700 ° C, 2.5 hours

Table 4

Incrustation effect

¹⁾ nb = was not determined

As can easily be seen, the ash content is lower when using the graft polymer 1 than with the copolymer A and thus the incrustation inhibition of the graft polymer 1 is also better.

Claims

1. Detergents and cleaning agents which contain at least one surfactant and a builder and, if appropriate, conventional additives, characterized in that they, as builder (I), contain 0.5 to 15% by weight of graft copolymers which are obtainable by free-radically initiated copolymerization of

(A) monomer mixtures

(a) monoethylenically unsaturated C ₄ to C ₈ dicarboxylic acids, their anhydrides or alkali and / or ammonium salts,

(c) optionally other monoethylenically unsaturated monomers which are copolymerizable with the monomers (a) and (b) and optionally

(B) monosaccharides, oligosaccharides, polysaccharides, oxidatively, hydrolytically or oxidized enzymatically degraded polysaccharides or chemically modified mono-, oligo- and polysaccharides

in the weight ratio (A): (B) from (95 to 20): (5 to 80), and

(II) contain 10 to 50% by weight of at least one alkali silicate.

2. Washing and cleaning agents according to claim 1, characterized in that they contain crystalline layered sodium silicates or crystalline sodium disilicates as component (II).

3. Use of mixtures of (I) graft copolymers which are obtainable by free-radically initiated copolymerization of (A) monomer mixtures

(b) monoethylenically unsaturated C ₃ -C ₁₀ -carboxylic acids or their alkali and / or ammonium salts,

(c) optionally other monoethylenically unsaturated monomers which are copolymerizable with the monomers (a) and (b) and optionally (d) monomers having at least two ethylenically unsaturated non-conjugated double bonds in the molecule in the presence of

in the weight ratio- (A): (B) from (95 to 20): (5 to 80), and

(II) Alkali silicates in the weight ratio (I): (II) of 1.5: 1 to 1: 100, as a builder in detergents and cleaning agents containing surfactants.