DK148120B - DETERGENT WITHOUT PHOSPHATE OR NITROGEN CONTAINERS - Google Patents

Description

148120

The present invention relates to a high-performance detergent without phosphate or nitrogen-containing builders, which detergent uses a builder system comprising a citrate salt and a mixture of an alkali metal silicate and an alkali metal carbonate.

The general awareness of the importance of improving the environment and avoiding devastating effects on the ecology has been greatly increasing, and as a result, extensive re-examinations of waste disposal methods have been carried out. Various studies of lakes, rivers, streams and groundwater have concluded that ordinary household detergents, especially those containing durable synthetic organic surfactants and phosphate builders, have had a detrimental effect on such water bodies. The surfactant organic compounds, which are not readily degraded after depletion from the kitchen sink, wash basin or washing machine, can find their way to natural streams, rivers, rivers and lakes.

The major detergent manufacturers seek to remove long-lasting synthetic organic surfactants from their products, such as the highly branched alkylarylsulfonates, which are non-biodegradable, and have replaced these with relatively readily degradable straight chain alkylbenzene sulfonates or similar materials which will be degraded. in short time.

Due to the highly desired building and the sequestering and soil suspending effects of the polyphosphates, in particular of the alkali metal tripolyphosphates and pyrophosphates, it has previously been difficult to remove them from detergents without significant loss in purity. Even 100 µ active synthetic organic surfactants have not been able to produce the same purification effect obtained by combinations of such compounds and polyphosphate (s). Currently, just about the only substitute for polyphosphates capable of substantially replicating their effects is nitrilotriacetic acid or a similar nitrilo triacetate, often referred to as NTA. However, recent laboratory studies and scientific studies have shown that NTA can be a harmful cause of cancer, and consequently there have been strict official regulations prohibiting or restricting its use. Therefore, in order to overcome these detrimental effects on the environment caused by the use of phosphates and nitrogen compounds in detergents, major activities are in progress to provide effective, safe and acceptable detergents that do not contain phosphate or nitrogen compounds as builder. The present invention relates to such detergents.

The detergent according to the invention is based on a simple, inexpensive and commercially available anionic surfactant as well as a fatty acid or similar soap, where everything is easily biodegradable. In addition, the material contains no polyphosphates or other phosphate builder salts or any nitrogen compounds as builders, but uses a mixture of alkali metal citrates, carbonates and silicates as builders.

Briefly, the high-performance detergent according to the invention comprises approx. 12 to 16% of a linear alkylarylsulfonate (LAS), 8 to 15% of soap, 15 to 25% of alkali metal citrate, 45 to 75% of a mixture of alkali metal carbonate and alkali metal silicates, 0 to 10% of clarifiers and other excipients, and moisture.

French Patent Specification No. 2,135,261 discloses a detergent without soap content, but which may contain, for example, an alkylbenzenesulfonate sodium salt, sodium silicate, sodium carbonate, sodium bicarbonate, sodium citrate, sodium sulfate and carboxymethyl cellulose, as described in Example 5. Agents of this kind usually require the presence of an anti-gene deposition agent (CMC) to reduce excessive foams, especially when the surfactant is an alkyl benzene sulfonate.

Accordingly, the detergent components disclosed in the disclosure disclosure and the amounts thereof make it generally necessary to use anti-repellant agents to avoid excessive foaming.

Only in Examples 6 and 7 of said French publication specification are CMC omitted, which is possible because the detergents disclosed therein differ substantially from the detergent of the present invention in that the anionic surfactant is not an ABS type surfactant as it is the case of the anionic sulfonate surfactant used in the detergent according to the invention. Excluding Example 5 of French Patent Specification No. 2,135,261, neither soap nor citrate is contained in the exemplified detergents, and the amount of at least two components of the detergents known therefrom is outside the amounts prescribed by the present invention. invention.

The detergent of the present invention is characterized in that it essentially consists of (a) approx. 12 to 16% by weight of a linear alkylarylsulfonate having an average alkyl chain length of about

10 to 16 carbon atoms, (b) approx. 8 to 15% by weight of soap selected from water-soluble salts of higher fatty or resin acids;

15 to 25% by weight of citric acid or a water-soluble salt of citric acid and (d) about 45 to 75% by weight of a builder salt mixture of alkali metal silicates and alkali metal carbonates where the weight ratio of sili = 4 U8120 cat to carbonate is from 1: 0.25 to 1 : 4.0.

The detergent of the invention is a very effective high performance detergent with cleaning properties substantially equal to or superior to the properties of conventional high performance detergents with a high phosphate content and a high content of nitrogenous builders.

The present detergent is low-foaming, non-yellowing and does not require the addition of the anti-repellant. It can be used for all textiles and at all temperatures, especially at low temperatures. As a detergent-active component of the detergent, a biodegradable anionic sulfonate surfactant and soap are used.

The detergent surfactant system of the invention is a two-part surfactant system, both of which are biodegradable. As a first component of the surfactant system, the detergent contains approx. 12 to 16% by weight, preferably approx. 14% by weight of an anionic higher alkylarylsulfonate, while the second component of the present high performance detergent surfactant system comprises from ca. 8 to 15% by weight, preferably approx. 10% by weight of a soap which is a water-soluble salt of a higher fatty acid or resin. By using the present surfactant system, a high performance detergent can be prepared which contains completely biodegradable materials.

Suitable synthetic anionic detergents for use as the first component of the detergent system of the present material include the higher alkyl monocarbon aromatic sulfonates such as the higher linear alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group, i.e. night, all of the decyl, un = decyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexa-decylbenzenesulfonate as well as the higher linear alkyl toluene, xylene and phenol sulfonates, alkylnaphthalenesulfonate, ammonium diamylnaphthalene and sulfonate = sulfonate

The preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, di- and triethanol = amine), the alkali metal (such as sodium and potassium) and the alkaline earth metal (such as calcium and magnesium) salts of the higher linear alkylbenzene sulfonates. , in particular the alkali metal salts of the higher linear al = f benzene sulfonates. The salt in question will conveniently be selected depending on the particular composition and the men therein.

The most preferred sodium alkylbenzenesulfonate surfactant (LAS) for use in the detergent of the invention has a straight-chain alkyl group having an average length of approx. 11 to 13 carbon atoms. The alkyl benzene sulfonate preferably has a high content of 3- (or higher) phenyl isomers and a correspondingly low content (somewhat peaks 50%) of 2- (or lower) phenyl isomers. Stated otherwise, the benzene ring is, to a large extent, preferably associated with the 3 or higher (e.g., 4, 5, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at 2 -or the 1 position, is correspondingly low. One such suitable surfactant type is described in U.S.A. U.S. Patent No. 3,320,174.

The second component of the detergent surfactant system belongs to the class of compounds known as soaps, such as the water-soluble salts of higher fatty acids or resin acids derived from fats, oils and waxes of animal, vegetable or marine origin. The soaps used are usually alkali metal salts, e.g., sodium and potassium salts of mixed higher fatty acids, such as the mixtures of acids obtained from natural, animal and vegetable fats and oils. Such soaps will generally comprise a large amount of saturated fatty acid soaps with chain lengths of 10 to 18 carbon atoms. The most preferred mixtures are obtained by mixing tallow and coconut oil fatty acids or by preparing soap from mixed portions of tallow and coconut oil. For purposes of the invention, such soaps will usually come from more than 50% sebum and preferably from 80 to 100% sebum, the remainder usually being coconut oil or substitute oil therefor. Other solubilizing cations may be used to prepare the desired soaps, such as from ammonia, triethanolamine, trimethylamine and other lower amines and alkanolamines, the soap cation being generally selected so as to be compatible with the sulfonate surfactant cation.

The citrate component of the detergent comprising from 15 to 25% by weight and in particular 20% by weight of the present agent can be added as citric acid or as a water-soluble citrate such as an alkali metal citrate, for example sodium, potassium or lithium citrate etc. , or ammonium citrate, amine citrate or alkanolamine citrate, etc. The citrate compounds can be used in anhydrous form in the form of hydrates, of which the mono-, di-trihydrate salts or mixtures thereof are suitable. The preferred citrate for use in the material of the invention is sodium citrate, with the preferred sodium citrate being the dihydrate.

In addition to the citrate component, the detergent contains approx. 45 to 75% by weight and most conveniently approx. 50% by weight of a mixture of an alkali metal silicate and an alkali metal carbonate in a weight ratio of silicate and carbonate of 1: 0.25-4, preferably a weight ratio of 1: 1-2 and most conveniently a weight ratio of 1: 1 .5. It is within this range and weight ratio that the combined silicate / carbonate mixture results in the exceptionally good building properties. characterizing the material of the invention so that the high performance detergent of the invention can function substantially as well as the known high performance phosphate and nitrilo-built detergents.

The alkali metal silicate used in the builder mixture of the material of the invention has an M 2 O: SiO 2: 1 to 1: 4, where M is an alkali metal selected from sodium, lithium and potassium, with sodium being preferred. The preferred weight ratio of MgO to SiO2 is 1.6: 1 to 1: 3, with 1: 2 being the most preferred. The silicate can be added in powder or granular form or in the form of a liquid aqueous solution and it can be added to the mixing container mixture used for spray drying the product, or it can be added to the spray dried detergent grains, or a portion can be added to the mixing container mixture and some are added.

The second component of the builder mixture for use in the detergent of the invention comprises an alkali metal carbonate, especially sodium = carbonate, which may come from any suitable source of this material, including dense and light soda. As stated above, the alkali metal silicate and alkali metal carbonate are present in a range of about 45 to 75% by weight and within a relative ratio of silicate to carbonate of from 1: 0.25-4. It is within this range that the material according to the invention achieves excellent cleaning and whitening properties.

148120 7

In addition to the primary components of the detergent of the invention, other adjuvants may be present in the detergent product to give it additional properties, either functional or aesthetic. Examples of such adjuvants include bactericides, e.g. tribromosalicylanilide, fungicides, dyes, pigments (water-dispersible), preservatives, ultraviolet light absorbers, textile softeners, additional builders in very small quantities and perfumes. Such materials will, of course, be selected for the desired properties of the finished product and must be compatible with the other ingredients of the product.

Although a single optical brightener can be used in the detergent of the invention, it is generally desirable to use a mixture thereof so as to obtain good clearing effects on cotton, nylon, polyesters and mixtures of such materials, and preserving the clearing effect. even in the presence of chlorine bleaches.

A good description of the different types of optical brighteners suitable for achieving these results is given in the article Optical Brighteners and Their Evaluation by Per S.Stensby and in a reprint of articles published in Soap and Chemical Specialties in April, May, July, August and September 1967, in particular on pages 3-5 thereof.

The cotton clearing agents are frequently referred to as "CC / DAS brighteners" and are derived from the reaction product of cyanuric acid chloride and the disodium salt of diaminostilebenz disulphonic acid. The polyamide clarifiers are generally either amino-coumarin or diphenylpyrasoline derivatives, and polyester clarifiers, which are also useful for polyamides, may be naphthotriazolyl starches. The clarifiers are usually present in the form of soluble salts, but they can also be added in the form of acids The cotton clearing agents usually comprise a large part of the clearing system and are generally accompanied by a small amount of an amide polyester clearing agent. Among the clearing agents used in the present systems are: "Calcofluor White ALF" (American Cyan amide), "ALF-N" (American Cyanamid), "SOF A-2001" (CIBA), 148120 8 "CWD" (Hilton-Davis), "Phorwite RKH" (Verona), "CSL" powder, "acid "(American Cyanamid)," CSL ", liquid monoethanolamine salt (American Cyanamid)," FB 766 "(Verona)," Blancophor PD "(GAF)," UNPA "(Geigy)," Tinopal RBS "(Geigy) and 1 , RBS 200 ”(Geigy).

It is an advantage of the detergent of the invention that the use of a soap-based material results in a low-foaming detergent which does not require any anti-repellant agents which are normally used in detergents containing no soap. It has been found that by the addition of a water-soluble soap of a higher fatty acid or a mixture of such soaps to a detergent, the foam can be adjusted as desired so that little or no foam is formed while maintaining a high level of purification.

Control of the foam level is important when considering the operation of an automatic washing machine. Most automatic household washing machines are top-loading types, which have a washing capacity of 57 to 68 liters. Due to the agitator design of these machines and the fact that the washrooms are open at the top, foam formed by the washing up does not interfere with the washing of the laundry, which could be the case in washing machines with horizontal axis or front filling. Such machines usually have a smaller water capacity which is on average from 26.5 to 34 liters, and the greater ratio of laundry to washing water usually allows the use of a smaller amount of detergent to produce the same degree of washing, provided that a foam lock does not prevent good contact between detergent solution and laundry. Although the foam can help cause particulate dirt to float away in an automatic top-loading washer, and although housewives in the past have associated good foaming with good cleaning performance, in recent years it has been considered desirable to limit the amount of foam formed using high performance detergents.

The detergent according to the invention will now be described in more detail in the following examples, in which all parts are weight percentages and temperatures are ° C. It is to be understood that the examples are given for the purpose of illustrating the invention only and should not in any way be construed as limiting it.

Example 1

A detergent based on soap - synthetic surfactant and containing no phosphate is specially formulated for use in low temperature washing, i.e. 20 ° C. This soap-based detergent does not require the use of a core soap dispersant surfactant or antigen scrubber.

14.0% linear alkylarylsulfonate 10.0% Colgate-Palmolive soap shavings (80% sebum, 20% coconut material) 20.0% G.D. sodium silicate (Philadelphia Quartz Co.) 30.0% sodium carbonate (Baker Co.) 20.0% sodium citrate (Baker Co.) 0.9% optical brightener 5.1% humidity

When using New Jersey tap water containing approx. 100 ppm, expressed as calcium carbonate, of magnesium and calcium hardness, the detergent according to Example 1 is evaluated in comparison with a commercially available phosphate-built detergent. Five fabrics are washed five times in a tergot cmeter laboratory washing machine at 20 ° C and 50 ° C and at a concentration of the detergent of 0.15% to show initial cleaning and any yellowing due to detergent soap. Each of the fabrics is stained with Piscatawayler before washing.

Reflectance figures for the washed fabrics are read on a Gardner Color-Gard Reflectometer after the first and fifth washings. The results are expressed as Rd values (higher values = better reflectance and whiteness) and b values (indicating yellowness, lower b numbers = less yellowing) as shown in Table I.

Table I

First wash 100 ppm, concentration 0.15%, sample textile at 20 ° C.

Phosphate-containing detergent Example 1_ for comparison_

Dirty Clean Dirty Clean area_ area_ area_ area_

Textile Rd b Rd b Rd b Rd b

Dac / Bom. 46.4 -1.1 86.0 -2.0 43.7 -1.4 85.2 -2.1

Spun / Dac. 57.7 / 2.5 83.9 / 5.4 42.6 / 1.2 85.2 -2.9 'Spun / Nylon 76.1 / 1.0 85.5 / 1.2 77.2 / 1.5 85.6 -1.2

Cotton 40.4 -1.5 87.5 -2.7 41.0 -2.7 87.5 -3.9

Wash / Wear 56.1 / 0.9 86.4 / 0.6 54.7 / 0.4 86.6 0.0 5th Wash of test textile pieces with added dirt at 20 ° C.

Phosphate-containing detergent _ Example 1 _ for comparison_

Dirty Clean Dirty Clean area_ area_ area_ area_

Textile Rd_ _b_ Rd_ _b_ Rd_ b Rd _b_

Dac / Bom. 64.2 -1.9 85.7 -2.5 51.5 -1.9 85.4 -2.5

Spun / Dac. 72.0 / 2.7 83.7 / 3.2 45.1 / 0.7 80.1 / 2.1

Spun / Nylon 84.8 -1.5 86.4 -2.3 85.2 -0.7 86.4 -1.1

Cotton 56.4 -5.1 88.5 -5.5 55.7 -4.1 86.7 -5.1

Wash / Wear 68.4 -0.3 86.6 -1.0 62.7 -0.6 86.9 -1.2 1st wash 100 ppm, concentration 0.15%, sample textile at 50 ° C.

Phosphate-containing detergent _ Example 1_

Dirty Clean Dirty Clean area area_ area_ area_

Textile Rd b Rd b Rd b Rd b

Dac / Bom. 46.0 -1.3 84.8 -1.8 38.1 -1.5 84.7 -2.3

Spun / Dac. 57.7 / 2.5 83.4 / 3.4 35.0 / 1.0 79.6 / 2.7

Spun / Nylon 77.5 -1.5 85.9 -1.8 77.4 -0.1 85.9 -0.3

Cotton 46.1 -2.3 87.7 -3.7 39.4 -2.9 87.7 -4.6

Wash / Wear 54.7 / 0.9 87.0 / 0.8 52.8 / 0.5 86.0 / 0.4 cont.

148120 11

Table I, cont.

o 5th wash of test textile pieces with added dirt at 50 ° C.

Phosphate-containing detergent - Example 1 for comparison

Dirty Clean Dirty Clean area_ area_ area_ area_

Textile Rd _b_ Rd b Rd _b_ Rd _b_

Dac / Bom. 59.6 -2.1 85.2 -2.5 46.0 -2.1 83.5 -2.7

Spun / Dac. 68.5 / 2.5 83.4 2.9 36.8 0.2 70.3 1.1

Spun / Nylon 84.9 -3.6 86.5 -4.0 85.0 -2.0 86.5 -2.3

Cotton 53.4 -4.9 88.1 -6.2 54.1 -6.2 88.3 -6.9

Wash / Wear 68.0 -0.6 86.6 -1.3 62.2 0.8 85.6 -1.5

The test results show that: 1. at both washing temperatures, the detergent improves the Rd values for contaminated area and no build-up of gullibility is observed on further washings; 2. the results of the 5th wash show that the washing temperatures do not seriously affect the significant superiority of the detergent of Example 1 relative to the phosphate-built detergent in connection with Dacron / cotton, spun-Dacron and "wash and wear" fabrics. The cleaning effect of the present detergent and phosphate-built detergents is substantially equivalent to washing at both 20 ° C and 50 ° C in the case of spun nylon and cotton.

Example 2 The following detergent is prepared and tested according to the procedure of Example 1: 12% triethanolamine linear alkylbenzene sulfonate (average chain length 11.5 carbon atoms) 14% soap (85% tallow, 15% coconut material) 25% sodium citrate dihydrate 22% sodium silicate (Na 2 O / SiO 2 = 1: 2.5) 27% sodium carbonate 12

The above material is equal to or superior to the comparable phosphate detergents in cold (20 ° C) and hot (50 ° C) washings.

Example 3

A detergent as shown in Table 2 is tested in accordance with the procedure of Example 1 to determine the cleansing properties and anti-yellowing properties. The detergent functions satisfactorily both in terms of purity and anti-yellowing properties, even after a 5th wash.

Table 2

Component Guard Parts

Linear potassium alkyl benzene sulfonate having 16-18 carbon atoms 14

Sodium soap (70% tallow, 30% coconut material) 10

Sodium citrate (dihydrate) 20

Sodium silicate _n (Na2O: SiO2 = 1.6: 1) J0

Sodium carbonate 30

Example 4

Example 1 is repeated except that the sodium citrate dihydrate is replaced by potassium citrate. This detergent functions adequately and has approximately the same cleaning properties as the detergent of Example 1.

Claims (4)

Example 5 The detergent composition of Example 1 is repeated except that the sodium carbonate is replaced by potassium and lithium carbohydrate in equal amounts with the same results. Claims. Detergent containing no phosphate or nitrogen-containing builders, characterized in that it consists essentially of (a) about 12 to 16% by weight of a linear alkylarylsulfonate having an average alkyl chain length of approx. 10 to 16 carbon atoms, (b) approx. 8 to 15% by weight of soap selected from water-soluble salts of higher fatty or resin acids; 15 to 25% by weight of citric acid or a water-soluble salt of citric acid; and (d) approx. 45 to 75% by weight of a builder salt mixture of alkali metal silicates and alkali metal carbonates where the weight ratio of silicate to carbonate is from 1: 0.25 to 1: 4.0. Detergent according to Claim 1, characterized in that (a) is a linear alkylbenzene sulfonate having an average alkyl chain length of approx. 11 to 13 carbon atoms, (b) the soap is selected from water-soluble salts of fatty acid having a chain length of from 10 to 18 carbon atoms, (c) the water-soluble salt of citric acid is sodium salt, and (d) the builder salt mixture is a mixture of sodium = silicate and sodium carbonate. Detergent according to claim 1, characterized in that the soap consists essentially of 80% salts of sebum fatty acid and 20% salts of coconut oil fatty acid and that the water-soluble salt of citric acid is sodium citrate dihydrate. Detergent according to claim 1, characterized in that it further contains less than 10% of optical brighteners, other auxiliaries, moisture and mixtures thereof.