RU2177985C1 - Synthetic cleansing agent for washing and whitening at low temperatures - Google Patents

Abstract

FIELD: synthetic cleansing agents for washing of fabrics. SUBSTANCE: cleansing agent contains, mas. %: sodium alkylbenzenesulfonate or its mixture with sodium alkylsulfonate or sodium salts with high fat acids, 8-13; polyoxyethyleneglycol ethers of stearic acid, 0.01-5, and/or oxyethylated of fat alcohols, 0.01-5; sodium tripolyphosphate, 21-24; sodium colored granulated tripolyphosphate RHODIA-PHOS, 1-4; sodium salt of copolymer of acrylic or maleic acids, 1-2; sodium ethylenediaminetetraacetate, 0.5; sodium salt of nitrilotriacetic acid, 1; sodiumcarboxymethylcellulose, 0.5; sodium soluble silicate, 4; ferment preparation "Totalaza", 1.5; optic whitener, 0.25; soda ash, 5-10; sodium percarbonate, 12; tetraacetylethylenediamine, 2-4; perfume, 0.2; water, 8; and sodium sulfate, the balance. Cleansing agent may contain, if necessary, mas. %: oxyethylated alkylfenols, 0-2; antiresorbed additive "DAR", 0-2; polyvinylpyrrolidone, 0-0.5; and polymethylsiloxane foam suppressor, 0-0.2. EFFECT: high washing and whitening ability at reduced washing temperatures; softening effect and renewal of articles appearance; reduced harmful action on metal parts of washing machines. 2 dwg, 1 tbl, 10 ex

Description

 The invention relates to the production of powdered synthetic detergents used for washing textiles.

 The development trend of synthetic detergent formulations is the development of compositions combining high detergency with respect to various gnoseology contaminants and low temperature composition with whitening ability. The beneficial effect of the composition on the fabric is also desirable, consisting in the absence of inlay, softening effect, increased brightness of dyed fabrics and the absence of the formation of spools formed during the wear of the products, and the protection of the elements of the washing machine from corrosion and scale formation.

A number of compositions are known to one degree or another meeting these requirements. So, for example, the known CMC formulation containing fatty alcohol sulfates, 40 wt. %; sodium alkylbenzenesulfonate - up to 10 wt. %; ethoxylated fatty alcohols, enzymes - up to 5 wt. %; complexing agents, including 1-hydroxyethane-1,1-diphosphonic acid - up to 1 wt. %; sodium perborate, antifoam - up to 5 wt. % - see German application 196 11013, C 11 D 1/83, C 11 D 3/306. The disadvantages of this composition include a low washing ability (~ 100%) with respect to pollution, low bleaching ability (~ 80%), achieved at high (> 75 ^o C) temperature. The composition does not provide a softening effect on the fabric. In addition, the composition of CMC determines its production by dry mixing followed by extrusion and granulation at pressures up to 200 atm. Most existing CMC plants have a technology based on spray drying of an aqueous solution of CMC composition in a tower by the counterflow method, which allows one to obtain a granular commercial product with a specific gravity of 400-500 g / dm ³ intended for the vast majority of household automatic washing machines manufactured in the world. The disadvantages of this formulation should also include its high cost associated with the use of a large number of expensive components. An estimate in December 2000 prices showed that the price of this composition on the market could be 100-150 rubles. / kg

 A detergent containing sorbitan monostearate or monopalmitate, anionic surfactants, oxygen-containing bleaches, protease and amylase class enzymes and excipients is described. See application EPO 0861885, C 11 D 3/39, C 11 D 1/83, claimed. 02/27/97, publ. 09/02/98. The disadvantages of this composition include a low washing ability (~ 100%), inability to remove grease and renew the appearance of products, as well as the lack of conditioning effect.

Higher results are achieved when synthetic detergents containing up to 60 wt.% Are used for washing textiles. % inorganic filler (zeolites, carbonates) anionic surfactants of the formula
RCH (OH) CHR-NR ² -YCOOM,
where R and R = H, aryl, alkyl or alkenyl; R ² = H or alkyl; Y = hydroxy or alkoxy substituted alkylene; M = N, an alkaline or alkaline earth metal ion, up to 30% nonionic surfactants with alkylene substituents, an oxygen-containing bleach, a bleaching activator and a protease class enzyme (up to 4 wt.%) - see German application 19624701, C 11 D 3/02. The washing ability of this composition according to GOST is 96, the whitening ability is 97.

The disadvantages of this formulation are
1. Low washing ability.

 2. Inability to remove fatty and starchy contaminants due to the absence of special enzymes in the composition.

 3. Lack of conditioning effect.

 4. The use of expensive and not commercially available substances as surfactants.

 5. Difficulty in handling thermally unstable and oxidizable non-ionic surfactants containing alkylene substituents at the quaternary nitrogen atom.

The best results are achieved using the composition — see US Pat. No. 4,806,253, MKI ⁴ D 06 M 11/00, containing a mixture of surfactants, including alkylbenzenesulfonate, ethoxylated alcohols, quaternary ammonium bases, animal-based sodium soaps; as well as antiresorbents, including sodium silicate, carboxymethyl cellulose and a copolymer of acrylic and maleic acids, a mixture of complexing agents, including sodium tripolyphosphate, sodium ethylene diamine tetra acetate and sulfonated zinc phthalocyanan; useful additives, including sodium perborate, enzymes, alkylamines, optical brighteners, antifoam and perfume, softening additive - smectite clay, filler - sodium sulfate.

This product is available in the form of granules. According to the description, the composition contains, by weight. %:
Anionic surfactants - 1 - 10
Cationic surfactants - 1 - 5
Nonionic surfactants - 1 - 5
Smectite clay - 2 - 7
Other components - 10 - 80
As a working option, the following composition, wt. %:
Anionic surfactants (alkylbenzenesulfonate) - 6.2
Cationic surfactants (dioctylmethylammonium chloride) - 1.6
Nonionic surfactants, including ethoxylated fatty alcohol - 1.0
Sodium Tripolyphosphate - 24.0
Smectite clay - 2.4
Sodium perborate - 20.0
Sodium Silicate - 8.0
Maleic Acrylic Acid Copolymer - 1.7
Alkylamine (methylamine) - 3.8
Carboxymethyl cellulose - 0.4
Enzymes (protease) - 0.5
Optical brighteners - 0.23
Ethylene diamine tetraacetate - 0.2
Sulfated Zinc Phthalocyanine - 2.5 • 10 ^-5
Perfumery fragrance - 0.5
Defoamer (polymethylsiloxane) - 2.7
Sodium Sulfate - 22.0
Water - Else
Due to the lack of specific data in the patent on washing, bleaching ability and the presence of a conditioning effect, we developed a sample of the above composition in laboratory conditions and studied the whole range of its consumer properties.

It was found that the washing ability of the composition reaches only 95% at 60 ^o C according to GOST 22567.15-96, which is understandable in terms of low content of surfactants (8.8 wt.%), As well as significant (up to 50%) adsorption of nonionic Surfactants on smectite clay (see Art. "Use of heterogeneous components in detergents" - Seifen, Ole, Fette, Wachse, 1988, 15). During adsorption, nonionic surfactants are removed from the zone of active action on the tissue, which reduces the effectiveness of the composition as a whole.

The whitening effect according to GOST 22567 at 60 ^o C is 75%, at 90 ^o C - 85%. The emollient effect was evaluated according to RD 6-40-00209645.2.1-92 "Aids for processing products after washing. Means for rinsing textiles. Methods for determining the emollient effect" and amounted to 10 points on cotton and 20 points on viscose.

Thus, the disadvantages of the composition include the following:
1. Low washing ability.

 2. Low whitening ability.

 3. Low softening effect.

 4. Strong unpleasant odor due to the presence of alkylamine.

 5. The use of expensive and not commercially available quaternary ammonium bases as surfactants.

 6. The use of smectite clay as a softening agent, since it is also not available in marketable form on the Russian market.

 However, despite these drawbacks, the described detergent is closest to the object of the invention and is selected as a prototype.

 The technical result of the claimed invention is to increase the effectiveness of a detergent with a whitening effect, remove all kinds of contaminants, giving the fabric extra softness, reduce the temperature of the wash, as well as reduce the harmful effects on the metal parts of washing machines.

 The goal is achieved in that the synthetic detergent for washing and bleaching at low temperatures contains a synergistic mixture of anionic and nonionic surfactants, antisorbents - soluble sodium silicate and sodium carboxymethyl cellulose, complexing agents - sodium tripolyphosphate, sodium ethylene diamine tetraacetate (trilon nitrate sodium trisulfate) acids (Trilon A), useful additives - sodium salt of a copolymer of acrylic and maleic acids (commercial product Sokalan SP5 from BASF ), enzymes, optical brightener and perfume, filler - sodium sulfate - and water, moreover, a mixture of sodium alkylbenzenesulfonate or its mixture with sodium alkyl sulfonate or sodium fatty acid salts with polyoxyethylene glycol stearic acid esters and / or ethoxylated fatty acids is used as surfactants alcohols and, if necessary, with ethoxylated alkyl phenols.

 It should be noted that all ratios of surfactants both between groups and within the latter are optimal, because they are selected on the basis of a mathematical model obtained as a result of detailed studies of the effect of the composition of surfactants on the washing ability of the product. As enzymes, the enzyme preparation “Totalase” is used, containing protease, amylase, lipolase and cellulase, which ensures the removal of all types of contaminants, freshens tissue and prevents the formation of spools. Additionally, the detergent contains colored granular sodium tripolyphosphate RHODIA-PHOS C90-S BLUE TX (blue), sodium percarbonate, whitening activator tetraacetylethylenediamine and soda ash as useful additives. If necessary, the product may contain a DAR antiresorption additive based on dicarboxylic and monocarboxylic acids, polyvinylpyrrolidone, carboxymethyl cellulose and sodium sulfate (TU U 05766379-002-96) and useful additives - polymethylsiloxane antifoam and polyvinylpyrrolidone, which provides an increased synergistic effect properties of the drug as a whole.

Thus, the claimed synthetic detergent contains, by weight. %:
Sodium alkylbenzenesulfonate or a mixture thereof with sodium alkyl sulfonate or sodium salts of higher fatty acids - 8.0 - 13.0
Stearic acid polyoxyethylene glycol esters and / or - 0.01 - 5.0
Oxyethylated fatty alcohols - 0.01 - 5.0
Oxyethylated alkyl phenols - 0 - 2.0
Sodium tripolyphosphate - 21.0 - 24.0
Colored Granular Sodium Tripolyphosphate RHODIA-PHOS - 1.0 - 4.0
Sodium salt of a copolymer of acrylic and maleic acids - 1.0 - 2.0
Ethylene diamine tetraacetate - 0.5
Sodium salt of nitrilotriacetic acid - 1.0
Sodium carboxymethyl cellulose - 0.5
Antisorption additive "DAR" - 0 - 2.0
Soluble sodium silicate (in terms of the mass fraction of SiO ₂ ) - 4.0
Enzyme preparation "Totalase" containing protease, amylase, lipolase and cellulase - 1.5
Optical Brightener - 0.25
Soda ash - 5.0 - 10.0
Sodium Percarbonate - 12.0
Tetraacetylethylenediamine - 2.0 - 4.0
Polyvinylpyrrolidone - 0 - 0.5
Perfumery fragrance - 0.2
Polymethylsiloxane defoamer - 0 - 0.2
Water - 8.0
Sodium Sulfate - Else
The invention consists in the following. High washing ability is achieved by the optimal detergent formula. Special experiments have established that increasing the total content of surfactants to 18 wt. % leads to an increase in washing ability. In the future, the dependence "washing ability - surfactant content" reaches saturation and an increase in the mass fraction of surfactants is impractical both from a technical and economic point of view. An illustration of this is shown in FIG. 1. The sixth order response equation describing the dependence at a confidence level of R = 0.99 is also given there.

где R= С₁₀-С₁₇ либо в смеси с алкилсульфонатом натрия формулы R-SO₃Na, где R= С₁₁-С₁₈ и натриевыми мылами на основе жирных кислот.As the anionic component, either pure alkylbenzenesulfonate of the formula can be used

where R = C ₁₀ -C ₁₇ or in a mixture with sodium alkyl sulfonate of the formula R-SO ₃ Na, where R = C ₁₁ -C ₁₈ and sodium soaps based on fatty acids.

As a nonionic component, it is advisable to use a mixture of ethoxylated fatty alcohols, polyoxyethylene glycol esters of stearic acid and ethoxylated monoalkylphenols C ₆ H ₄ O (C ₂ H ₄ O) _n H, where n = 10-12.

 Non-ionic surfactants, in addition to providing a certain proportion of the washing ability of the composition, are responsible for the softening effect on the tissue.

 In FIG. 2 shows the dependence of the softening effect of the composition on the content of the sum of nonionic surfactants. It was found that the optimal value of this value is not less than 7 wt. % It should be noted that in the presence of a system of oxygen-containing bleaches, the softening effect of nonionic surfactants is 1.5-1.7 times less than in the absence of them. However, the given values are quite sufficient, since the softening effect is additional for the claimed CMC formulation.

The selected synergistic mixture of surfactants and their ratio are the result of special research work and are described by a mathematical model of five sixth order response equations:
Y = 88.007 + 5.102x ₁ -0.7954x ₁ ² + 0.0276x ₁ ³ + 0.0031x ₁ ⁴ -0.0002x ₁ ⁵ -5е10 ^-6 x ₁ ⁶
Y = 99.034 + 7.2776x ₂ -4.05539x ₂ ² + 1.0981x ₂ ³ -0.1608x ₂ ⁴ + 0.0119x ₂ ⁵ -0.0003x ₂ ⁶
Y = 94.174 + 15.152x ₃ -11.259x ₃ ² + 4.3714x ₃ ³ -0.9018x ₃ ⁴ + 0.0924x ₃ ⁵ -0.0037x ₃ ⁶
Y = 92.009-0.5037x ₄ + 0.9502x ₄ ² -0.0713x ₄ ³ -0.0225x ₄ ⁴ + 0.0042x ₄ ⁵ -0.0002x ₄ ⁶
Y = 99.003 + 1.2569x ₅ + 1.2033x ₅ ² -0.5589x ₅ ³ + 0.0828x ₅ ⁴ -0.0051x ₅ ⁵ + 0.0001x ₅ ⁶
where Y is the washing ability of the model composition
x ₁ - total content of surfactants
x ₂ is the ratio of "sodium (I) alkylbenzenesulfonate: sodium (II) alkylsulfonate"
x ₃ - the ratio of "sodium alkylbenzenesulfonate: soap (III)"
x ₄ - ratio "sodium alkylbenzenesulfonate: ethoxylated alkyl phenol (IY)"
x ₅ is the ratio of sodium alkylbenzenesulfonate: ethoxylated fatty alcohol (Y).

 It is well known that the properties of surfactants for any indicator that depends on surface tension is an additive quantity. This circumstance allows us to build a series of optimal ratios of surfactants in CMC based on the analysis of differential dependencies. So, if the content of sodium alkylbenzenesulfonate in the composition is taken as a unit, the series of maximum values of the mass ratios of surfactants in CMC obtained by solving the above system of equations in differential form, taking into account the detergency data of polyoxyethylene glycol esters of stearic acid (stearox YI), will look as follows way: I: II: III: IY: YI: Y = 1: 0.5: 0.3: 0.25: 0.25: 0.17.

 As can be seen from the above formulations, it fully complies with these requirements.

 The high washing ability of the proposed composition and the soft effect on the fabric is provided, in addition to surfactants, by the composition of complexing agents, antiresorbents, useful additives and fillers. The base of synthetic detergents worked out in the process of research (without surfactants) has a washing ability in relation to the standard of 92%.

 The high content of complexing agents prevents the formation of scale on the metal parts of washing machines (especially heating elements) and significantly increases their service life. So, when using the inventive system in laboratory washing of samples (250 washes), no formation of scale and corrosion was detected.

 The use of colored granular sodium tripolyphosphate brand RHODIA PHOS (blue stilbene) increases the washing ability of CMC by 5-10%.

 Thanks to the integrated enzyme system, the proposed CMC formulation removes stains of protein, vegetable, fat and starch composition well, and the presence of cellulase updates the appearance of products and prevents the formation of pellets.

 The presence of sodium percarbonate - tetraacetylethylenediamine in the formulation of the system provides a mild whitening effect at low temperatures.

The technical result of this invention is the complex interaction of surfactants, complexing agents and useful additives, providing high washing and bleaching effect on the fabric at low (from 40 ^o C) temperatures, removing all types of stains, updating the appearance of products with a noticeable conditioning effect.

 Comparison of the proposed synthetic detergent with known compositions of a similar purpose shows that the use of a synergistic system of surfactants in combination with the components of the CMC base can achieve a washing ability with respect to the generally accepted standard based on sodium alkylbenzenesulfonate, defined in accordance with GOST 22567.15-95 - 130-135 %

The use of an oxygen-containing bleaching system of sodium percarbonate - tetraacetylethylenediamine in combination with other CMC components allows to achieve a bleaching ability of 120-125% according to GOST 22567.11-82. It should be noted that bleaching fabrics, like washing, is possible at temperatures from 40 ^o C.

 The use of stearic acid polyoxyethylene glycol esters, hydroxyethylated fatty alcohols and hydroxyethylated monoalkyl phenols as nonionic surfactants makes it possible to achieve a noticeable conditioning effect (40-60 points according to RD 6-40-00209645.2.1-92) due to the adsorption of nonionic surfactants on the surface of the tissue (0.110 -0.145% based on the weight of the treated tissue).

 The presence of polyvinylpyrrolidone in the formulation preserves the color of the products, and in combination with nonionic surfactants and cellulase improves the appearance of the products and prevents the formation of pellets.

 Thus, the proposed formulation for the achieved effect exceeds the achieved level of technology.

 The inventive synthetic detergent obtained on existing technological equipment by spray drying.

 The proposed powdered synthetic detergent is characterized by high consumer properties, technologically, economically, both in production and in application. The composition is based on available raw materials.

 The invention is illustrated by examples of its implementation.

 Example 1

 In laboratory conditions, a sample was prepared according to the recipe selected as a prototype. The test results according to standard methods are shown in the table.

 Example 2

A sample of the proposed detergent contains, by weight. %:
1. Sodium alkylbenzenesulfonate - 8.0
2. Sodium alkyl sulfonate - 4.0
3. Polyoxyethylene glycol esters of stearic acid - 5.0
4. Oxyethylated fatty alcohols - 1.0
5. Sodium tripolyphosphate - 21.0
6. Sodium tripolyphosphate colored - 4.0
7. Sodium salt of a copolymer of acrylic and maleic acids - 2.0
8. Ethylene diamine tetraacetate (trilon B) sodium - 0.5
9. Sodium salt of nitrilotriacetic acid - 1.0
10. Sodium carboxymethyl cellulose - 0.5
11. Soluble sodium silicate (in terms of the mass fraction of SiO ₂ ) - 4.0
12. The enzyme preparation "Totalase" - 1.5
13. Optical brightener - 0.25
14. Soda ash - 10.0
15. Sodium percarbonate - 12.0
16. Tetraacetylethylenediamine - 4.0
17. Polyvinylpyrrolidone - 0.5
18. Perfumery fragrance - 0.2
19. Polymethylsiloxane defoamer - 0.2
20. Water - 8.0
21. Sodium Sulfate - Rest
Synthetic detergent was obtained and tested analogously to example 1. The test results are shown in the table.

 Example 3

A detergent similar to example 2 contains, by weight. %:
Sodium Alkylbenzenesulfonate - 13.0
Stearic acid polyoxyethylene glycol esters - 5.0
and does not contain oxyethylated fatty alcohols and sodium alkyl sulfonate. In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 4

A detergent similar to example 2 contains, by weight. %:
Sodium alkylbenzenesulfonate - 11.0
Oxyethylated Fatty Alcohols - 5.0
Sodium soap (sodium salts of higher fatty acids) - 1.0
Oxyethylated Monoalkylphenols - 1.0
and does not contain stearic acid polyoxyethylene glycol esters. In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 5

A detergent similar to example 2 contains, by weight. %:
Sodium alkylbenzenesulfonate - 11.0
Stearic acid polyoxyethylene glycol esters - 1.0
Oxyethylated Fatty Alcohols - 2.0
Oxyethylated Monoalkylphenols - 2.0
Sodium soap - 1,0
In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 6

A detergent similar to example 2 contains, by weight. %:
Sodium Tripolyphosphate - 24.0
Sodium Tripolyphosphate Colored - 1.0
In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 7

A detergent similar to example 2 contains, by weight. %:
Acrylic and maleic acid copolymer sodium salt - 1.0
In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 8

A detergent similar to example 2 contains, by weight. %:
Soda ash - 5.0
In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 9

A detergent similar to example 2 contains, by weight. %:
Tetraacetylethylenediamine - 2.0
In other components, the composition is identical to example 2. The test results are shown in the table.

 Example 10

A detergent similar to example 2 contains, by weight. %:
Antisorption additive "DAR" - 2.0
and does not contain polyvinylpyrrolidone. In other components, the composition is identical to example 2. The test results are shown in the table.

 When using a detergent containing components in the declared ranges of values (other than in the presented examples), the indicated technical result is also achieved.

 Note: the arithmetic mean of four parallel measurements was taken as the result.

 The proposed synthetic detergent has high consumer properties (high washing ability, bleaching ability, softening effect, improving the appearance of products, the absence of scale formation on the metal parts of washing machines), based on available raw materials, technologically.

 The positive effect is improving the quality of products without capital costs for installing new equipment and changing the scheme of material production flows.

 According to the proposed technology, in 2000, 100 tons of product were produced according to the recipe declared by CMC. The product is recommended for production.

Claims (1)

Synthetic detergent for washing and bleaching at low temperatures, containing a mixture of surfactants, antiresorbents - soluble sodium silicate and sodium carboxymethyl cellulose, complexing agents - sodium tripolyphosphate, sodium ethylenediaminetetraacetate (Trilon B) and sodium salt of nitrilotriacetic acid, nitric acid trisole salt, and maleic acids, enzymes, optical brightener and perfume perfume, filler - sodium sulfate and water, characterized in that in quality surfactants use a mixture of sodium alkylbenzenesulfonate or its mixture with sodium alkyl sulfonate or sodium salts of fatty acids with polyoxyethylene glycol esters of stearic acid and / or ethoxylated fatty alcohols and, if necessary, with ethoxylated alkyl phenols, the enzyme preparation “Totalaza” is used as enzymes amylase, lipolase and cellulase, and additionally contains as useful additives - colored granular sodium tripolyphosphate RHODIA-PHOS, p sodium bicarbonate, tetraacetylethylenediamine and soda ash and optionally additionally contains an antiresorbent - DAR antiresorption additive and useful additives - polyvinylpyrrolidone and polymethylsiloxane antifoam in the following ratio of incoming components, wt. %:
Sodium alkylbenzenesulfonate or a mixture thereof with sodium alkyl sulfonate or sodium salts of higher fatty acids - 8.0-13.0
Stearic acid polyoxyethylene glycol esters and / or 0.01-5.0
Oxyethylated fatty alcohols - 0.01-5.0
Oxyethylated alkyl phenols - 0-2.0
Sodium tripolyphosphate - 21.0-24.0
Colored Granular Sodium Tripolyphosphate RHODIA-PHOS - 1.0-4.0
Sodium salt of a copolymer of acrylic and maleic acids - 1.0-2.0
Ethylene diamine tetraacetate - 0.5
Sodium salt of nitrilotriacetic acid - 1.0
Sodium carboxymethyl cellulose - 0.5
Antisorption additive "DAR" - 0-2.0
Soluble sodium silicate (in terms of the mass fraction of SiO ₂ ) - 4.0
Enzyme preparation "Totalase" containing protease, amylase, lipolase and cellulase - 1.5
Optical Brightener - 0.25
Soda ash - 5.0-10.0
Sodium Percarbonate - 12.0
Tetraacetylethylenediamine - 2.0-4.0
Polyvinylpyrrolidone - 0-0.5
Perfumery fragrance - 0.2
Polymethylsiloxane defoamer - 0-0,2
Water - 8.0
Sodium Sulfate - Else

Images