EA017243B1 - Builder detergent composition - Google Patents

Abstract

The present invention provides an effective builder composition comprising two precipitating builders which are (a) an alkali metal carbonate and (b) an alkali metal silicate; calcium carbonate; and a building enhancer. This building enhancer is a compound capable of precipitating magnesium ions from hard water selected from the group comprising alkali or alkaline earth metal oxides or hydroxides and alkali metal aluminate, zincate or titanate.

Description

FIELD OF THE INVENTION

The invention relates to a composition of a detergent component for use in the composition of a detergent effective in softening hard water, which simultaneously contains calcium and magnesium ions. The invention also relates to a solid detergent composition comprising the composition of the detergent component of the invention.

State of the art

The invention relates to a composition of a detergent component. Under the composition of the detergent component is understood to be a composition that softens hard water. By softening is meant a process in which the amount of dissolved alkaline earth metal ions, for example calcium and magnesium ions present in hard water, is reduced to a desired low concentration. It is believed that this low concentration of dissolved alkaline earth metal ions enhances the use of the surfactant used in cleaning surfaces, in particular fabrics, thereby providing consumers with more economical detergents of better quality. More specifically, this invention relates to washing clothes.

Soaps that are salts of alkali metals and fatty acids were used to wash laundry. When washing laundry with soaps, the washing efficiency is lower if washed in hard water, that is, in water containing a large amount of dissolved salts of calcium and magnesium. Ions of dissolved calcium and magnesium react very quickly with alkali metal cations (sodium or potassium) of soap, resulting in the formation of calcium and magnesium soap, which is insoluble in water, and therefore washing in hard water provides poor washing. With the advent of synthetic detergents, which are alkali metal salts and long chain synthetic acids derived from petroleum, similar problems persist. Common synthetic detergents are linear alkyl benzene sulfonates, alpha olefin sulfonates and primary alkyl sulfates, which belong to the class of anionic surfactants. Also known are surfactants of non-ionic, cationic, amphoteric and zwitterionic nature. When washing dirty laundry with synthetic surface-active substances in hard water, dirt is also poorly washed compared to washing in softer water.

In the detergent compositions, compounds were used that react predominantly with dissolved calcium and magnesium ions present in hard water, known as determinants. Well-known determinant components are alkali metal carbonates, silicates and phosphates and structural compounds such as zeolites. Sodium carbonate, also known as soda ash, is an inexpensive and widely used detergent component in detergent formulations. Detergents, such as phosphates and / or zeolites, are used in superior detergents because they have better detergents, but are more expensive. Constantly work was carried out to create increasingly efficient and fast systems of detergent components using cheaper materials. In addition, many believe that the use of phosphates in detergents causes eutrophication of rivers and other natural water systems. Thus, a lot of effort was spent on the development of faster and / or more efficient systems of detergent components using sodium carbonate as the main raw material.

Document I8 3957695 (1976, Beau Vgok. Co) discloses a detergent composition based on sodium carbonate as a detergent component, which also includes finely ground calcium carbonate, the specific surface area of which is from about 30 to 100 m ² / g, together with an active compound or a mixture of detergent compounds, which upon use does not form an insoluble calcium salt. The composition may also further include from about 5 to about 30% sodium silicate by weight of the composition.

I8 4049586 (1977, Rtoset & Sach. Co.) Describes an aerosol detergent, including in particular: (a) from about 0.5 to about 50 wt.% Particles of dry calcium carbonate as an additive with an average diameter of from about 0.01 up to about 0.50 microns; (B) from about 5 to about 70 wt.% A detergent component selected from the group consisting of alkali metal carbonates, bicarbonates and sesquicarbonates and mixtures thereof; (c) from about 5 to about 70 wt.% alkali metal pyrophosphate; and (6) from about 5 to about 40 wt.% a water-soluble detergent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof. The composition may also further include from about 5 to about 40% sodium silicate by weight of the composition.

Thus, at present, detergent compositions have been known and used for some time, including precipitating components such as sodium carbonate and sodium silicate, together with calcium carbonate.

The inventors of the present invention have found that the bonding provided by the compositions of the prior art did not occur as fast and complete as the bonding would have been desirable to provide better laundering of users' fabrics when they are washed in hard water.

The inventors of the present invention have found that when using two precipitating components

- 1 017243 nents, namely, alkali metal carbonate and alkali metal silicate, together with the seed for precipitation of calcium carbonate, the inclusion of a selective class of detergent enhancers provides better binding, both in scale and in the degree of decrease in the concentration of dissolved calcium and dissolved ions magnesium, which helps to wash contaminated fabrics when washing in hard water.

Thus, an object of the present invention is to provide a composition of a detergent component that is more effective in binding hard water than compositions available in the art.

Another objective of the present invention is to provide a composition of the detergent component, which more effectively reduces the concentration of ions of both calcium and magnesium in hard water, compared with the compositions available in the prior art.

Another objective of the present invention is to provide a detergent composition that provides better washing of dirty fabrics in comparison with compositions of the prior art, especially when washing in hard water.

SUMMARY OF THE INVENTION

According to a first aspect of the present invention, there is provided a washing component composition comprising (ί) two precipitating components which are (a) alkali metal carbonate and (b) alkali metal silicate;

(i) calcium carbonate; and (iii) a detergent enhancer, which is a compound capable of precipitating magnesium ions from hard water, selected from the group consisting of alkali metal or alkaline earth metal oxides or hydroxides and alkali metal aluminate, zinc or titanate.

In a second aspect of the present invention, there is provided a detergent composition comprising a surfactant and a detergent composition of the first aspect of the present invention.

Disclosure of invention

The invention provides a method for softening hard water, in particular for washing soiled fabrics. The composition is more effective if the injected hard water contains both dissolved calcium and dissolved magnesium ions. The method includes dissolving / dispersing four materials in water, namely (ί) alkali metal carbonate; (ίί) alkali metal silicate, (w) calcium carbonate, and (ίν) detergent enhancer, which is a compound capable of precipitating magnesium ions from water, selected from the group consisting of alkali or alkaline earth metal oxides or hydroxides and aluminate, zinc or alkali metal titanate.

Preferred detergent enhancers are sodium or potassium hydroxide; calcium oxide; calcium hydroxide; and aluminate, zincate and sodium or potassium titanate. More preferred detergent enhancers are calcium oxide, calcium hydroxide, or alkali metal aluminate or zincate. Preferably, the detergent enhancer is present in the range of 0.1 to 7.5%, more preferably 0.1 to 5%, and most preferably 1 to 3% by weight of the detergent composition. Without reference to theory, it is believed that the inclusion of these selective amplifiers of the detergent components helps remove MD ions. It is believed that the presence of enhancers of detergent components maintains the required pH of the solution, which promotes the removal of magnesium ions by precipitation in the form of magnesium hydroxide. In this process, the concentration of free Ca ions increases, which precipitates in the form of calcium carbonate due to the presence of precipitating components.

In a preferred aspect of the present invention, the detergent composition comprises a complexing agent selected from aminopolycarboxylic acid, aminopolyphosphonic acid, nitrilotriacetic acid, or salts thereof.

Better binding is achieved if the complexing agent is dissolved in water at least 30 seconds after the precipitating components, namely alkali metal carbonate and alkali metal silicate, are dissolved / dispersed in water.

Aminopolycarboxylic acids are compounds having the formula

NOOSSN ₂ ^ _χ CH ₂ COOH

N - sn ₂ - sn ₂ -Ν NOOS SN? ' ⁷ k to

In the above formula, if K. is represented by —CH ₂ —COOH, then the compound is ethylenediaminetetraacetic acid (EDTA).

If K is represented

- 2 017243 _/ sn ₂ - COOH - CH, - CH, - N \

CH ₂ COOH This compound is diethylene triamine pentaacetic acid. Aminopolyphosphonic acids are compounds having the formula n ₂ about ₃ p-cn _2h ^ CH ₂ -PO ₃ H ₂

N - sn ₂ - sn ₂ - N H ₂ O ₃ P-CH ₂ - ^ \ |?

In the above formula, if B is -CH2-PO3H2, then the compound is ethylenediaminetetramethylphosphonic acid. This compound is marketed under the brand name ΌΕΟυΕδΤ 204 ™.

In the above formula, if B is represented by _x sn ₂ -po ₃ n ₂ - CH, - CH, - N \

sn ₂ - PO ₃ H _{2 The} compound is diethylene triamine pentamethylphosphonic acid. This compound is marketed under the brand name ΌΕΟυΕδΤ 206 ™.

Nitrilotriacetic acid has the chemical formula C ₆ H ₉ NO ₆ and is also known as aminotriacetic acid.

Preferably not more than 20%, more preferably not more than 10%, most preferably not more than 5% of the complexing agent is dissolved in water during the first 30 s, more preferably during the first 45 s after the precipitating components are dissolved / dispersed in water. Examples of preferred complexing agents are the sodium or potassium salt of ethylenediaminetetraacetic acid, diethylene triamine pentaacetic acid, ethylenediaminetetramethylphosphonic acid or diethylenetriaminepentamethylphosphonic acid.

Thus, preferably, the complexing agent is present in a sustained release form to achieve the desired dissolution profile. The inventors have found that one way to achieve this is to incorporate a complexing agent into a particle of a certain size in the range of 0.3 to 3 mm, more preferably in the range of 0.75 to 2 mm.

The composition of the detergent component includes a precipitating component, which is an alkali metal silicate. The alkali metal silicate is preferably sodium silicate or potassium silicate, more preferably sodium silicate. Sodium silicate is a colorless compound of sodium and silicon oxides. It has a number of chemical formulas in which the content of sodium oxide (Na ₂ O) and silicon dioxide or silica (81O ₂ ) varies. It is soluble in water, and it is obtained by the reaction of silica (sand) and sodium carbonate at a high temperature in the range from 1200 to 1400 ° C. An aqueous solution of sodium silicate is called liquid glass. Sodium silicates, the ratio of Na ₂ O: 81O ₂ in which varies from 1: 1.6 to 1: 4, are known as colloidal silicates. They are usually sold in the form of aqueous solutions from 20 to 50%. Of the various types of sodium silicates available, the preferred compound for use in the composition of the invention is alkaline sodium silicate or sodium metasilicate. Its concentration in the water is in the range of 27-39%, and the ratio №O: ₂ occupies 8 is in the range from 3.0 to 3.5. An alkali metal silicate is preferably present in the range of 1 to 40% by weight of the detergent component composition.

The composition of the detergent component according to the invention includes another precipitating component, which is an alkali metal carbonate. The alkali metals are preferably sodium or potassium, with sodium being preferred. Thus, the most preferred alkali metal carbonate is sodium carbonate. The alkali metal carbonate is preferably present in the range of 5 to 70%, more preferably in the range of 10-50 wt.% Of the composition of the detergent component.

The composition of the detergent component of the invention includes a seed for precipitating calcium carbonate, which is calcium carbonate. Calcium carbonate may be calcite or aragonite, most preferably calcite. Calcite is preferably calcite with a large specific surface area. Preferably, the specific surface area of calcium carbonate is more than 18 m ² / g, more preferably more than 30 m ² / g, most preferably more than 60 m ² / g. Calcium carbonate is preferably present in dialazone from 5 to 40 wt.% The composition of the detergent component.

The composition of the detergent component according to the invention ensures that the concentration of Ca ^{2+ ions} in the injected hard water is reduced from about 140 · 10 ^-6 to less than about 1-10 ^{-6 in} less than about 2 minutes, and optimal concentration conditions of less than 0 are achieved. 3-10 ^{-6 in} less than 2 minutes.

The composition of the detergent component according to the invention also ensures that the concentration of MD ^{2+ ions} in the injected hard water is reduced from about 40-10 ^-6 to less than about 6-10 ^{-6 in} less than 2

- 3 017243 min, and optimal concentration conditions are achieved in less than about 2 · 10 ^{-6 in} less than 2 minutes. An advantage of the method according to the invention is that it requires a substantially lower amount of traditional complexing components, such as water-soluble phosphates. In a more preferred aspect, the composition of the invention is substantially free of such a component as water soluble phosphates.

According to a preferred aspect of the invention, the composition of the detergent component of the invention comprises a seed capable of precipitating magnesium ions. Examples of such seeds are magnesium carbonate and dolomite. According to a preferred aspect of the invention, it is provided that magnesium carbonate or dolomite is present in an amount of 5-40 wt.% The composition of the detergent component.

According to a preferred aspect of the invention, there is provided a detergent composition comprising a detergent composition according to the first aspect of the invention and a surfactant selected from any class of anionic, nonionic, cationic, zwitterionic or amphoteric surfactants. Thus, the invention also provides a method for cleaning tissue, comprising reacting contaminated tissue with water that has been bound by the composition of the detergent component of the invention, wherein the water further comprises a surfactant. The most suitable are those substances that are widespread and inexpensive types, that is, anionic surfactants. Suitable anionic synthetic detergents are linear alkyl benzenesulfonates, alpha olefin sulfonates and primary alkyl sulfates. Linear alkylbenzenesulfonates (L8) are ideally suited because they are widespread, inexpensive and have very good effects as surfactants. You can use sodium or magnesium salts of acids L˧. The method according to the invention works better if the surfactant enters the water in a delayed manner with respect to the precipitating components and calcium carbonate. Preferably, the surfactant is in a dissolved state after 15-600 s, more preferably after 30-480 s, most preferably after 45-300 s after binding of water by the method of the invention. In this regard, the inventors of the present invention prefer the linear salt of linear alkylbenzenesulfonic acid to be a surfactant. A method of providing a delayed dissolution of a surfactant in water is to incorporate the linear linear alkylbenzenesulfonic acid magnesium salt into particles ranging in size from 0.1 to 2 mm.

Preferably, the detergent composition is present in the range of 5 to 80% by weight of the detergent composition. The surfactant is preferably present in the range of 5 to 90%, more preferably 10 to 50%, most preferably 15 to 35% by weight of the detergent composition. The detergent composition is preferably in solid form, i.e. in the form of powder, granules, bars or tablets. The most preferred form of the detergent composition is in the form of a powder or granules.

According to yet another aspect of the present invention, there is provided the use of a composition of a detergent component of the invention for softening hard water containing both calcium and magnesium ions.

The alkali metal carbonate is preferably present in the range from 10 to 70%, more preferably from 15 to 60% and most preferably from 25 to 50 wt.% Of the detergent composition. Calcium carbonate is preferably present in the range from 3 to 50%, more preferably from 5 to 40%, and most preferably from 10 to 30 wt.% Of the detergent composition.

According to yet another aspect of the present invention, there is provided the use of a detergent composition of the invention for washing fabrics in hard water containing both calcium and magnesium ions.

Below the invention will be illustrated by the following non-limiting examples.

Examples

Examples 1-5. Kinetics of binding.

Experiments were conducted using different compositions of the detergent components, as shown in the table. 1, in accordance with the following method for studying binding efficiency.

200 cubic meters was poured into a glass beaker. cm of hard water, the French hardness of which was 48 ° P, that is, water containing 128 · 10 ^-6 Ca ^{2+ ions} and 38.4 · 10 ^- 6 MD ^{2+ ions} . Various materials were added to this solution, namely sodium carbonate, calcite and sodium metasilicate 9Н ₂ О so that the concentration of sodium carbonate was 0.9 grams per liter (g / l), the concentration of calcite was 0.5 g / l and the concentration sodium silicate was 0.75 g / L. The effect of adding various enhancers of detergent components was investigated. The measurements were performed as follows.

The solution was stirred with a glass rod for 45 s. At predetermined periods of time after adding the binding components with a syringe, a sample was taken and filtered through a microfilter into 5-cc glass vials. see. The concentration of Ca ^{2+ ions} and MD ² 'ions was determined by EDTA titration as described below.

Measurement of total ion concentration (calcium and magnesium).

- 4 017243

The method included titration with EDTA (disodium salt of ethylenediaminetetraacetic acid) using EBT (E1us11gots B1ask-T) as an indicator. About 2 ml of the test solution was pipetted into a 150 ml conical flask. The solution was diluted with approximately 10 ml of water. To it was added 5 ml of ammonia chloride buffer with pH 10. About 35 mg of 1% EBT in a solution of potassium nitrate was added. A red wine color solution was obtained. A standardized EDTA solution was poured dropwise from the burette with constant stirring. As more EDTA was added, the color gradually changed from the color of red wine to violet. The endpoint was determined by a sudden measurement of color from purple to blue. The total concentration of ions (calcium and magnesium) was calculated by the following formula:

Total ion concentration = volume of EDTA * concentration of EDTA / volume of the test solution taken.

The concentration in terms of French rigidity was calculated by the formula:

Total ion concentration in ° Р = (Total ion concentration in 10 ' ⁶ ) / 4 for Ca ²⁺

The total concentration of ions in ° p = (The total concentration of ions in 1O ' ^b ) / 2.4 for MD ²

The data are summarized in table. one.

Table 1

Example 1 Example 2 Example 3 Example 4 Example 5 Detergent amplifier Missing Hydroxide Hydroxide Oxide Aluminate component calcium calcium calcium sodium Concentration in g / l - 0.05 oh 1 0.05 0.25 Time minutes Total ° P Total ° G Total ° G Total T Total ° G 0 48 48 48 48 48 2 8 7 5 7 6 5 5 3,5 2 2 3 fifteen 2,5 1.25 one one one

The data in the table. 1 indicate that better binding, both in terms of lower final water hardness and faster binding kinetics, was obtained by using the composition of the detergent component of the invention as compared with the composition of the detergent component of the prior art.

Examples 6-8.

Experiments using the composition of the detergent component of example 2 were carried out as shown in table. 1, except that a complexing agent was additionally used, namely ethylenediaminetetraacetic acid (EDTA), either simultaneously with other ingredients or with some delay relative to other ingredients. The results are summarized in table. 2 together with the result of example 2 for comparison.

table 2

Example 2 Example 6 Example 7 Example 8 EDTA Concentration, Ι0 ' ⁶ Not added thirty thirty 60 Particle size EDTA, mm As a solution As a solution 0.85-1.7 Time minutes • In 2 minutes after others Along with others Along with others 0 48 48 48 48 2 7 5 5 3 5 3,5 3,5 4 2 fifteen 1.25 2 one 0.5

- 5 017243

The data in the table. 2 indicate that when using a complexing agent in addition to an amplifier of the detergent components, better bonding is ensured, both in terms of faster kinetics and in terms of lower final water hardness.

Examples 9-12. Washing fabrics.

Various washing experiments were carried out using the following method. 700 ml of water with a hardness of 48 ° B (containing Ca: MD ions in a ratio of 2: 1) was poured into a 1 L steel container. Nine diagnostic indicators were taken (three of each of the following No. РК 10Ό, №ΡΚ20Ό and А89), №ΡΚ10Ό is a cotton fabric having combined soiling, No. 20Ό is a polyester-cotton fabric having combined soiling, and Ά89 is a cotton fabric having a different type of combined contamination. The experiments were carried out with a liquid: tissue ratio of 50: 1. The compositions were added to water (at a rate of 4 g / L) and mixed for 5 minutes at 90 rpm to dissolve the composition. Then a tissue was placed in the liquid and left to soak for 15 minutes. After that, washing was carried out for 30 minutes with shaking at 90 rpm. Then the tissues were rinsed 3 times for 3 minutes. After this, the tissue was dried in air. The reflectivity of the fabric was measured before and after washing with an OTDR at a wavelength of 460 nm. We used the indicator AK * 460, which is the difference in reflectivity of the erased and non-erased tissue, and the average value for three diagnostic indicators was taken.

Example 9 is a detergent composition according to the invention.

Example 10 is a detergent composition similar to the composition in example 9, but without the inclusion of an amplifier of detergent components.

Example 11 is the product Κίη AFuapesF. which is one of the best sodium carbonate detergents available in the Indian market. The compositions in examples 9 and 10 are shown in table. 3.

Table 3

Example nine 10 eleven Surface-active substance Mg8A8 McLAZ KAZ The concentration of surfactant, wt.% 20,0 20,0 16,0 Sodium carbonate, wt.% 30,0 30,0 35.0 ForkalU, wt.% 16.7 16.7 8.0 Sodium silicate, wt.% 25.0 25.0 - Sodium hydroxide, wt.% 1.7 - -

8TRP, wt.% - - 6.0 Others, wt.% up to 100 up to 100 up to 100

In the table. higher:

MgA8 is a magnesium salt of linear alkylbenzenesulfonic acid.

IAb§ is a sodium salt of linear alkylbenzenesulfonic acid.

ForkalU (Rogue1i) is a commercially available calcite with a specific surface area of 18-20 m ² / g.

8TPP is sodium tripolyphosphate.

Others are primarily fillers, which are sodium chloride, sodium sulfite and moisture.

Comparative data on the washing of various fabrics are given in table. 4 below.

Table 4

The data in the table. 4 indicate that better laundering is achieved with the detergent composition when the detergent amplifier of the invention is turned on. In addition, the composition according to the invention provides better laundering compared to one of the best commercially available products of this class.

Thus, the invention provides a composition of a detergent component that provides

- 6 017243 faster binding compared with methods existing in the state of the art, in particular, if hard water contains both calcium and magnesium ions. Therefore, contaminated tissues are washed better.

Claims (13)

CLAIM 1. The composition of the washing component, including: (ί) two precipitating components, which are (a) an alkali metal carbonate and (b) an alkali metal silicate; (ίί) calcium carbonate; and (iii) a detergent enhancer, which is a compound capable of precipitating magnesium ions from hard water, selected from the group consisting of alkali metal or alkaline earth metal oxides or hydroxides and alkali metal aluminate, zincate or titanate. 2. The detergent composition of claim 1, wherein said detergent enhancer is calcium hydroxide, calcium oxide or aluminate or alkali metal zincate. 3. The composition of the detergent component according to claim 1 or 2, in which the amplifier of the detergent components is present in the range from 0.1 to 7.5 wt.% The composition of the detergent component. 4. The composition of the detergent component according to any one of the preceding paragraphs, further comprising a complexing agent selected from aminopolycarboxylic acid, aminopolyphosphonic acid, nitrilotriacetic acid or their salts. 5. The composition of the detergent component according to claim 4, in which the particle size of the complexing agent is in the range from 0.3 to 3 mm 6. The composition of the detergent component according to any one of the preceding paragraphs, in which the alkali metal silicate is present in the range from 1 to 40 wt.% The composition of the detergent component. 7. The composition of the detergent component according to any one of the preceding paragraphs, in which said alkali metal carbonate is present in the range from 5 to 70 wt.% The composition of the detergent component. 8. The composition of the detergent component according to any one of the preceding paragraphs, in which calcium carbonate is present in the range from 5 to 40 wt.% The composition of the detergent component. 9. The composition of the detergent component according to any one of the preceding paragraphs, further comprising a seed capable of precipitating magnesium ions, which is selected from magnesium carbonate or dolomite. 10. The composition of the detergent, including: (ί) the composition of the detergent component according to any one of the preceding paragraphs and (s) a surfactant selected from any class of anionic, nonionic, cationic, zwitterionic or amphoteric surfactants. 11. The detergent composition of claim 10, in which said composition of the detergent component is present in the range from 5 to 80 wt.% The composition of the detergent. 12. The detergent composition of claim 10 or 11, wherein said surfactant is a linear linear alkylbenzenesulfonic acid magnesium salt. 13. The detergent composition according to item 12, in which the particle size of said magnesium salt of linear alkylbenzenesulfonic acid is in the range from 0.1 to 2 mm. 4 ^^ Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2