ES2353935T3 - IMPROVEMENT SYSTEM OF DETERGENCE FOR A DETERGENT COMPOSITION. - Google Patents

Abstract

A detergency builder system for a detergent composition, comprising: (i) a water soluble alkali metal carbonate; (ii) 5% to 50% by weight of the detergent improver system of a seed to precipitate calcium carbonate which is calcium carbonate; and (iii) a detergency co-improver which is a dicarboxylic acid or salt thereof, wherein said detergency co-improver has an average particle size of less than 150 micrometers.

Description

TECHNICAL FIELD

The invention relates to a system improving the detergency for use in detergent compositions. The invention relates more particularly to a system detergency builder that ensures more suppression rapid calcium ions wash solutions, to same time that it is less expensive than improver systems of detergency based on phosphates and zeolites.

BACKGROUND AND RELATED TECHNIQUE

Soaps that are alkali metal salts of acids greases have been traditionally used for applications of personal washing Soaps have also been used for laundry wash. In the laundry wash with soaps, the washing efficiency is lower than when washing in water hard. Hard water refers to water that has levels high levels of dissolved calcium or magnesium salts. Ions of dissolved calcium and magnesium react very quickly with the alkali metal cation (sodium or potassium) of the soap, leading to the formation of a calcium soap that is insoluble in water and therefore leads to a scarce detergency With the advent of detergents synthetic, which are alkali metal salts of acids from long chain originating in oil, the same persists trouble. Most synthetic detergents to use Common include linear alkyl benzene sulphonates, alpha olefin sulfonates and primary alkyl sulfates that belong to the class of anionic surfactants. They also know each other non-ionic, cationic, amphoteric and surface-active surfactants

hybrid ions The cleaning performance of most

synthetic surfactants are also affected by washing in hard water.

Compounds that react preferentially with the dissolved calcium and magnesium ions present in hard water, thus maintaining the desired high concentration of detergent in its active form, have been used in compositions detergents These compounds or mixtures of compounds are known as detergency builders. Breeders commonly known detergents are carbonates, silicates, alkali metal phosphates and compounds structured zeolite type. Metal carbonates alkalines such as sodium carbonate, commonly referred to as soda, are very cheap and are widely used as detergency builder in detergent formulations of low cost. High quality detergents use detergency builders such as phosphates and / or zeolites, since which have better detergency enhancing properties Although they are more expensive. There has been a continued work for develop more efficient and faster improver systems using less expensive materials. In addition, the use of phosphates in detergents are believed by many people who are responsible for the eutrophication of rivers and other aqueous structures natural Therefore, a great effort has been made to develop detergency builder systems more rapids using calcium carbonate as the main subject cousin.

EP 0234818 (Unilever, 1987) describes a detergent composition containing (i) an active system detergent comprising a mixture of (a) a component

active anionic non-soap detergent; (b) a component

active non-ionic detergent and (c) soap; (ii) a carbonate of water-soluble alkali metal and (iii) a material of carbonate in the form of water insoluble particles which is a seed crystal for calcium carbonate; characterized by a specific combination of weight ratios of various detergent active components. The system detergency builder in this post is a mix of soda and calcium carbonate. There have been many improvements in this technology and many have been put into circulation products that are improvements over this basic technology in the that a combination of soda and calcium carbonate is used. The present inventors have determined that the best systems currently available detergency builders, which they use sodium carbonate as the detergency builder basic, still do not provide detergency improvement desired fast and there are improvement options in this technology, that can be perceived by consumers in cleaning of your laundry load or in terms of the costs of products. The present inventors have found that the use of the specific detergency builder system described in EP 0234818 together with a co-improver of the

detergency

specific provides a improvement from the

detergency

very fast that no be got never with

Previously with similar systems.

US 7186677 (Henkel, 2007) describes a method for producing surfactant granules having a good solubility and variable apparent densities that comprises (a) providing a mixture of surfactants anionic and detergency builder acids that have

a weight ratio of 1: 100 to 1:20 of acid improving the

surfactant acid detergency; and (b) contact the mix with at least one solid neutralizing agent. Acid detergency builder is selected from acid citric, tartaric, succinic, malonic, adipic, maleic, fumaric, oxalic, gluconic, nitrilotriacetic, aspartic or ethylenediaminetetraacetic acid, among many other acids, in which the detergent builder acid has a size of particles below 200 µm.

The use of a combination of calcium carbonate and sodium carbonate in a detergency builder system for detergent compositions it is known from the documents CA 379772, US 4473485, WO 9840455 and CA 991942.

Therefore, it is an object of the present invention provide a detergency builder system for a detergent composition that provides an improvement in faster detergency compared to at least part of the prior art for similar systems.

It is another object of the present invention to provide a detergency builder for a composition detergent that provides an improvement in detergency fast while having a lower cost in comparison with at least part of the systems of the technique previous.

SUMMARY OF THE INVENTION

The invention provides a system that improves the detergency for a detergent composition, comprising:

(i) a water soluble alkali metal carbonate;

(ii) 5% to 50% by weight of the system improving the detergency of a seed to precipitate carbonate

calcium which is calcium carbonate; Y

(iii) a detergency co-improver that is an acid dicarboxylic or salt thereof, wherein said co-enhancer of the detergency has an average particle size of less than 150 micrometers

It is preferred that the water solubility of the co-enhancer of the detergency is more than 1 g / l at 25 ° C.

Particularly preferred dicarboxylic acids are oxalic, malonic and succinic acid.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a system improving the detergency for a detergent composition. A component of the detergency builder system is a carbonate of water soluble alkali metal. Alkali metal is preferably sodium or potassium, sodium being preferred. Therefore, the most preferred alkali metal carbonate is sodium carbonate The alkali metal carbonate is preferably present in an amount in the range of 10% to 90%, more preferably 25% to 90%, most preferably 45% to 80% by weight of the system improving the detergency

Another important element of the system improving the detergency of the invention is a seed to precipitate calcium carbonate. Through “a seed to precipitate calcium carbonate ”means a compound that has the ability to act as a seed for precipitation of calcium carbonate in aqueous media. The seed for precipitate calcium carbonate is a material in the form of particles substantially insoluble in water. This material in the form of water insoluble particles may be present

in the detergency builder system or be generated in

situ when the detergency builder system is dispersed in water. The most preferred aspect provides the particulate material substantially insoluble in water that is present in the improver system of the detergency The particulate material substantially insoluble in water is calcium carbonate. He calcium carbonate can be calcite or aragonite and, more preferably, it is calcite. Calcite is preferably high surface area calcite. Preferably, the Calcium carbonate seed has a surface area of more than 20 m2 / g, more preferably more than 30 m2 / g, most preferably more than 60 m2 / g. The seed to precipitate Calcium carbonate is present in an amount in the range from 5% to 50%, more preferably from 10% to 40%, what more preferably from 15% to 30% by weight of the system detergency builder.

The detergency builder system of the invention comprises a detergency co-improver which is an acid dicarboxylic or a salt thereof. The co-improver of the detergency preferably has a water solubility of more than 1 g / l at 25 ° C. Preferred dicarboxylic acids are choose between oxalic acid, malonic acid or acid succinic, with oxalic acid being the most preferred. Salts Preferred dicarboxylic acid are metal salts alkali or ammonium, the salts of alkali metals. The detergency co-improver is present in an amount in the range of 2% to 20%, plus preferably from 4% to 12% by weight of the improver system of the detergency The invention works best when the co

detergency builder is present in the form of a

powder, that is, in the form of low particle size. He average particle size of the detergency co-improver is less than 150 micrometers, more preferably less than 75 micrometers Ideally, the detergency co-improver is molecularly dispersed in the detergent composition in which the improving system of the detergency This can be achieved by dissolving the detergent trough in water and spraying the solution on the detergent composition or system detergency builder and then drying until desired moisture content.

The detergency builder system of the invention provides detergency improvement kinetics relatively fast, faster than the systems of the prior art The detergency builder system ensures that the ion concentration of Ca2 + ions in the Water provided is reduced from approximately 200 ppm to less from, or about 1.2 ppm, more preferably up to less than, or about 1.0 ppm, more additionally preferred to less than, or about 0.5 ppm, optimally less than, or about 0.3 ppm in about 30 seconds The improving system of the detergency of the invention is preferably substantially free of detergency builders phosphates Additionally, more preferably the system detergency builder is substantially free of zeolite detergency builders.

According to another aspect of the invention, a procedure to prepare a system to improve the

detergency for a detergent composition comprising

mix powders of a soluble alkali metal carbonate in water, 5% to 50% by weight of the system improving the detergency of a seed to precipitate carbonate calcium, which is calcium carbonate; and a co-improver of the detergency which is a dicarboxylic acid or a salt of same.

In the above procedure, the detergent feeder powders have an average size of particles of less than 150 micrometers, more preferably less than 75 micrometers

In a preferred aspect, the procedure of the invention comprises:

(i)

dissolve dicarboxylic acid or its salts in water to form a solution;

(ii)

dry mix the powders of a metal carbonate water soluble alkaline with 5% to 50% system weight detergency builder, from a seed to precipitate calcium carbonate, which is calcium carbonate, to form a mixture of powders; Y

(iii) mixing said solution of step (i) with the powder mixture of stage (ii). The solution is preferably sprayed on the powder mixing during the mixing stage (iii).

According to another aspect of the present invention, provides a detergent composition comprising (i) the detergency builder system according to the invention and (ii) a surfactant selected from any one of the class anionic, nonionic, cationic hybrid or amphoteric ion. The detergency builder system of the invention can

be present in an amount in the range of 5% to 80%,

more preferably 15% to 60%, most preferably 25% to 50% by weight of the detergent composition. Surfactants suitable are commonly used compounds as agents of surface activity provided in textbooks Well-known "Surface Active Agents", Volume I of Schwartz and Perry and "Surface Active Agents and Detergents", Volume II from Schwartz, Perry and Berch.

According to another aspect of the present invention, provides a procedure to prepare a composition detergent comprising dry mixing powders of a surfactant selected from any one of the classes anionic, nonionic, cationic, hybrid or amphoteric ion with the powders of the detergency builder system present invention

Still, according to another aspect of the present invention, provides a procedure to prepare a composition detergent comprising the steps of:

(i)

dissolve a dicarboxylic acid or salts thereof in water to form a solution;

(ii)

dry mix the powders of a surfactant selected from any one of the anionic classes, not ionic, cationic hybrid or amphoteric ion with a water soluble alkali metal carbonate and 5% to 50% in weight of the detergency builder system, of one seed to precipitate calcium, which is calcium carbonate, to form a mixture of powders; Y

(iii) mixing said solution of step (i) with the

powder mixture of stage (ii). Preferably, the method comprises a step of

Dry the detergent composition to a moisture content

of less than 10%.

The invention will be illustrated below by means of following non-limiting examples.

EXAMPLES

Comparative Examples A to F

These are examples of systems improving the detergency of the prior art.

Several improver compositions of the detergency and were added to hard water containing 200 ppm of calcium ions at concentrations such as those shown in the Table 1. Disodium oxalate, when used, was added. after crushing to a powder at an average size of particles of approximately 145 micrometers. He studied the kinetics of detergency improvement by measuring the concentration of Ca2 + ions, at various periods of time, and the data are collected in Table 1. The method to determine The concentration of Ca2 + is given below:

Measurement of calcium ion concentration

The method included a degree with EDTA (salt of ethylene diamino tetraacetic acid disodium) using EBT (eriochrome black - T) as indicator. They pipetted approximately 2 ml of calcium ion solution in a 150 ml conical flask. The solution was diluted with approximately 10 ml of water. To this 5 ml of ammonia-ammonium chloride buffer, pH 10. Additionally, approximately 35 mg of 1% EBT in solution was added of potassium nitrate. A wine red color was obtained. Be added a standardized EDTDA solution drop by drop from a burette with constant agitation. As it was added more EDTA, the color changed gradually from wine red to

-11 violet. The end point was identified by a sudden change colored from violet to blue. Ion concentration Calcium was calculated using the formula:

image 1

Table 1

Comparative example

Sodium carbonate g / l HSAC, g / l Disodium oxalate, g / l Time, s Calcium ion concentration, ppm

TO

1.5 0 0 60 10.4

B

1.5 0 0 300 1.8

C

1.5 0.5 0 60 4.7

AND

1.5 0.5 0 120 1.2

F

1.5 0 0.4 30 3.6

G

1.5 0 0.4 60 1.7

Note: HSAC means high surface area calcite with a surface area of (20-30) m2 / g.

The comparative examples of the interior technique are

10 capable of bringing the concentration of Ca2 + ions below from 200 ppm to a minimum of approximately 1.2 to 2 ppm and the necessary time is about 1 to 2 minutes (comparative examples E and G being better). Examples 1 to 6

These are examples like those of the invention that have a combination of sodium carbonate, HSAC and oxalate of disodium

Various improver compositions of the detergency and were added to bore containing 200 ppm of 20 calcium ions at concentrations such as those shown in the Table 2. In Examples 1 to 5, the system improving the detergency was a dry mixture of sodium carbonate and

high surface area calcite (HSAC) to which

sprayed a solution of disodium oxalate in water and mixed. In example 6, the disodium oxalate granules they were crushed first to give a powder with a average particle size of approximately 145

5 micrometers The disodium oxalate powder is then Dry mixed with sodium carbonate and HSAC. The Kinetics of detergency improvement were studied by measuring the concentration of Ca2 + ions at various periods of time. The results are summarized in Table 2.

10 Table 2

Comparative example

Sodium carbonate g / l HSAC, g / l Disodium oxalate, g / l Time, s Calcium ion concentration, ppm

one

1.5 0.5 0.1 30 1.2

2

1.5 0.5 0.1 60 0.7

3

1.5 0.5 0.15 30 1.0

4

1.5 0.5 1.15 60 0.4

5

1.5 0.5 0.3 30 0.28

6

1.5 0.5 0.3 30 0.96

The data in Table 2, when compared to

data in Table 1, indicate that the system improving the

detergency of the invention provides improvement kinetics

15 of the relatively faster detergency compared with technique detergency builder systems previous. Comparative example H and examples 7 and 8 These are examples related to system performance

20 detergency builders that are part of the invention (examples 7, 8) compared to systems prior art detergency builders (example comparative H).

Various improver compositions of the

detergency and were added to bore containing 200 ppm of calcium ions at concentrations (in grams per liter or g / l) as shown in Table 3. The improving efficacy of the detergency was studied by measuring the ion concentration CA2 +, 2 minutes after the addition of the compositions and the data is presented in Table 3. The method for

Ca2 +

determine the concentration of is the same as previously provided:

Table 3

Comparative example

Sodium carbonate g / l HSAC, g / l Disodium oxalate, g / l Calcium ion concentration, ppm

Comparative Example H

1.5 0.5 0 1.2

Example 7

1.5 0.5 0.3 0.4

Example 8

1.5 0.5 0.42 0.28

10 Note: Oxalic acid was used in previous experiments with a particle size of <0.075 mm.

The data in Table 3 indicate that the inclusion of dicarboxylic acid together with oxalic acid in a system

15 sodium carbonate / calcite detergency builder provides a more effective detergency improvement in comparison with a detergency builder system prior art Comparative Examples I to N and Examples 9 to 11

20 These examples refer to the cleaning performance of fabrics cleaned with detergent compositions of the invention in comparison with commercial detergent products.

The detergent compositions were used to clean various test samples, as shown in Table 4. 25 The WFK10D (composite dirt on cotton cloth) had

an initial reflectance of approximately 45, WFK20D

(dirt composed of poly-cotton cloth) of approximately 40 and WKK30D (composite dirt on fabric polyester) of about 40. All compositions detergents had linear alkyl-benzene-sodium sulfonate as the active surfactant at approximately 0.7 g / l in the washing liquid The detergency builder systems of the various detergent compositions in the liquid of Washing were as follows:

SURF EXCEL®: 1.02 g / l STPP + 0.89 g / l carbonate sodium + 0.07 g / l HSAC

RIN ADVANCED®: 0.16 g / l STPP + 1.4 g / l carbonate sodium + 0.3 g / l HSAC

Examples 9 to 11: 1.5 g / l sodium carbonate + 0.5 g / l HSAC + 0.4 g / l disodium oxalate.

STPP is sodium tripolyphosphate.

The cost of the compositions that are of the invention (Examples 9 to 11) is comparable to the RIN composition ADVANCED® and approximately 30% lower than the composition SURF EXCEL®. The water used to clean had an index of hardness of 48 FH. The protocol used to clean is provided below.

The experiments were carried out on a tergotometer. The various compositions were dissolved in the tergotometer flask for 10 minutes at a speed of 90 rpm. The test samples were then rinsed three times at a liquid to clothing ratio of 25. The samples were then dried. Then the reflectance of the samples was measured. The average reflectance data (ΔR 460) was taken on three different samples.

The reflectance data is provided in the

-15 next Table 4.

Table 4

Examples

Product Test sample ΔR 460

Comparative Example I

SURF EXCEL® WFK10D 20.0

Comparative Example J

ADVANCED® RIN WFK10D 17.4

Example 9

Within the invention WFK10D 19.6

Comparative Example K

SURF EXCEL® WFK20D 14.9

Comparative Example L

ADVANCED® RIN WFK20D 12.2

Example 10

Within the invention WFK20D 17.8

Comparative Example M

SURF EXCEL® WFK30D 16.7

Comparative Example N

ADVANCED® RIN WFK30D 14.3

Example 11

Within the invention WFK30D 19.2

The data in Table 4 indicate that the composition 5 detergent according to the invention provides equal cleaning

or higher compared to the best detergent product SURF EXCEL®, but at a lower cost. Besides, the detergent composition of the invention provides a superior cleaning for all test samples in

10 comparison with RIN ADVANCED®, at the same cost.

-16

Claims (11)

1. A detergency builder system for a detergent composition, comprising: (i) a water soluble alkali metal carbonate; (ii) 5% to 50% by weight of the system improving the detergency of a seed to precipitate carbonate calcium which is calcium carbonate; Y (iii) a detergency co-improver that is an acid dicarboxylic or salt thereof, wherein said co-enhancer of the detergency has an average particle size of less than 150 micrometers

2.

A detergency builder system according to the claim 1, wherein said co-enhancer of the detergency has a water solubility of more than 1 g / l at 25 ° C

3.

A detergency builder system according to a any of the preceding claims, wherein said dicarboxylic acid is selected from oxalic acid, Malonic acid or succinic acid.

Four.

A detergency builder system according to a any of the preceding claims, wherein said detergency co-enhancer is present in a amount in the range of 2 to 20% by weight of the system detergency builder.

5.

A detergency builder system according to a any of the preceding claims, wherein said alkali metal carbonate is present in a amount in the range of 10 to 90% by weight of the system detergency builder.

6. A procedure to prepare an improvement system of the detergency for a detergent composition, which comprises mixing powders of an alkali metal carbonate water soluble, 5% to 50% by weight of the system improving the detergency of a seed to precipitate carbonate calcium, which is calcium carbonate; and a co-improver of the detergency which is a dicarboxylic acid or a salt of same, said detergency co-improver having a average particle size of less than 150 micrometers. 7. A procedure to prepare an improvement system of the detergency for a detergent composition according to the claim 6, comprising the steps of:

(i)

dissolve dicarboxylic acid or its salts in water to form a solution;

(ii)

dry mix powders of a metal carbonate water soluble alkaline with 5% to 50% system weight detergency builder, from a seed to precipitate calcium carbonate, which is calcium carbonate, to form a mixture of powders; Y

(iii) mixing said solution of step (i) with the powder mixture of stage (ii). 8. A detergent composition comprising:

(i)

a detergency builder system according to a any one of claims 1 to 5 above; Y

(ii)

a surfactant selected from any one of the anionic, nonionic, cationic, ion classes Hybrids or amphoteric.

9.

A detergent composition according to claim 8, wherein said detergency builder system is present in an amount in the range of 5 to 80% by weight of the detergent composition.

10.

A procedure to prepare a composition detergent, comprising the step of dry mixing powders of a surfactant selected from any one of the anionic, nonionic, cationic, hybrid ion classes or

5 amphoteric with the detergency builder system according to a any one of claims 1 to 5 above. 11. A procedure to prepare a composition detergent, which comprises the steps of: (i) dissolve dicarboxylic acid or its salts in water 10 to form a solution, said acid or its salts having a average particle size of less than 150 micrometers; (ii) dry mixing the powders of a surfactant selected from any one of the anionic classes, not ionic, cationic hybrid or amphoteric ion with a 15 alkali metal carbonate soluble in water and 5% to 50% in weight of the detergency builder system, of one seed to precipitate calcium carbonate, which is carbonate of calcium, to form a mixture of powders; Y (iii) mixing said solution of step (i) with the 20 powder mixture of stage (ii).