WO2017027944A1

WO2017027944A1 - Detergent composition with good enzymatic stability and high performance for washing fabrics and surfaces

Info

Publication number: WO2017027944A1
Application number: PCT/BR2016/050190
Authority: WO
Inventors: Elvis Araújo BARRETO; Marcos Roberto Bettani; Josiane FABRI; André Messias Krell PEDRO; Juliana Pierobon STELLE; Rafael Fernando De Santi UNGARATO; Marcelo Attie VIEIRA; Adriana Guerra MAGANHOTTO
Original assignee: Oxiteno S.A. Indústria E Comércio
Priority date: 2015-08-14
Filing date: 2016-08-12
Publication date: 2017-02-23
Also published as: BR102015019623A2; BR112018002897A2; MX2018001840A; CO2018001287A2; AR105710A1; PE20181190A1; CL2018000388A1; BR112018002897B1

Abstract

The present invention relates to detergent compositions with good enzymatic stability and high performance for washing fabrics and surfaces, comprising a combination of surfactants and at least one enzyme. For that purpose, a composition is proposed comprising at least one surfactant selected from anionic, amphoteric and non-ionic surfactants, the anionic surfactant being at least sodium lauryl ether sulphate (SLES) or linear alkylbenzene sulphonate (LAS), and the amphoteric surfactant being at least amine oxide (AO) or cocamidopropyl betaine (CAPB). Furthermore, the at least one enzyme is selected from the group consisting of protease, amylase, mannanase, lipase, pectin lyase and cellulase.

Description

"DETERGENT COMPOSITION OF GOOD ENZYMATIC STABILITY AND HIGH PERFORMANCE FOR WASHING FABRICS AND SURFACES"

FIELD OF INVENTION

The present invention relates to good enzymatic stability and high performance detergent compositions for washing fabrics and surfaces comprising a combination of surfactants and at least one enzyme.

BACKGROUND OF THE INVENTION

The surfactant compounds are amphiphilic substances, that is, they have in their molecular structure groups with antagonistic characteristics. In all surfactant molecules there is a polar group that has affinity for water (and other polar compounds), called a hydrophilic group. In the same molecule, there is also the so-called hydrophobic group, which by its nonpolar nature, has no affinity for water, but rather for oily substances (or, generally, supporting substances), often called lipophilic grouping.

In summary, surfactants are substances that modify surface and interfacial tensions, resulting in a number of related properties and applications.

Alkyl sulphates, together with alkyl ether sulphates are the most widely used products as foam surfactants in hair cosmetics, liquid soaps, oral hygiene products, among other applications. Among the alkyl sulfates, the most important are lauryl sulfates that have wide application in the cosmetic industry. The main characteristics of alkyl sulfates are their high foaming power, high viscosity reserve, good water solubility, pleasant odor and complete biodegradability.

[005] Lauryl ether sulfates, by their differentiated properties, are More hydrophilic than their non-ethoxylated counterparts, they have low eye and skin irritability, low cloudiness, easy viscosity control from electrolyte addition, and greater resistance to water hardness.

Also, as anionic surfactants are alkyl sulfosuccinates, of excellent wetting power.

The prior art discloses some compositions used for cleaning produced from surfactant combinations.

US 7,608,573 refers to the use of nonionic and anionic surfactants and others (solvent and short synthetic chain). The cleaning composition can be used for washing clothes and surfaces.

[009] This reference claims a heavy natural cleansing composition consisting of sodium lauryl sulfate, amine oxic Cn, Ci2-amine oxic i ₄ at pH 7 to 13. Furthermore, it is mentioned the optional use of some materials such as dyes, bleaches, thickeners and enzymes.

US2010 / 0184633 mentions the use of sulfoestolide surfactants as well as their derivatives and salts. The composition is useful for stain removal applications.

This patent claims the use of a sulfo-solid surfactant with at least one additional surfactant. It is mentioned that the secondary surfactant could be selected from a group of surfactants, including lauryl ether sulfonate. A group of surfactants to stabilize foams is further suggested, in which the use of lauryl cocoamidopropyl betama and lauryl dimethyl amine oxide is mentioned.

US 2010/0234271 refers to the use of nonionic and anionic surfactants and others (solvent and short synthetic chain). The cleaning composition can be used for cleaning clothes, soft and hard surfaces and cleaners.

The composition consists of sodium lauryl sulfate and a hydrophobic synthetic surfactant selected from amine oxide. Optional ingredients such as enzymes, dyes, builders and fragrances are also described.

Further, it is mentioned that the composition does not contain some molecules, including alkyl ether sulfates, linear alkylbenzene sulfonate (LAS), linear alkylbenzene sulfonate acid (HLAS) or nonylphenol ethoxylate.

WO 2003/041667 describes a composition comprising a stabilized enzyme with at least 30% water. However, this reference aims to seek benefits in skin care (skin smoothness, skin softness, etc.). It is mentioned that the composition provides an enzyme-containing personal care product wherein the enzyme has high stability and activity.

First, this foregoing reveals a stabilized enzyme composed of an osmoprotectant selected from the group comprising oxide amine. The use of protease as an enzyme and the use of enzyme inhibitor selected from the group of aryl boronic acid derivatives are described.

It is disclosed that the composition comprises a surfactant from the anionic, nonionic, zwitterionic amphoteric and cationic surfactant group. The types of surfactants are restricted to alkyl ether sulfates, alkyl amidopropyl betaines, alkyl betaines and the like, including mixtures thereof.

The document further discloses an enzyme-containing personal care product wherein said enzyme is stable in storage and active in the skin.

However, the art still needs the development of an efficient surfactant system for cleaning compositions, especially liquid detergent for washing fabrics and surfaces, which, in combination with enzymes, can provide superior performance and physical and enzymatic stability with respect to the usual detergent compositions found on the market and described in the state of the art.

SUMMARY OF THE INVENTION

Broadly, the invention proposes a detergent composition comprising a combination of surfactants for use in washing fabrics and surfaces. The combination of surfactants comprises at least one anionic surfactant, an amphoteric surfactant and a nonionic surfactant and at least one enzyme. This combination ensures good enzymatic stability and better performance, allowing the use of a lower active content than commonly used on the market.

BRIEF DESCRIPTION OF THE FIGURES

The above and additional advantages will be more apparent to those skilled in the art from the description below and the accompanying figures:

Figure 1 shows a graph resulting from the enzymatic stability test at 30 ° C for the surfactant combinations 1, 2 and 3 defined below.

Figure 2 shows a graph resulting from the enzymatic stability test at 37 ° C for surfactant combinations 1, 2 and 3.

Figure 3 is a graph resulting from the oil and fat stain performance test of compositions containing surfactant combinations 1 and 2 prepared according to the present invention, and compositions 5 and 6 compatible with the state of the art.

Figure 4 shows a graph resulting from the protein performance test of surfactant combinations 1 and 2 prepared in accordance with the present invention, and prior art compositions 5 and 6.

Figure 5 shows a graph resulting from the starch performance test of surfactant combinations 1 and 2 prepared in accordance with the present invention, and prior art compositions 5 and 6. Figure 6 shows a graph resulting from the complex spot performance test of surfactant combinations 1 and 2 prepared in accordance with the present invention, and prior art compositions 5 and 6.

Figure 7 shows a graph resulting from the particulate spot performance test of surfactant combinations 1 and 2 prepared in accordance with the present invention, and prior art compositions 5 and 6.

Figure 8 is a graph resulting from the pectin stain performance test of surfactant combinations 1 and 2 prepared according to the present invention and prior art compositions 5 and 6.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a detergent composition comprising a combination of surfactants and at least one tissue and surface washing enzyme.

More specifically, the detergent composition of the present invention comprises a combination of surfactants comprising at least one anionic, amphoteric and nonionic surfactant selected from at least one enzyme.

The anionic surfactant is at least one of sodium lauryl ether sulfate (SLES) and linear alkylbenzene sulfonate (LAS) and the amphoteric surfactant is at least one of amine oxide (AO) and cocamidopropyl betaine (CAPB).

In addition, the nonionic surfactant used in the detergent composition prepared according to the present invention has a degree of ethoxylation ranging from 3EO to 10EO.

Preferably, the at least one enzyme is selected from the group comprising protease, amylase, mannanase, lipase, pectin lyase and cellulase.

More preferably, the protease enzyme is Savinase or

Liquanase and is present in the composition in a ratio ranging from 0.1% to 1%.

In addition, the enzymes further comprise a multi-enzyme mixture consisting of amylase, mannanase, lipase and pectin lyase, wherein this multi-enzyme mixture is present in the composition in a ratio ranging from 0.2% to 0.6%.

The total content of the surfactant combination present in the detergent composition of the present invention ranges from 6% to 20% by weight, significantly lower than the contents of the commonly marketed compositions.

The detergent composition produced according to the present invention has a pH range ranging from 7 to 10.

To prove the inventiveness of the surfactant combination of the present invention, enzymatic stability and performance tests were performed, which are presented below.

ENZYMATIC STABILITY TEST

For the enzymatic stability test, five surfactants were prepared with fixed mixing ratios:

Surfactant 1: SLES;

Surfactant 2: CAPB;

Surfactant 3: LAS (30%) / 7EO (70%);

Surfactant 4: AO (30%) / 10EO (70%);

Surfactant 5: SLES (30%) / 7EO (70%).

These surfactants were associated with the following enzymes: protease, amylase, mananase, lipase and pectin lyase, each tested individually.

More specifically, in combinations 1, 2, 3 and 4, protease Savinase was used, whereas in combination 5 the protease used was Liquanase.

For the enzymatic stability test, all proposed runs were prepared under stability conditions as follows:

- Temperature (° C): 30 and 37

- Time period (weeks): Start, 4 and 8

The approval criterion after 8 weeks was:

- "Excellent" performance (green band) if the results are above 70% to 100%;

- "Satisfactory" performance (yellow band) if results are between 50% and 70%;

- "Unacceptable" performance (red band) if results are below 50%.

The method for protease enzyme activity analysis was performed with the aid of Konelab 30 Analyzer at 0, 4 and 8 weeks and the results were provided in KNPU (S) SX.

Firstly, the dimethyl casein compound present in the standard solution prepared for the test is hydrolyzed by the proteolytic enzyme into small peptides as shown below:

The primary amino groups formed in this process react with trinitrobenzene sulfonic acid (TNBS) to form a colored complex as shown below:

The increase in absorption is proportional to the reaction rate and thus to the activity of the enzyme.

For the test, the following reagents / substrates were prepared:

- Dodecanol polyoxyethylene solution (Brij 35), 15% w / v

- Solution of 2,4,6-trinitrobenzene sulfonic acid 0,2% w / v.

- Sodium sulphite loading solution, NaS0 ₃ 20% w / v (1,59

M NaSO ₃ ).

- 0.05 M borate buffer, pH 9.0.

- N, N-Dimethyl casein 0.32%, pH 8.0 (DMC 0.32%).

- 0.32% DMC with S0 ₃ (0.064 M NaS0 _3), DMC-SX.

To prepare the standard solution, the following steps were taken:

(a) weigh a quantity of standard enzyme corresponding to 2,40 units of KNUP (S) SX;

b) Dissolve in 0.05 M borate buffer and pH 9.0 in a 500 mL volumetric flask;

c) Shake on a magnetic stirrer for 30 minutes;

d) The standard curve is a 7 point curve with a factor 4 between the lowest and highest standard points. The recommended total dilution volume is 1200 μL. Standard solutions are prepared by diluting the loading solution with 0.05 M borate buffer and pH 9.0 in a diluter directly into sample cups according to the table. below, down, beneath, underneath, downwards, downhill:

For preparation of the sample to be tested, a known enzyme content was used and proceeded as described below:

(a) Weigh approximately 0,5 - 1,0 g of sample and dissolve in a volumetric flask with 0,5 M borate buffer and pH 9,0;

b) Shake on a magnetic stirrer for 15 to 45 minutes; c) The samples are further diluted with 0.5 M borate buffer and pH 9.0 to achieve an activity of approximately 0.30 mKNPU (S) SX / ml;

d) Adding the surfactant combination according to the present invention.

After sample and reagent preparation, 0.32% DMC reagents with SO3 and 0.2% TNBS are placed in Konelab, along with the standard solution and sample.

The enzyme activity of the samples is determined with respect to a standard curve. Based on the abs / min results for standard enzymes, a standard with the activities of standard solutions in mKNPU (S) SX / mL is plotted on the x-axis of the graph, while the abs / min values of standard solutions are plotted on the y axis. To plot the graph, a logit / log4 algorithm is used.

The enzyme activity values of the diluted samples are taken from the standard curve. Sample activity is calculated using the following formula:

Activity KNUP (S) SX / g =, where

S = reading the standard curve in mKNPU (S) SX / ml;

V = Volume of the volumetric flask used in mL;

F = Dilution factor for second dilution;

W = sample weight in g; and

1000 = mKNPU (S) SX to conversion factor

KNPU (S) SX.

The method for activity analysis of the enzymes amylase, mannanase, lipase and pectin lyase is also performed by the Konelab 30 Analyzer at 0, 4 and 8 weeks and the results are provided in SNUX.

By this method, 1,4-alpha-D-glucanohydrolase in the samples and the alpha-glucosidase enzyme in the reagents hydrolyze the substrate (4,6-ethylidene (G) -p-nitrophenyl (Gi) -alpha-D -maltoeptaoside (ethylidene-G PNP)) to yellowish glucose and p-nitrophenol.

The rate of p-nitrophenol formation can be observed by the

Konelab 30. By expressing the reaction rate, it is possible to verify the enzymatic activity.

For the test, the following reagents / substrates were prepared:

- Brij 35 solution, 15% w / v;

- 3M calcium chloride stabilizer with 0.25% Brij loading solution;

- 1% stabilizer (0.03M calcium chloride with Brij

0.0025%);

To prepare the standard solution, proceed as follows:

(a) weigh a quantity of standard enzyme corresponding to 26,6 units of SNUX;

(b) transfer the standard to a 250 ml volumetric flask containing approximately 200 ml of demineralized water;

c) Add 2.5 ml of 3M calcium chloride stabilizer with 0.25% Brij loading solution and fill up to 250 ml with demineralized water (106.5 SNUX / ml);

d) Shake on a magnetic stirrer for at least 5 minutes;

e) From the loading solution the following standard solutions are prepared by dilution. The total volume is 1200 μΕ. The 1% stabilizer (0.03M calcium chloride with 0.0025% Brij) is used as the diluent for all subsequent dilutions. The standard curve is a 7 point curve with a factor 3 between the lowest and highest standard points.

Specimens to be tested should be diluted at least

50 times and prepared as described below:

(a) weigh approximately 1,0 g of sample and dissolve in a volumetric flask with demineralized water;

(b) Add demineralized water equivalent to about three quarters of the volume of the volumetric flask; c) Add 3 M calcium chloride stabilizer with 0.25% Brij loading solution equivalent to 1% of the total volume of the flask and fill with demineralized water;

d) Shake for approximately 15 minutes on a magnetic stirrer;

e) The samples are further diluted with 1% stabilizer (3 M calcium chloride with 0.25% Brij loading solution) in the diluter. Dilution in the diluter is done directly in the sample vial;

f) Adding the surfactant combination according to the present invention;

g) Each weighing is analyzed once in the Konelab analyzer.

The analysis of the samples comprises the following steps:

(a) pipette 200 μΐ alpha-glucosidase into the cuvettes; (b) Pipette 16 μΐ of standard or sample solution into the cuvettes; (c) alpha-glucosidase and enzyme solution are incubated for 300 seconds;

d) 20 μΐ of substrate is pipetted into the cuvettes. The glucosidase / amylase / substrate mixture is incubated for 180 seconds; e) Absorption is measured every 18 seconds. A total of seven absorption measurements are performed on each sample.

The activity of enzyme samples is determined with respect to a standard curve. A graph of the known concentration of the x-axis pattern versus the response of the Konelab 30 y-axis analyzer equipment is established by the Analytical Administration program using a logit / log4 algorithm.

[0063] Results are calculated automatically in the program.

Analytical Administration and sample enzyme activity in SNUX / g is calculated using the following formula:

[0064] SNUX activity / g = where

S = reading the standard curve in mSNUX / ml;

V = Volume of the volumetric flask in mL;

F = Dilution factor for second dilution;

W = sample weight in g; and

1000 = mSNUX to SNUX conversion factor.

Test results at 30 ° C are shown in the graph of the

Figure 1. It can be seen that the combination of surfactants 1, 2, 3 and 5 associated with enzymes presents optimal results and the combination of surfactant 4 presents satisfactory results.

Figure 2 shows results for the enzymatic stability test at 37 ° C, evidencing good stability of the surfactant combinations of the present invention, even under severe temperature and time conditions.

PERFORMANCE TEST

For the performance test, two combinations of surfactants with fixed mixing ratios according to the present invention and two surfactants known from the state of the art were prepared.

Combinations of surfactants prepared in accordance with present invention are presented below:

1) SLES / Oxide Amine (90/10);

2) SLES / Cocamidopropyl Betaine / Oxide Amine (80/10/10).

The surfactants known in the art and used in the comparative test are:

5) Linear Sodium Alkylbenzene Sulfonate / Sodium Alkyl Ether Sulfate / Alkylpolyoxylated

6) Linear Sodium Alkylbenzene Sulfonate / Sodium Alkyl Ether Sulfate / Nonionic surfactant Polyalkylethoxylate

The test was performed to compare the performance of surfactants with respect to cleaning stains that are most common to consumers. Stains were grouped to balance the stain load, avoiding excessive concentration of dirt in the same group. The list of spots used in the test is shown below:

Importantly, the same enzymes were employed in the test in order to make the comparison possible.

Figure 3 shows the performance result in the oil and fat group through the boxplot graph. It is noted that the performance of surfactant combinations 1 and 2 is clearly superior to surfactants 5 and 6 known in the art.

The same conclusion can be seen in the graphs of the

Figures 4 to 8.

From the results of the demonstrated tests, it can be concluded that the surfactant combinations prepared according to the present invention far outperform the surfactants known in the art with respect to various types of stains and dirt present on the fabric and surface.

Claims

1. Detergent composition of good enzymatic stability and high performance for washing fabrics and surfaces, characterized in that it comprises at least one anionic, amphoteric and nonionic surfactant selected;

wherein the anionic surfactant is at least one of sodium lauryl ether sulfate (SLES) and linear alkylbenzene sulfonate (LAS);

wherein the amphoteric surfactant is at least one of amine oxide (AO) and cocamidopropyl betaine (CAPB); and

at least one enzyme.

Composition according to Claim 1, characterized in that the nonionic surfactant has a degree of ethoxylation ranging from 3EO to 10EO.

Composition according to Claim 1 or 2, characterized in that the enzyme is selected from the group consisting of: protease, amylase, mannanase, lipase, pectin lyase and cellulase.

Composition according to any one of the preceding claims, characterized in that the protease enzyme is selected from savinase and liquanase and is in a ratio ranging from 0.1% to 1%.

Composition according to any one of the preceding claims, characterized in that the enzyme comprises a multi-enzyme mixture consisting of amylase, mannanase, lipase and pectin lyase.

Composition according to any one of the preceding claims, characterized in that the multi-enzyme mixture is present in the composition in a proportion ranging from 0.2% to 0.6%.

Composition according to any one of the preceding claims, characterized in that the surfactant combination content of the detergent composition is from 6% to 20% by weight.

Composition according to any one of the preceding claims, characterized in that the pH range ranges from 7 to 10.