KR101087354B1 - Structured liquid detergent composition - Google Patents

Abstract

The present invention relates to a structured liquid detergent composition, wherein the liquid detergent composition of the present invention comprises (a) anionic surfactant; (b) a nonionic surfactant represented by the following formula (1); (c) electrolytes; And (d) a cationic polymer:
<Formula 1>
RO- (EO) xH
The liquid detergent composition of the present invention does not degrade the shear peeling property even after long-term storage at room temperature or high temperature to provide the desired flow characteristics, it is excellent in phase stability because no phase separation occurs.

Description

Structured liquid detergent composition

The present invention relates to a structured liquid detergent composition, and in particular, to maintain the necessary shear properties by maintaining the shear thinning properties intact even during long-term storage at high temperature, excellent phase stability does not occur phase separation It relates to a structured liquid detergent composition.

Structured liquid detergent compositions exist in which the detergent active material is dispersed in an aqueous phase in a lamellar droplet structure, which is a planar lamellar structure and / or spherulite. Lamellar droplets have an onion-like structure in which the detergent active material is a concentric double layer, and water or electrolyte is trapped between the layers. In general, structured liquid detergent compositions can be used to impart consumer desired flow and appearance properties due to the presence of lamellar droplet structures as well as suspend particulate solids that are insoluble in water.

However, in the case of preparing a suspension or the like using such a lamellar droplet structure, as the volume fraction of the lamellar droplets increases, the viscosity may increase and the viscosity may be increased to the point where the product cannot follow. It is necessary to have this shear peeling characteristic. In addition, the liquid detergent composition including the lamellar droplet structure has a problem in that the dispersed phase and the aqueous phase are separated during prolonged storage at a high temperature or even room temperature, thereby weakening phase stability and shear peeling characteristics.

In order to solve this problem, various detergent compositions having improved shear peeling properties and phase stability during long-term storage have been studied and proposed, but the composition having a surfactant content of about 30% is insufficient for a satisfactory viscosity and phase stability. . US 2005/0176610 A1 attempts to improve the long-term storage stability of gel detergents on lamellae using specific amounts of non-neutralized fatty acids, but does not mention storage stability at high temperatures due to improved stability at room temperature. US 6174846 B1 discloses a liquid detergent composition with a small change in viscosity even when repeated freezing and thawing using a specific hydrophilic emulsifier dipolyhydroxystearate, but does not mention viscosity and phase stability at high temperatures. not.

An object of the present invention to solve the above problems is to maintain the shear thinning properties intact even in the long-term storage at high temperature as well as to give the necessary flow characteristics, structured structure does not occur phase separation is excellent It is to provide a liquid detergent composition.

The present invention to achieve the above object,

(a) anionic surfactants;

(b) a nonionic surfactant represented by the following formula (1);

(c) electrolytes; And

(d) providing a structured liquid detergent composition comprising a cationic polymer:

<Formula 1>

RO- (EO) x-H

(In Formula 1,

R is a straight or branched chain alkyl or alkenyl group having 10 to 15 carbon atoms,

EO is ethylene oxide,

x represents the average added mole number of ethylene oxide, and is 7-15.)

The electrolyte may be a halide of alkali metal or ammonium, a nitrate of sodium metal or ammonium or sodium citrate.

The cationic polymer may be used alone or a mixture thereof selected from the group consisting of polyquaternium-7, polyquaternium-10, polyquaternium-11, and polyquaternium-46.

The anionic surfactant may be included in 5 to 20 parts by weight based on the composition.

The nonionic surfactant may be included in an amount of 5 to 15 parts by weight based on the composition.

The electrolyte may be included in an amount of 5 to 15 parts by weight based on the composition.

The cationic polymer may be included in an amount of 0.01 to 1 part by weight based on the composition.

The structured liquid detergent composition of the present invention may have shear peel properties to impart the desired viscosity. In other words, it does not flow out of the container during weighing and is convenient to use with little force.

The composition of the present invention is excellent in phase stability because the shear peeling property does not deteriorate and phase separation does not occur even after long-term storage at room temperature or high temperature.

The composition of the present invention has the advantage of being easy to weigh when used as a liquid gel type, dust does not fly compared to the powder detergent, and can be used directly applied to a specific area with high contamination, as well as powder detergent can occur when stored for a long time The disadvantages of lumping are also compensated for.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

Structured liquid detergent compositions of the present invention comprise (a) anionic surfactants; (b) nonionic surfactants; (c) electrolytes; And (d) a cationic polymer.

The liquid detergent composition of the present invention includes two or more surfactants and an electrolyte, and the surfactant has an onion-like structure composed of concentric double layers, and has a lamellar droplet structure in which water or an electrolyte is trapped between the layers, and has the lamellae. The droplet structure is a form dispersed in an aqueous phase. In addition, the liquid detergent composition of the present invention can not only suspend solid particles by being structured as described above, but also have shear thinning properties to provide desired fluidity, and excellent high temperature stability.

The (a) anionic surfactant plays a role in imparting a cleaning power to the composition.

The anionic surfactant can be used without limitation to those known in the art, specifically, a sulfate-based, sulfonate-based or other anionic surfactant can be used.

Specifically, the sulfate-based surfactant may be an alkyl sulfate represented by the following Chemical Formula 1 or an alkyl ether sulfate represented by the following Chemical Formula 2:

<Formula 1>

ROSO ₃ M

In Chemical Formula 1, R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably about 10 to 16 carbon atoms, more preferably about 12 to 14 carbon atoms, and M is ammonium, sodium, potassium and mono-, di-, triethanol It is a water soluble cation selected from the group consisting of amines. Specific examples of the sulfate-based surfactants include fatty alcohol sulfates (AS) having 10 to 18 carbon atoms, fatty alcohol ethoxy sulfates (AES) having 10 to 16 carbon atoms, and the like. In more detail, sodium lauryl sulfate, sodium laureth sulfate, ammonium lauryl sulfate, ammonium laureth sulfate and the like may be used, but are not limited thereto.

<Formula 2>

RO (C ₂ H ₄ O) _n SO ₃ M

In Chemical Formula 2, R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably about 10 to 16 carbon atoms, more preferably about 12 to 14 carbon atoms, and n is an integer of 1 to 10 carbon atoms. That is, the alkyl ether sulfate may contain 1 to 10 moles of ethylene oxide per molecule. M is a water soluble cation selected from the group consisting of ammonium, sodium, potassium and mono-, di-, triethanol amines.

Specifically, the sulfonate-based surfactant may be a straight alkyl benzene sulfonate having 10 to 14 carbon atoms (LAS), an alpha olefin sulfonate having 12 to 18 carbon atoms (AOS), and the like, and sodium, potassium, magnesium, and ammonium salts thereof. And ethanol amine salts can also be used.

Specific examples of the other anionic surfactants include sodium, magnesium, ammonium salts and ethanol amine salts such as fatty acids and alkylsulfo succinic acid. The said anionic surfactant can be used individually or in mixture of 2 or more types of anionic surfactant mentioned above.

The anionic surfactant may be included in 5 to 20 parts by weight based on the composition. If less than 5 parts by weight of the liquid detergent composition is not only difficult to structure, but also difficult to have a shear peeling properties, when added in excess of 20 parts by weight, the use of a high viscosity increase, low usability, high cost burden has a problem of low commerciality There may be.

The (b) nonionic surfactant has excellent washing power and forms a lamellar droplet structure together with the anionic surfactant.

The nonionic surfactant may be preferably represented by the following general formula (1):

<Formula 1>

RO- (EO) x-H

In Formula 1, R is a linear or branched alkyl group or alkenyl group having 10 to 15 carbon atoms, EO means ethylene oxide, and x represents an average added mole number of ethylene oxide, preferably 7 to 15 days. have. If the added mole number of ethylene oxide is within the above range, the cleaning power is excellent and the detergent may not be agglomerated and solubility may be improved.

The nonionic surfactant may be included in an amount of 5 to 15 parts by weight based on the composition. If it is included in less than 5 parts by weight, the washing power is reduced and performance as a laundry detergent may be lowered. If it is added in excess of 15 parts by weight, the phase stability may be lowered and phase separation may occur when stored for a long time, and due to high cost burden, it is not commercially available. Losing can be a problem.

The (c) electrolyte serves as a structuring agent for structuring the surfactant used in the present invention and allows the structured liquid detergent composition to have shear peeling properties.

The electrolyte is a salt of a monovalent anion and a monovalent cation comprising an alkali metal or ammonium halide, in particular an alkali metal or ammonium halide, alkali metal or ammonium such as, for example, potassium chloride, sodium chloride, potassium iodide, sodium bromide and ammonium bromide Nitrate or sodium citrate may be used, but is not limited thereto. Preferably sodium chloride, sodium citrate or mixtures thereof can be used.

The electrolyte may be included in 5 to 15 parts by weight based on the composition. When included in less than 5 parts by weight, it is difficult to structure the liquid detergent composition, when included in more than 15 parts by weight, the stability of the liquid detergent composition is lowered due to problems such as phase separation during high temperature storage.

The cationic polymer (d) serves to maintain the shear peeling property when the structured liquid detergent composition is stored at a high temperature or at room temperature for a long time, and improves phase stability.

Specifically, the cationic polymer may be used alone or a mixture thereof selected from the group consisting of polyquaternium-7, polyquaternium-10, polyquaternium-11, and polyquaternium-46. Preferably, polyquaternium-7 which is a copolymer of acrylamide and diaryldimethyl ammonium chloride can be used.

The cationic polymer may be included in an amount of 0.01 to 1.0 parts by weight, and preferably 0.1 to 0.5 parts by weight, based on the composition. When included in less than 0.01 parts by weight, the phase stability effect at high temperature storage is insignificant, when included in excess of 1.0 parts by weight may reduce the shear peeling properties and washing power of the viscosity.

The liquid detergent composition of the present invention comprises an additive which is a single or mixture thereof selected from the group consisting of preservatives, enzymes, flavors, silicone antifoams and dyes according to the needs of those skilled in the art.

The additive may be included in an amount of 0.01 to 15 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight, based on the composition. The content may vary depending on the object, purpose and cleaning method of the object to be cleaned, and a person skilled in the art can arbitrarily adjust the content within the range that does not impair the washing power or the human and environmental stability and storage stability against contamination adhered to the fiber. .

The liquid detergent composition of the present invention includes water as the remaining components in addition to the above components. Water may be present trapped inside the lamellar droplet structure.

In addition, the liquid detergent composition of the present invention is preferably alkaline to obtain an effective cleaning power, the pH of the aqueous solution containing the above-mentioned components is preferably 8.0 to 12. High pH above 12 is not safe for home use. The pH can be adjusted by adding a suitable alkaline substance.

The liquid detergent composition of the present invention is prepared by mixing the aforementioned components by conventional methods known in the art. Of the above-mentioned components, the components serving as structuring agents are mixed last to structure the liquid detergent composition. The liquid detergent composition prepared in this manner has a shear peeling characteristic, even when stored at high temperature, the shear peeling characteristic does not deteriorate, and thus has a necessary flow characteristic, and phase separation does not occur, and thus phase stability is excellent.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. This is for the purpose of illustrating the invention only, and thus the scope of the invention is not limited.

< Example  1 to 9> Preparation of Liquid Detergent Composition

To prepare a liquid detergent composition structured by conventional methods known in the art with the composition of Table 1 below. In Table 1, the unit is parts by weight, and the sum is 100.

ingredient Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example
8 Example 9 Anionic Surfactants 1 ¹⁾ 10 10 10 10 10 10 10 10 10 Anionic surfactant 2 ²⁾ 5 5 5 - 5 5 5 5 5 Nonionic Surfactants ^{3 )} 5 10 15 5 5 5 5 5 5 Sodium chloride 10 10 10 10 5 15 10 10 10 Polyquaternium-7 ⁴⁾ 0.5 0.5 0.5 0.5 0.5 0.5 0.1 1.0 0.01 Additive ^{5 )} 5 5 5 5 5 5 5 5 5 water Balance Balance Balance Balance Balance Balance Balance Balance Balance pH (adjust with NaOH) 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0

1) Straight-chain alkyl benzene sulfonate (LAS) neutralized with benzene sulfonic acid (ASCO 96; AKCamtec Co., Ltd.) having an alkyl group having 10 to 14 carbon atoms with sodium

2) Alkyl ethoxy sulfate (AES) neutralized with sodium with 3 moles of ethylene oxide added to a fatty alcohol having 10 to 16 carbon atoms

3) Polyoxyethylene alkyl ether (AEO) wherein R is C ₁₂ 75%, C ₁₄ 25% mixed alkyl group in Formula 1, EO alone has an average added mole number of 9 moles and HLB value of 13.4

4) Average molecular weight is 1.6 x 10 ⁶ (GPC, MALLS)

5) mixture of preservatives, pigments, silicone antifoams, enzymes and flavorings

< Comparative example  1 to 8> Preparation of Liquid Detergent Composition

To prepare a liquid detergent composition in the same manner as in the above Example 2 composition. In Table 2, the unit is parts by weight, and the sum thereof is 100.

ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative example 7 Comparative example
8 Anionic Surfactants 1 ¹⁾ 3 15 10 10 10 10 10 10 Anionic surfactant 2 ²⁾ - 10 5 5 5 5 5 5 Nonionic Surfactants ^{3 )} 10 10 20 5 5 5 10 3 Sodium chloride 10 10 10 3 20 10 10 10 Polyquaternium-7 ⁴⁾ 0.5 0.5 0.5 0.5 0.5 - 1.5 0.5 Additive ⁵⁾ 5 5 5 5 5 5 5 5 water Balance Balance Balance Balance Balance Balance Balance Balance pH (adjust with NaOH) 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0

1) straight-chain alkyl benzene sulfonate (LAS) obtained by neutralizing benzene sulfonic acid (ASCO 96; AKCamtec Co., Ltd.) having an alkyl group having 10 to 14 carbon atoms with sodium;

2) Alkyl ethoxy sulfate (AES) neutralized with sodium with 3 moles of ethylene oxide added to a fatty alcohol having 10 to 16 carbon atoms

3) Polyoxyethylene alkyl ether (AEO) wherein R is C ₁₂ 75%, C ₁₄ 25% mixed alkyl group in Formula 1, EO alone has an average added mole number of 9 moles and HLB value of 13.4

4) Average molecular weight is 1.6 x 10 ⁶ (GPC, MALLS)

5) mixture of preservatives, pigments, silicone antifoams, enzymes and flavorings

< Experimental Example  1> Shear Peeling Characteristics and Fluidity Evaluation

The measurement of shear peeling properties was carried out using a rotary viscometer (Brookfield RVT). The measurement temperature of the viscosity was measured while changing the rotational speed of a viscometer to 5, 20 at 25 degreeC. The spindle number used was measured using No. 5, and the composition of the examples and the comparative example was measured in a 500 ml beaker while maintaining a constant temperature and humidity conditions.

Judging of the shear peeling characteristics is determined by measuring the viscosity at the rotational speed 5, 20 using a rotational viscometer, calculating the shear peeling value calculated according to the following formula, and then determining the shear peeling characteristic and fluidity according to the evaluation criteria shown in Table 3. The results are shown in Table 4 and Table 5.

* Shear Peel Value = (A-B) / 100

A: Viscosity at Speed 5

B: Viscosity at Speed 10

Shear Peeling Characteristics
○: excellent (shear peeling value 300 or more) (Triangle | delta): Normal (shear peeling value 100 or more and less than 300) X: Poor (less than 100 shear peeling number)
liquidity
○: excellent (30,000 cP or less) △: normal (30,000 to 50,000 cP) ×: defective (more than 50,000 cP)

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example
8 Example 9 Shear peelability ○ ○ ○ ○ △ ○ ○ ○ ○ liquidity ○ ○ △ ○ ○ △ ○ ○ ○

ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative example
8 Shear peelability × △ △ × △ ○ × × liquidity ○ × × ○ × ○ ○ ○

As shown in Tables 4 and 5, most of the compositions of Examples were excellent in shear peeling properties and flowability, and the compositions of Comparative Examples were generally poor in shear peeling property and fluidity. In particular, it can be seen that the compositions of Comparative Examples 1 and 4 containing less anionic surfactant and sodium chloride have poor shear peelability, and that the compositions of Comparative Examples 2 and 5 containing more anionic surfactant and sodium chloride have poor fluidity.

< Experimental Example  2> high temperature stability evaluation

In the high temperature phase stability evaluation, the detergent compositions of the Examples and Comparative Examples were stored at high temperature (40 ° C.) for 4 weeks, and then visually observed the phase stability of the composition based on the criteria shown in Table 6 to determine the high temperature phase stability. The results are shown in Tables 7 and 8.

Shear peeling properties for high temperature storage were evaluated according to the criteria as in Table 3 above, and the results are shown in Tables 7 and 8.

Phase stability ◎ very good (no phase separation phenomenon) ○: Excellent (fine phase separation occurs) △: normal (partial phase separation) ×: defective (complete phase separation)

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example
8 Example 9 Phase stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Shear peelability ○ ○ ○ ○ △ ○ ○ ○ ○

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative example 7 Comparative example
8 Phase stability × △ △ × △ × △ △ Shear peelability × △ △ × △ ○ × ×

According to Table 7 and Table 8, in the case of the liquid detergent composition of the embodiment it can be seen that not only the phase stability is very excellent during long-term storage at high temperature but also maintains the shear peeling characteristics. On the other hand, the compositions of Comparative Examples 1 and 4 containing less anionic surfactant or sodium chloride had poor phase stability. In addition, the composition of Comparative Example 6 containing no cationic polymer maintained shear peelability but was poor in phase stability. Therefore, it can be seen that the cationic polymer should be included in order to maintain the shear peelability and to provide excellent phase stability when stored at a high temperature for a long time.

As described above, the liquid detergent composition of the present invention is a composition in which the detergent active material is structured into a lamellar droplet structure including two or more surfactants and an electrolyte, which has shear peeling properties to suspend solid particles and provide desired flow characteristics. In addition, even after long-term storage at high temperature, the shear peeling characteristics are maintained and the phase stability is excellent, so that no phase separation occurs.

Claims (7)

(a) anionic surfactants;
(b) a nonionic surfactant represented by the following formula (1);
(c) electrolytes; And
(d) a structured liquid detergent composition comprising a cationic polymer:
<Formula 1>
RO- (EO) xH
(In Formula 1,
R is a straight or branched chain alkyl or alkenyl group having 10 to 15 carbon atoms,
EO is ethylene oxide,
x represents the average added mole number of ethylene oxide, and is 7-15.) The method of claim 1,
Structured liquid detergent composition, characterized in that the electrolyte is a halide of alkali metal or ammonium, nitrate or sodium citrate of alkali metal or ammonium. The method of claim 1,
Wherein said cationic polymer is a sole or mixture thereof selected from the group consisting of polyquaternium-7, polyquaternium-10, polyquaternium-11 and polyquaternium-46. The method of claim 1,
Structured liquid detergent composition, characterized in that the anionic surfactant is included in 5 to 20 parts by weight based on the composition. The method of claim 1,
A structured liquid detergent composition, wherein the nonionic surfactant is included in an amount of 5 to 15 parts by weight based on the composition. The method of claim 1,
Structured liquid detergent composition, characterized in that the electrolyte is contained in 5 to 15 parts by weight based on the composition. The method of claim 1,
A structured liquid detergent composition, wherein the cationic polymer is included in an amount of 0.01 to 1.0 parts by weight based on the composition.