KR20120039772A - Liquid detergent composition - Google Patents

Abstract

PURPOSE: A liquid detergent composition is provided to enhance phase stability at low temperature storage and to be specifically useful for a drum-typed washing machine. CONSTITUTION: A liquid detergent composition comprises a non-ionic surfactant which is represented by chemical formula 1: R1-O-(EO)x-(PO)y-H, an aliphatic acid salt, and a cationic polymer. In the chemical formula 1, R1 implies alkyl or alkenyl of C10-16 straight-chain or a branched chain. EO implies ethylene oxide, x indicates average addition moles of the ethylene oxide, and the values are 5-20. PO implies propylene oxide, Y indicates average addition moles of propylene oxide and the values are 0.5-5.

Description

Liquid detergent composition

The present invention relates to a liquid detergent composition, and more particularly, to a concentrated liquid detergent composition having high rinsing power against various contaminations and having excellent rinsing property and excellent phase stability at low temperature storage.

Recently, as interest in the environment has increased, interest in concentrated liquid detergents has increased, and the use of less washing water and less damage to clothing has been increased due to changes in the laundry environment. However, since the drum type washing machine uses a free-fall washing method, a large amount of bubbles are generated during washing, thereby lowering the rinsing efficiency. In order to solve this problem, various detergent compositions characterized by low foaming have been studied and proposed. However, there is still little suggestion for a detergent composition having satisfactory rinsability.

JP-A 1996-067896 discloses a detergent with foaming ability to control bubbles in the washing process and to the rinsing step by using a combination of specific amino alkyl modified silicone oils and inorganic silica or inorganic silica derivatives having a specific specific surface area. . However, the formulation of the detergent is a powder form and when the silicone oil and inorganic silica is applied to the liquid detergent has the disadvantage that the phase separation occurs.

In addition, in the case of liquid detergents, there are disadvantages in that the detergent composition becomes uneven due to phase separation of bubble control components during low temperature storage, or precipitation or insoluble component of insoluble components occurs. Receive.

The present invention was devised to solve the above-mentioned problems, and an object of the present invention is to provide a liquid detergent composition having excellent rinsing ability and excellent phase stability at low temperature storage while having high cleaning power against various contaminations.

In order to achieve the above object, the present invention is a non-ionic surfactant represented by the following formula (1); Fatty acid salts; And a cationic polymer, the liquid detergent composition comprising:

<Formula 1>

R ₁ -O- (EO) _x- (PO) _y -H

In Chemical Formula 1,

R ₁ means a straight or branched chain alkyl group or alkenyl group having 10 to 16 carbon atoms,

EO means ethylene oxide,

x represents the average added mole number of ethylene oxide, and is 5-20,

PO means propylene oxide,

y represents the average added mole number of a propylene oxide, and is 0.5-5.

In one embodiment of the present invention, the nonionic surfactant may be included in an amount of 40 to 80 parts by weight based on the whole composition.

In one embodiment of the present invention, the fatty acid salt may be included in an amount of 0.5 to 10 parts by weight based on the whole composition.

In addition, in one embodiment of the present invention, the cationic polymer may be included in an amount of 0.05 to 1 parts by weight based on the whole composition.

Fatty acid salts that may be used in the present invention are preferably, but are not limited to, alkali metal salts, alkaline earth metal salts, alkanol amine salts or alkyl alkanol amine salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms.

Cationic polymers that can be used in the present invention are preferably, but not limited to, copolymers of acrylamide and diallyldimethylammonium chloride or copolymers of acrylamide, diallyldimethylammonium chloride and acrylic acid.

In one preferred embodiment of the present invention, the liquid detergent composition of the present invention can be used in a drum type washing machine.

The liquid detergent composition of the present invention as described above,

First, it shows high washability and rinsing efficiency due to low bubble generation and fast rinsing property, which is suitable for washing and rinsing of drum type washing machines with low rinsing number.

Second, there is no phase separation even when stored for a long time at low temperature, there is no precipitation, suspended matter.

Third, the liquid detergent type is easy to measure when used, there is an advantage that the dust does not fly compared to the powder detergent, it can also be used directly applied to a specific area of high pollution. Powdered detergents also compensate for the disadvantages such as lumps that can occur during long-term storage.

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

In order to achieve the above object, the present invention is a non-ionic surfactant represented by the following formula (1); Fatty acid salts; And a cationic polymer, the liquid detergent composition comprising:

<Formula 1>

R ₁ -O- (EO) _x- (PO) _y -H

In Chemical Formula 1,

R ₁ means a straight or branched chain alkyl group or alkenyl group having 10 to 16 carbon atoms,

EO means ethylene oxide,

x represents the average added mole number of ethylene oxide, and is 5-20,

PO means propylene oxide,

y represents the average added mole number of a propylene oxide, and is 0.5-5.

The nonionic surfactants used in the present invention provide the cleaning power against various contaminations and have the advantage of low irritation.

In one embodiment of the present invention, the non-ionic surfactant may be included in 40 to 80 parts by weight, preferably 50 to 70 parts by weight based on the total composition. If the content of the nonionic surfactant is less than 40 parts by weight, the cleaning power may be lowered due to the characteristics of the present concentrated liquid detergent using a smaller amount than the general liquid detergent. When the content of the non-ionic surfactant exceeds 80 parts by weight, the phase stability may be lowered, and phase separation may occur when stored for a long time. When used in a drum type washing machine, the rinsing property may be lowered, and the commercial cost may be lowered due to high cost.

The fatty acid salt used in the present invention not only contributes to the improvement in washing power, but also reduces the amount of bubbles generated in the initial stage of washing so that the cleaning component does not remain in the garment, thereby improving rinsability in the drum type washing machine. In addition, when used in combination with the cationic polymer serves to further improve the rinsability of the non-ionic surfactant by reducing the amount of air bubbles as a whole from the initial to the final rinsing of the laundry.

The fatty acid salt used in the present invention may be in the form of neutralized saturated or unsaturated fatty acid having 12 to 18 carbon atoms with alkali metal, alkaline earth metal, alkanol amine or alkyl alkanol amine, but is not limited thereto.

In one embodiment of the invention, the fatty acid salts used are alkali metal ions such as sodium, potassium and the like; Alkaline earth metal ions such as magnesium and calcium; Alkanolamins such as ethanol amine, diethanolamine, and triethanolamine; Or one or more selected from salts having a cationic polarity such as alkyl alkanolamin such as monomethyl diethanolamin and dimethyl ethanolamin.

The fatty acid salt used in the present invention may be included in an amount of 0.5 to 10 parts by weight, and preferably 1 to 5 parts by weight, based on the total composition. If the amount is less than 0.5 parts by weight, the effect of increasing the rinsing property is insignificant, and when added in excess of 10 parts by weight may reduce the stability of the composition.

The cationic polymer used in the present invention acts continuously in the rinsing step when used in combination with the nonionic surfactant and the fatty acid salt to reduce the amount of bubbles generated and to bubble the bubbles to improve the rinsability, and the cleaning component is used for the clothing. It plays a role of not remaining in.

The cationic polymer used in the present invention may be a copolymer of acrylamide and diallyldimethylammonium chloride or a copolymer of acrylamide, diallyldimethylammonium chloride and acrylic acid.

In one embodiment of the invention, the cationic polymer used may be a single or a mixture thereof selected from the group consisting of polyquaternium-7, polyquaternium-39, preferably of acrylamide and diallyldimethylammonium chloride. Polyquaternium-7 which is a copolymer can be used.

Cationic polymer used in the present invention may be included in 0.05 to 1 parts by weight, preferably 0.05 to 0.5 parts by weight based on the whole composition. When included in less than 0.05 parts by weight the effect of increasing the rinsing is insignificant, and when included in more than 1 part by weight may be decontamination.

The cationic polymer used for this invention can use the molecular weight 1.0 * 10 <^3> -1.0 * 10 <^8> , Preferably it is 1.0 * 10 <^5> -1.0 * 10 <^6> . When the molecular weight is less than 1.0 × 10 ³ , the effect of increasing rinsing property is insignificant. The molecular weight is 1.0 × 10 ⁸ . If exceeded, decontamination may be reduced.

The liquid detergent composition of the present invention may further comprise a liquid paraffin oil. The liquid paraffin oil not only contributes to the improvement of washing power, but also serves as a rinse aid to reduce the amount of air bubbles and to reduce the amount of non-ionic surfactant remaining on the fabric at the last stage of washing to improve rinsability. In addition, there is also an effect of improving the rinseability of the nonionic surfactant when used in combination with the nonionic surfactant.

The liquid paraffin oil has a melting point of −40 to 5 ° C., a boiling point of 110 ° C. or more, and contains 12 to 40 carbon atoms.

The liquid paraffin oil may be included in an amount of 0.01 to 5 parts by weight, and preferably 0.01 to 3 parts by weight, based on the composition. When included in less than 0.01 parts by weight rinsing performance improvement effect may be difficult to achieve the object of the present invention with added liquid paraline oil, when contained in more than 5 parts by weight may reduce the washing power and the stability of the composition There is concern.

The liquid detergent composition of the present invention may further include an anionic surfactant to improve the washing power. The liquid detergent composition of the present invention can be used as an anionic surfactant known in the art without limitation, but preferably linear or branched alkylbenzene sulfonic acid, alkyl sulfuric acid, alkenyl sulfuric acid, alpha sulfone fatty acid ester, alpha olefin sulfide Phonic acid, alkyl ether sulfonic acid, alkyl ether carboxylic acid, alkenyl ether carboxylic acid, alkanesulfonic acid, sulfo succinic acid alkyl ester, acylamino alkanesulfonic acid, alkyl ester sulfonic acid, alkenyl ester sulfonic acid, alkyl ether, alkenyl ether and these Only one selected from the group consisting of salts or mixtures thereof can be used.

In a preferred embodiment of the present invention, alkylbenzenesulfonic acid or a salt thereof having an alkyl group having 10 to 20 carbon atoms; Polyoxyethylene alkyl ether sulfonic acid or its salt whose average carbon number of an alkyl group is 10-20, and ethylene oxide average addition mole number is 0.5-6; Alkyl or alkenyl ester sulfonic acid or its salt which has a C10-C20 alkyl group or alkenyl group; And it may include a single or a mixture thereof selected from the group consisting of alpha olefin sulfonic acid or a salt thereof having 10 to 20 carbon atoms.

Counter ions of such anionic surfactants include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium and calcium, alkanolamines such as ethanolamine, diethanolamine and triethanolamine, monomethyl diethanolamine and dimethyl ethanol. Those selected from those having a cationic polarity such as alkyl alkanolamines such as amines can be used.

The anionic surfactant may be included in an amount of 0.1 to 15 parts by weight, and preferably 0.1 to 10 parts by weight, based on the composition. When included in less than 0.1 part by weight, the effect of improving the washing power is insignificant, and when included in an amount exceeding 15 parts by weight, the stability of the composition may be lowered.

In addition, the liquid detergent composition according to the present invention may be used in combination with an appropriate amount of conventional additives such as solubilizers, enzymes, preservatives, chelating agents, fragrances, antifoaming agents and dyes in a range that does not impair the effects of the present invention. The solubilizer may be preferably propylene glycol, but is not limited thereto.

The additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight based on the composition, but may vary in content depending on the object, purpose, and cleaning method of the object to be cleaned, and the cleaning power for contamination adhered to the fiber. Alternatively, one of ordinary skill in the art can arbitrarily adjust the content thereof within a range not impairing human and environmental stability and storage stability.

The liquid detergent composition of the present invention includes water as the remaining components in addition to the above components. The components are mixed with water to form a liquid detergent composition.

It is preferable that the liquid detergent composition of the present invention is alkaline to obtain an effective cleaning power, and 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 can be effectively used in a drum type washing machine, which maintains excellent washing power and has excellent rinsing ability, so that a large amount of bubbles are generated during washing, thereby lowering washing efficiency and lowering rinsing efficiency.

Through the following Examples and Comparative Examples will be described in detail a preferred embodiment of the present invention. However, the configuration shown in the drawings and embodiments described herein is only one of the most preferred embodiment of the present invention and does not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

< Example  1 to 10> Preparation of Liquid Detergent Composition

The liquid detergent composition of the present invention was prepared by a conventional method known in the art, and the composition ratio thereof is shown in Table 1.

ingredient Example One 2 3 4 5 6 7 8 9 10 Nonionic Surfactants ^{1 )} 60 40 60 60 60 60 60 60 60 60 Fatty acid salt ^{2 )} 5 5 5 5 5 10 One 5 5 5 Cationic Polymer-1 ³⁾ 0.3 0.3 0.3 1.0 0.1 0.3 0.3 0.3 0.3 Cationic Polymer-2 ⁴⁾ 0.3 Propylene glycol 5 5 5 5 5 5 5 5 5 5 Floating paraffin oil One Anionic surfactant ^{5 )} 5 Additive ^{6 )} 2 2 2 2 2 2 2 2 2 2 water Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Sum 100 100 100 100 100 100 100 100 100 100

1) Nonionic surfactant: Polyoxyethylene propylene alkyl ether in which R is C12 75%, C14 25% mixed alkyl group in formula (1), and EO and PO average added molar sum is 9. (Ecosurf SA 9: Dowchemical).

2) Fatty acid salts: 14 saturated fatty acid salts neutralized with sodium.

3) Cationic polymer-1: cationic polymer having polyquaternium 7 (MERQUAT 550, Nalco company), molecular weight 1.6 × 10 ⁶ , acrylamide as monomer, DADMAC (diallyldimethylammonium chloride).

4) Cationic polymer-2: cationic polymer with polyquaternium 39 (MERQUAT 3330, Nalco company), molecular weight 1.6 × 10 ⁶ , acrylic acid, acrylamide and DADMAC as monomer.

5) Anionic surfactant: The linear alkyl benzene sulfonate (LAS) which neutralized the benzene sulfonic acid (ASCO 96; AKcamtech Co., Ltd.) which has an alkyl group of 10-14 carbon atoms with sodium.

6) Additives: Mixtures of preservatives, pigments and flavorings.

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

The liquid detergent composition of the comparative example was manufactured by the same method as the said Example, and the composition ratio is shown in Table 2.

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 Nonionic surfactant 60 60 60 60 60 60 85 30 Fatty acid salt 5 - 5 - 10 5 5 5 Cationic Polymer-1 - - 0.3 0.3 1.5 0.3 0.3 Cationic Polymer-3 ⁷⁾ 0.3 - - - - - - Propylene glycol 5 5 5 5 5 5 5 5 additive 2 2 2 2 2 2 2 2 water Balance Balance Balance Balance Balance Balance Balance Balance Sum 100 100 100 100 100 100 100 100

7) Cationic polymer-3: Cationic polymer having polyquaternium 6 (MERQUAT 100, Nalco company), molecular weight 1.6 × 10 ⁶ , DADMAC (Diallyl Dimethyl ammonium chloride) as monomer.

< Experimental Example  1> Rinseability  evaluation

Rinsing evaluation was performed using a front-load washing machine (LG Electronic). Washing temperature was adjusted to 40 ℃ and washed for 30 minutes, rinsing was carried out twice for 5 minutes each. Dewatering of the laundry was performed at 800 rpm for 5 minutes.

The sample used for the measurement used 20 ml of each of the compositions of Examples 1-10 and Comparative Examples 1-8, and 1.2 kg of cotton towels were used for the rinsability measurement.

Rinsing was determined according to the evaluation criteria shown in Table 3 based on the amount of bubbles generated in the rinsing step by marking the scale from 0 to 25 on the transparent window of the washing machine, the results are shown in Table 4 and Table 5.

Rinsing criteria ◎: Very good (bubble generation amount is less than indication scale 1) ○: Excellent (bubble generation amount indication scale 1-3) △: Normal (bubble generation amount indication scale 3-5) X: Poor (Bubble generation amount exceeds display scale 5)

Example
One Example
2 Example 3 Example
4 Example 5 Example 6 Example 7 Example
8 Example
9 Example 10 Rinseability ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎

Comparative example
One Comparative example
2 Comparative Example 3 Comparative example
4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Rinseability △ X △ △ ◎ ◎ △ ◎

According to Tables 4 and 5, the liquid detergent compositions of Examples are excellent in rinsing properties, but do not contain fatty acid salts or cationic polymers or are not copolymers of acrylamide and diallyldimethylammonium chloride as cationic polymers. It can be seen that the compositions of the comparative examples using homopolymers of allyldimethylammonium clyde have moderate or poor rinsing properties.

< Experimental Example  2> cleaning power rating

Detergency evaluation was performed using a stirred mixed detergent tester (Tergotometer, United States Testing Co., Inc.) mainly used for laboratory use. The tester was operated at a rotational RPM 120 at a cleaning power measurement temperature of 25 ° C., and the sample amount was 0.333 ml of the sample in 1 L of water. The washing time was performed twice for 10 minutes and for 3 minutes for rinsing.

The artificial contaminants used for the measurement were C12 (Center For Testmaterials BV) and 10D (wfk Testgewebe GmbH). Each contaminated cloth was a contaminated cloth made of cotton, oil, protein contamination and sebum contamination, cut into a size of 8 × 8 cm and used for 6 samples.

For each contaminated cloth before and after washing, the cleaning effect was determined by measuring the whiteness with a colorimeter (Japan testing Co., INC.) And determining the cleaning power calculated according to the following equation according to the evaluation criteria shown in Table 6, and the result Are shown in Table 7 and Table 8.

% Cleaning power = {(C-B) / (A-B)} * 100

A: whiteness of white cloth

B: contaminant whiteness before cleaning

C: contaminant whiteness after washing

Cleaning power evaluation criteria
(C12; face) ◎ very good (more than 45% of washing power) ○: Excellent (washing power 40-45%) △: normal (washing power 35-40%) X: Poor (less than 35%)
Cleaning power evaluation criteria
(10D; face) ◎ very good (more than 45% of washing power) ○: Excellent (washing power 40-45%) △: normal (washing power 35-40%) X: Poor (less than 35%)

Example
One Example
2 Example 3 Example
4 Example 5 Example 6 Example 7 Example
8 Example
9 Example
10 C12; if ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 10D; if ◎ ○ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎

Comparative example
One Comparative example
2 Comparative Example 3 Comparative example
4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 C12; if ◎ ◎ ◎ ◎ ◎ X ◎ △ 10D; if ◎ ◎ ◎ ◎ ◎ X ◎ X

As shown in Table 7 and Table 8, the compositions of the examples were all excellent in washing power, but the composition of Comparative Example 6 in which the amount of the non-ionic surfactant is used less than 10 parts by weight and the amount of the cationic polymer used in Comparative Example 6 In the case of, the cleaning power is poor.

< Experimental Example  3> Low temperature phase stability evaluation

The detergent compositions of Examples and Comparative Examples were stored at low temperature (-5 ° C.) for 10 days and then the low temperature phase stability was determined according to the criteria shown in Table 9, and the results are shown in Table 10 and Table 11.

Low temperature phase stability ◎: Very good (no phase separation phenomenon, excellent fluidity) ○: Excellent (fine suspension occurs, fluidity is normal) △: moderate (severe suspension, low fluidity) X: Poor (phase separation, no fluidity)

Example
One Example
2 Example 3 Example
4 Example 5 Example 6 Example 7 Example
8 Example
9 Example 10 Low temperature
Phase stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Comparative example
One Comparative example
2 Comparative Example 3 Comparative example
4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Low temperature phase stability ○ ◎ ◎ ◎ X ○ △ X

According to Tables 10 and 11, the liquid detergent compositions of Examples 1 to 8, while the low temperature phase stability is very excellent, the composition of Comparative Example 8 in which the non-ionic surfactant exceeds 40 parts by weight, the amount of the fatty acid salt used a comparative example For the composition of 5 it can be seen that the low temperature phase stability is moderate or poor.

As described above, the liquid detergent composition of the present invention has excellent washing power and low-temperature phase stability against various contaminations, and particularly, it has excellent rinsing properties, and is suitable for use in a drum washing machine having a lot of bubbles and a low rinsing water as well as a general washing machine. .

Claims (7)

Nonionic surfactant represented by the formula (1);
Fatty acid salts; And
A liquid detergent composition comprising a cationic polymer:
<Formula 1>
R ₁ -O- (EO) _x- (PO) _y -H
In Chemical Formula 1,
R ₁ means a straight or branched chain alkyl group or alkenyl group having 10 to 16 carbon atoms,
EO means ethylene oxide,
x represents the average added mole number of ethylene oxide, and is 5-20,
PO means propylene oxide,
y represents the average added mole number of a propylene oxide, and is 0.5-5. The liquid detergent composition of claim 1, wherein the nonionic surfactant is included in an amount of 40 to 80 parts by weight based on the whole composition. The liquid detergent composition of claim 1, wherein the fatty acid salt is included in an amount of 0.5 to 10 parts by weight based on the total composition. The liquid detergent composition of claim 1, wherein the cationic polymer is included in an amount of 0.05 to 1 parts by weight based on the whole composition. The liquid detergent composition according to claim 1, wherein the fatty acid salt is an alkali metal salt, alkaline earth metal salt, alkanol amine salt or alkyl alkanol amine salt of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. The liquid detergent composition of claim 1, wherein the cationic polymer is a copolymer of acrylamide and diallyldimethylammonium chloride or a copolymer of acrylamide, diallyldimethylammonium chloride and acrylic acid. The liquid detergent composition of claim 1, wherein the liquid detergent composition is used in a drum type washing machine.