KR102166028B1 - Liquid detergent composition - Google Patents

Abstract

The present invention relates to a liquid detergent composition. More specifically, the liquid detergent composition of the present invention controls the viscosity using an amphoteric surfactant without using a thickener or a structured surfactant system, and secures stability while containing an alkaline substance for long-term storage and use. It is stable and can maintain high transparency, has excellent usability, and is economical.

Description

Liquid detergent composition {LIQUID DETERGENT COMPOSITION}

The present invention relates to a liquid detergent composition. More specifically, the present invention relates to a liquid detergent composition that uses an amphoteric surfactant to control viscosity, improve transparency and phase stability, without using a thickener or structured surfactant system.

In general, a thickener is used to adjust the formulation of a liquid detergent, evenly disperse the composition or active ingredient in the liquid detergent, and maintain the phase stability of the product for a long time. Thickeners widely used in liquid detergents include thickeners such as acrylic acid-based synthetic polymers, and natural thickeners such as colloidal silica or gums and celluloses are also used.

For example, in International Patent Application WO93/021299, baking soda is dispersed using an acrylic acid-based polymer thickener, and European Patent No. 630179 is a natural gum (natural gum) for stabilization of liquid detergent compositions containing enzyme components. gum) is applied.

However, in general, acrylic acid-based polymer thickeners have a disadvantage of increasing the cost when liquid detergent is applied, and when an acrylic polymer that is difficult to dissolve in water is applied, a premixer step of solubilizing in water using a homomixer must be added. There are drawbacks. In addition, although xanthan gum or cellulose is more economical than acrylic polymer thickeners, a heating process is required to solubilize in water, and phase stability is weakened under conditions of acid, alkali, low temperature and high temperature. Recently, some raw materials have significantly improved water solubility by supplementing these shortcomings of acrylic acid, gum, and cellulose thickeners, but they are expensive, so the economic feasibility decreases when applied to products. There is a drawback that it does not slip, but rather slips or does not dissolve easily in water.Even though the dispersibility of effective particles and microbubbles is good with a high viscosity using a thickener, when applied to liquid detergents, the flow is poor, making it uncomfortable to use. I can.

Therefore, as in the prior art, it does not use a thickener that is expensive or difficult to process when applied, and is economical as a combination of a surfactant and an electrolyte, and has excellent dispersion stability at room temperature and high temperature, but has good flowability and excellent usability, and cleaning power There is a need for development for this excellent liquid detergent composition.

The present invention is to solve the above problems, an object of the present invention, anionic surfactant or nonionic surfactant; Amphoteric surfactants; And an alkaline substance; by providing a liquid detergent composition comprising an amphoteric surfactant and one or more surfactants, a stable liquid detergent capable of stabilizing an alkaline substance and maintaining a transparent phase by controlling the viscosity It is to provide a composition.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present invention, anionic surfactant 1 to 60% by weight or nonionic surfactant 1 to 60% by weight; 1 to 30% by weight of zwitterionic surfactant; And 0.5 to 15% by weight of an alkaline substance; provides a liquid detergent composition comprising.

The zwitterionic surfactant is a group consisting of amino propyl betaine having 8 to 22 carbon atoms, carboxy betaine having 8 to 22 carbon atoms, disodium coco ampodiacetate having 8 to 22 carbon atoms, and sulfo betaine having 8 to 14 carbon atoms One or more can be selected from.

The alkali substance is a salt of a monovalent or polyvalent organic or inorganic acid, bicarbonate, carbonate, phosphate, polyphosphate, pyrophosphate, triphosphate, tetraphosphate, silicate, metasilicate, polysilicate, hydroxide, alkali metal salt, and mixtures thereof One or more may be selected from the group consisting of.

The liquid detergent composition may have a transparency of 1 to 30 NTU.

The liquid detergent composition may have a viscosity of 50 to 1000 cP.

The liquid detergent composition further comprises one or more additives selected from the group consisting of an organic solvent, a detergent adjuvant, a stabilizer, an enzyme, a preservative, a fragrance, a dye, a viscosity modifier, a metal ion sealant, a thickener, a solubilizer, and a pH adjuster. can do.

The pH of the liquid detergent composition may be 8 to 12.

The present invention provides a liquid detergent composition that maintains transparency and is stable even at high temperatures by stabilizing an alkaline substance and adjusting the viscosity by using the viscoelastic characteristics of an amphoteric surfactant and one or more surfactants mixed without the use of a thickener. By doing so, it is possible to solve the problem of the conventional liquid detergent, which has a phenomenon in which precipitates are generated or becomes opaque when an alkaline substance is contained, and while maintaining the stability and transparency of the liquid detergent, it is possible to increase cleaning power.

Hereinafter, embodiments of the present invention will be described in detail. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms used in the present specification are terms used to properly express a preferred embodiment of the present invention, which may vary depending on the intention of users or operators, or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the contents throughout the present specification.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

The liquid detergent composition of the present invention comprises 1 to 60% by weight of an anionic surfactant or 1 to 60% by weight of a nonionic surfactant; 1 to 30% by weight of zwitterionic surfactant; And 0.5 to 15% by weight of an alkaline substance.

The anionic surfactant is preferably a sulfonate-based anionic surfactant, a sulfate-based anionic surfactant, or a mixture thereof.

In the case of products that must exhibit detergency, ionic surfactants, especially anionic surfactants, are known to have excellent detergency, and if two or more mixtures are used than a single anionic surfactant, synergistic effect in detergency is achieved. As can be seen, it is preferable to use a mixture of a sulfonate-based anionic surfactant and a sulfate-based anionic surfactant.

Preferred sulfonate-based anionic surfactants include alkylbenzene sulfonates, olefin sulfonates, secondary alkane sulfonates, alpha sulfonate methyl/ethyl esters, or these, wherein the alkyl group is a linear or branched alkyl having 9 to 18 carbon atoms. Mixtures of can be used. More specifically, an alkylbenzene sulfonate having 9 to 15 carbon atoms, preferably an alkylbenzene sulfonate having an alkyl group having 12 to 15 carbon atoms, or an alkane sulfonate having 12 to 18 carbon atoms, preferably an alkane sulfonate having 14 to 16 carbon atoms Nates, or olefin sulfonates having 8 to 18 carbon atoms, preferably olefin sulfonates having 12 to 18 carbon atoms can be used. As another sulfonate-based anionic surfactant, esterified products of alpha sulfo fatty acids, such as coconut oil, palm kernel oil, and alpha-sulfonate methyl/ethyl esterified products of tallow fatty acids may also be used.

A preferred sulfate-based anionic surfactant may be an alkyl ether sulfonate represented by the following formula (1),

In the formula of Formula 1,

R ₁ is an alkyl group having 8 to 16 carbon atoms, preferably an alkyl group having 10 to 16 carbon atoms, more preferably an alkyl group having 12 to 14 carbon atoms,

M is a cationic salt, preferably sodium, potassium, ammonium or alkanol ammonium, more preferably sodium,

n is an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 2 to 5.

As another preferred sulfate-based anionic surfactant, a sulfuric acid monoester compound of a primary or secondary alcohol having 8 to 18 carbon atoms, a sulfuric acid monoester compound of an aliphatic primary alcohol containing 1 to 6 ethylene oxide, and an ethoxylated secondary alcohol Or sulfuric acid monoester compounds of alkylphenols, sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides, or mixtures thereof may be used.

The nonionic surfactant, which is a component of the liquid detergent composition of the present invention, may be those commonly used in the field. Preferred nonionic surfactants include primary or secondary alcohol-based nonionic surfactants having a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms containing 1 to 25 moles of ethylene oxide, and a straight chain having 8 to 22 carbon atoms. Alternatively, an alkyl polyglycoside nonionic surfactant having a branched alkyl or alkenyl group may be used. In addition, as a fatty acid amide-based nonionic surfactant, a fatty acid amide system having a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms and a fatty acid amide in the form of ammonia amide, monoethanol amide, diethanol amide or isopropanol amide Nonionic surfactants can be used.

The amphoteric surfactant of the liquid detergent composition of the present invention includes a structure in which an anion and a cation are present in the molecular structure at the same time. For example, the amphoteric surfactant is an anion and an acetic acid (-COOH) group, a sulfonic acid (-SO) ₃ H), and containing a group or a sulfate (-O-SO ₃ H), a cation may be a nitrogen-containing group in the quaternary ammonium form. For example, as the amphoteric surfactant, carboxy betaine (RN ⁺ (CH ₃ ) _2- CH ₂ COO-) and sulfo betaine (RN ⁺ (CH ₃ ) _2- CH ₂ CH ₂ CH ₂ SO _3- ) amphoteric surfactant, amine oxide type amphoteric surfactant, amide amino acid type amphoteric surfactant, etc. More specifically, the amphoteric surfactant has 8 to 22 carbon atoms. One or more may be selected from the group consisting of amino propyl betaine, carboxy betaine having 8 to 22 carbon atoms, disodium coco amphodiacetate having 8 to 22 carbon atoms, and sulfo betaine having 8 to 14 carbon atoms. Alkylamidopropylbetaine of to 22 can be used as the amphoteric surfactant, and the alkyl group is preferably a lauryl group having 12 carbon atoms.

The content of the surfactant in the liquid detergent composition of the present invention is 1 to 60% by weight of an anionic surfactant or 1 to 60% by weight of a nonionic surfactant; And 1 to 30% by weight of an amphoteric surfactant.

In addition, with respect to the liquid detergent composition of the present invention, the anionic surfactant or nonionic surfactant is preferably contained within 60% by weight, more preferably within 45% by weight, and most preferably within 30% by weight.

It is preferable that the amphoteric surfactant is contained in an amount of 1 to 30% by weight. If the content is less than 1% by weight, there is a problem that the stability over time of the product is poor, and if it exceeds 30% by weight, the stability of the product may be impaired.

The liquid detergent composition of the present invention contains an alkaline substance, which serves to increase repulsion between laundry and contaminants in the composition, thereby exhibiting an effect of increasing the cleaning power of the liquid detergent composition.

As the alkaline substance, any component that is completely soluble in water can be used. (Here, completely soluble in water means that it is completely soluble in water at 20° C. based on the standard amount of laundry detergent. The general standard amount is 30 L of water and 30 ml of detergent) More specifically, the alkaline substance is, As salts of monovalent or polyvalent organic or inorganic acids, bicarbonate, carbonate, phosphate, polyphosphate, pyrophosphate, triphosphate, tetraphosphate, silicate, metasilicate, polysilicate, hydroxide, alkali metal salt, or mixtures thereof may be used. More preferably, bicarbonate, phosphate, silicate, carbonate, or a mixture thereof may be used, and sodium, potassium, calcium, magnesium, zinc, aluminum, iron, and the like may be used as counter cations of the anion of such a salt.

The content of the alkaline substance may be 0.5 to 15% by weight, more preferably 1 to 10% by weight based on the liquid detergent composition. If the content of the alkali substance is less than 0.5% by weight, the increase in cleaning power is insignificant, and if it is more than 15% by weight, the solubility may deteriorate and precipitation may occur.

The liquid detergent composition of the present invention may further include an electrolyte other than the alkaline material. In the composition containing a surfactant, the electrolyte exhibits a gradual effect and exhibits various effects, such as enhancing dispersion stability of effective particles and air bubbles.

As an electrolyte other than the alkaline substance, chloride, bromide, iodide, acetate, citrate, sulfate, or a mixture thereof may be used as a salt of a monovalent or polyvalent organic or inorganic acid. More preferably, chloride, citrate, sulfate or mixtures thereof may be used. Sodium, potassium, calcium, magnesium, zinc, aluminum, iron, and the like may be used as counter cations of the anions of these salts.

The electrolyte content is preferably 0.5 to 10% by weight based on the liquid detergent composition. When the content of the electrolyte is less than 0.5% by weight, the effect of the electrolyte is insignificant because the increasing effect and dispersion stability are lowered, and when the content of the electrolyte is more than 10% by weight, there is a problem that salts of the electrolyte may interfere with the structuring of surfactants.

The liquid detergent composition of the present invention may have a transparency of 1 to 30 NTU. The transparency of the present invention has an NTU value of 30 or less, more preferably about 20 or less, as determined by the following transparency test .

When the liquid detergent composition of the present invention is commercialized by mixing each raw material, the viscosity of each product must be adjusted. In order to adjust the viscosity, the desired viscosity can be obtained by changing the composition and content of an appropriate amount of solubilizing agent and surfactant. In particular, the viscosity of the liquid detergent composition of the present invention is preferably in the range of 50 to 1000 cP while maintaining the room temperature (25 ℃). If the viscosity is less than 50 cP, the effective particles and microbubbles are not stable at high temperature and cycle conditions of -15 to 40°C and may settle or float. If the viscosity exceeds 1000 cP, the viscosity is too high and There are difficulties.

The liquid detergent composition of the present invention, in addition to the above-described components, additionally thickener, solubilizer, organic solvent, detergent adjuvant, stabilizer, enzyme, preservative, fragrance, dye, within the range not impairing the object of the present invention, It may further include one or more additives selected from the group consisting of a viscosity modifier, a metal ion sealant, and a pH modifier.

The solubilizing agent of the present invention includes polyethylene glycol, glycerin, propylene glycol, alkanols having 1 to 4 carbon atoms, alkylaryl sulfonates, carboxylic acid sulfates, carboxylic acid sulfonate salts, urea, hydrocarboxylate, Carboxylate or mixtures thereof may be used. The alkanol having 1 to 4 carbon atoms may be methanol, ethanol, propanol, isopropanol, straight-chain or branched butanol.

As the thickener of the present invention, inorganic salts such as sodium chloride, water-soluble polymers such as hydroxyethylcellulose and xanthan gum, and fatty acid alkanol amides are known. Among them, fatty acid alkanol amides have been widely used because not only a thickening effect but also a bubble increasing effect is obtained by combining with a surfactant such as an alkyl ether sulfate type surfactant.

As the organic solvent, mono- or polyhydric alcohol may be used. Specifically, those having 1 to 4 carbon atoms may be used, such as methanol, ethanol, propanol, isopropanol, butanol, glycerin and mixtures thereof.

The fragrance may be a commonly used aromatic compound, chemically synthesized or extracted from natural materials, and known in the art.

The preservative may be ethanol, phenoxy ethanol, benzisothiazolinone, methylchloroisothiazolinone, methylisothiazolinone, pentindiol, parabens, sodium benzoate, and the like, but is not limited thereto.

The pH adjusting agent is excellent in removing oil stains, and any low molecular weight organic or arbitrary organic compound that provides neutrality is possible. Preferably, monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide liquid alkali and citric acid, malic acid, salicylic acid, tartaric acid, lactic acid, acetic acid, sorbic acid, benzoic acid and the like are possible.

The pH of the liquid detergent composition of the present invention may range from 8 to 12. It is preferably a pH of 8.5 to 9.5. If the pH is less than 8, the surfactants containing ethylene oxide are decomposed by hydrogen ions, so the performance as a surfactant may be degraded, or the effect of the alkaline electrolyte may decrease and the cleaning power may decrease. If the pH exceeds 12, it may have contacted the human body. When it comes to skin, it can cause problems.

The metal ion encapsulant can be used to increase the formulation and phase stability of the liquid composition of the present invention, EDTA, EDTA-2Na, EDTA-4Na, DTA, NTPA, phosphates, polyacrylic acid, gluconic acid, sorbate, One or more selected from the group consisting of sodium bicarbonate and the like can be used.

In addition, the enzyme is used to further increase the cleaning effect of the liquid detergent composition, mainly alkaline proteolytic enzymes may be used, and specifically, may be used by selecting from the group consisting of proteases, lipases, amylases, and mixtures thereof. The content of the enzyme is preferably 0.01 to 1% by weight, which is a typical range of the enzyme based on the total composition.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

● Preparation of Examples and Comparative Examples

A liquid detergent composition was prepared with the composition and content shown in Table 1 below. The mixture was stirred to obtain a homogeneous liquid phase. Examples 1 and 2 include sodium lauryl ether sulfate as an anionic surfactant and polyoxyethylene lauryl ether as a nonionic surfactant in a ratio of 1:1 (Example 1) or 2:1 (Example 2). And in Example 3, only sodium lauryl ether sulfate, an anionic surfactant, was used in an amount of 30% by weight. As the zwitterionic surfactant, 2.5% by weight of lauryl/myristyl betaine (Example 1) or 5% by weight (Examples 2 and 3), and 5% by weight of sodium bicarbonate were used as an alkaline substance. Contains modifiers and water. On the other hand, in Comparative Examples 1 and 2, only sodium dodecylbenzenesulfonate was used as an anionic surfactant, sodium triplyphosphate 20% by weight as an alkali substance, sodium chloride was used as an electrolyte, and in addition, a pH adjuster, a thickener, and water were used. It was prepared including.

ingredient Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Sodium dodecylbenzenesulfonate 20 20 Sodium lauryl ether sulfate 10 10 30 Polyoxyethylene lauryl ether 10 5 Lauryl/myristyl betaine 2.5 5 5 Sodium hydroxide One One One One One Sodium chloride 2 2 2 2 2 Sodium bicarbonate 5 5 5 Sodium tripolyphosphate 20 20 Acrylic acid polymer One water q.s. q.s. q.s. q.s. q.s.

● Evaluation of Examples and Comparative Examples

The following evaluation was performed on the liquid detergent compositions of Examples and Comparative Examples.

1. pH measurement

In order to confirm whether the transparency and stability are maintained even in alkaline, the pH of each Example and Comparative Example is measured, which is shown in Table 2 below by measuring the pH value using a pH meter (Orion 550A) manufactured by Thermo.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Product pH 9.3 9.2 9.1 11.2 11.3 1g/L pH 8.9 8.8 9.0 10.6 9.8

In Table 2, it can be seen that the pH is high in all the compositions of Examples 1 to 3 and Comparative Examples 1 and 2, and the phase stability and transparency of the liquid detergent composition can be compared on the premise that the pH is high.

2. Transparency evaluation

Transparency is the turbidity of the detergent stock solution, measured at 455 nm using a 2100AN Turbidimeter manufactured by HACH (according to USEPA method 180.1), and is shown in Table 3 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Transparency (NTU) 15 20 17 230 450 Transparency after 12 weeks 20 25 20 Sedimentation Phase separation

According to Table 3, Examples 1 to 3 and Comparative Examples 1 and 2 all contain an alkaline substance, but Examples 1 to 3 in which anionic surfactant, nonionic surfactant, and amphoteric surfactant were used in an appropriate weight %. 3, the liquid phase was transparent, whereas Comparative Examples 1 and 2, which did not match this ratio, were found to be opaque. When anionic surfactant, nonionic surfactant, and amphoteric surfactant are used in an appropriate weight %, an alkaline substance can be stabilized in the composition, and thus precipitation as a precipitate or phase separation is prevented, and thus the liquid detergent composition It can be seen that it contributes to keeping the transparency high.

3. Viscosity and stability evaluation

The viscosity was measured based on a Brookfield LV digital viscometer #4 spindle at 25° C., 60 rpm, and is shown in Table 4 below.

Storage stability was confirmed by assuming the conditions that may appear when a user uses and stores a liquid detergent. Each of the liquid detergent compositions of Examples 1 to 3, Comparative Example 1 and Comparative Example 2 was put in a transparent PET container and stored under each condition, and changes with time were observed. The main subject to be checked in the appearance temporal observation is shown in Table 4 below by checking whether there is a deterioration phenomenon such as whether the phase of the contents is separated.

4. Evaluation of cleaning power

To evaluate the cleaning power of the liquid detergent, a stirring mixed cleaning power tester for laboratory use (Terg-o-tometer) was used. The washing power measurement temperature was operated at 20° C. at a rotation speed of 100, and the sample amount was 1 liter of water and 1 g of sample was used, the washing time was 10 minutes, and the rinsing was performed twice for 3 minutes each. The artificial contaminant cloth used for the measurement was a wet artificial contaminant from the Japan Laundry Science Association. Wet artificial soiling cloth was 5cm X 5cm in size and 8 sheets per sample were used. The washing effect for each contaminated cloth before and after washing was measured using a color difference meter (Nippon denshoku) and compared using Equation 1 below. For the comparative detergent, a standard liquid detergent of Korean industrial standard synthetic detergent was used, and compared with this, if the washing power was superior, it was marked as good, and if the washing power was not superior, it was marked as bad.

5. Results of evaluation of viscosity, stability and cleaning power

Table 4 below shows the viscosity of Examples 1 to 3 and Comparative Examples 1 and 2, and the stability and washing power for 3 months.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Viscosity (cP) 220 310 350 10040 2040 Cleaning power Good Good Good Good Good Long-term stability
3 months stability stability stability Sedimentation Phase separation

As can be seen from Table 4, Examples 1 to 3 and Comparative Examples 1 and 2 all showed good results in washing power, which is the basic performance of a liquid detergent, but unlike the Examples, Comparative Examples 1 and 2 had very high viscosity, In addition, during long-term storage, it was confirmed that phase separation occurred while causing phenomena such as turbidity or precipitation. This phenomenon is, when the surfactants, including amphoteric surfactants, are included in an appropriate weight %, the viscosity of the liquid detergent composition may be adequately, but when the viscosity of the liquid detergent composition is not adequately, Comparative Example 1 and As can be seen from the result of 2, the alkali material in the composition reacts, which causes a precipitate or phase separation phenomenon in the composition. In conclusion, due to the formation of such precipitates, the viscosity in the composition is very high. On the other hand, in Examples 1 to 3 in which surfactants were mixed in an appropriate weight %, it can be seen that the liquid phase is stable and transparency is maintained even after 3 months.

As described above, although the present invention has been described by a limited embodiment, the present invention is not limited to the above embodiment, and various modifications and variations are possible from these descriptions by those of ordinary skill in the field to which the present invention belongs. Do. Therefore, the scope of the present invention is limited to the described embodiments and should not be defined, but should be defined by the claims to be described later as well as equivalents to the claims.

Claims (7)

1 to 60% by weight of anionic surfactant or 1 to 60% by weight of a nonionic surfactant;
1 to 30% by weight of zwitterionic surfactant; And
Including 0.5 to 15% by weight of an alkaline substance,
The pH is 8 to 12, the liquid detergent composition.
The method of claim 1,
The zwitterionic surfactant is a group consisting of amino propyl betaine having 8 to 22 carbon atoms, carboxy betaine having 8 to 22 carbon atoms, disodium coco ampodiacetate having 8 to 22 carbon atoms, and sulfo betaine having 8 to 14 carbon atoms One or more selected from the liquid detergent composition.
The method of claim 1,
The alkali material is one or more selected from the group consisting of bicarbonate, carbonate, phosphate, polyphosphate, pyrophosphate, triphosphate, tetraphosphate, silicate, metasilicate, polysilicate, hydroxide, alkali metal salt, and mixtures thereof, Liquid detergent composition.
The method of claim 1,
The liquid detergent composition, the transparency of which is 1 to 30 NTU, liquid detergent composition.
The method of claim 1,
The liquid detergent composition will have a viscosity of 50 to 1000 cP, a liquid detergent composition.
The method of claim 1,
Liquid detergent further comprising one or more additives selected from the group consisting of organic solvents, detergent adjuvants, stabilizers, enzymes, preservatives, fragrances, dyes, viscosity modifiers, metal ion encapsulants, thickeners, solubilizers and pH adjusters Composition.
delete