KR100397421B1 - Liquid detergent composition comprising linear magnesium alkylbenzenesulfonate - Google Patents

Abstract

The present invention relates to a liquid detergent composition, 7 to 15% by weight of a linear alkylbenzenesulfonate magnesium salt as a first surfactant; 1-7% by weight of alkyl ether sulfate as second surfactant; It is characterized by containing 0.01 to 0.2% by weight of cellulose gum as a thickener and having a neutral pH.

The composition of the present invention has excellent cleaning power by using an alkylbenzenesulfonic acid magnesium salt as a surfactant, and can exhibit an excellent cleaning effect even in a small amount.

Description

Liquid detergent composition containing linear magnesium alkylbenzenesulfonate

The present invention relates to a liquid detergent composition, and more particularly, a linear alkylbenzenesulfonate magnesium salt as a first surfactant, an alkyl ether sulfate as a second surfactant, cellulose gum as a thickener and a neutral pH. The present invention relates to a liquid detergent composition having a rich foam and excellent sustainability of the foam.

In general, a detergent is used as a cleaning component in the dishwashing liquid detergent, which is largely divided into anionic surfactants, nonionic surfactants, and amphoteric surfactants. Representative anionic surfactants include linear alkyl benzene sulfonates, alkyl sulfonates, alkyl ether sulfonates, and alpha olefin sulfonates. Nonionic surfactants include polyoxyethylene alkyl ether derivatives and fatty acid alkyl amides. As amphoteric surfactants, alkyl amine oxides, alkylbatines and the like are commonly used components.

In particular, linear alkyl benzene sulfonate, an anionic surfactant widely used as a main component of dishwashing liquid detergents, is the most used raw material in the tax service industry because it has excellent cleaning power against oil contamination and low raw material prices.

As the linear alkyl benzene sulfonate, an appropriate amount of alkyl benzene sulfonic acid sodium salt neutralized with sodium hydroxide, alkyl sulfate or alkyl ether sulfate, alpha olefin sulfonate, and the like is generally used in the kitchen liquid detergent composition. In the domestic market, low-cost dish detergents are commercially available.

The inventors also found that linear alkylbenzenesulfonate magnesium salts have excellent cleaning ability against oil and other pollutions, rather than linear alkylbenzenesulfonate sodium salts, while developing a dish detergent composition having a composition similar to the above type. The invention has been completed of a dishwashing agent which exhibits the same cleaning power in a smaller amount than the dishwashing agent composition containing sodium fonate salt.

Accordingly, it is an object of the present invention to provide a liquid detergent composition which has excellent cleaning ability by using an alkylbenzenesulfonic acid magnesium salt as a surfactant and can exhibit excellent cleaning effect in a small amount.

In order to achieve the above object, the present invention is a linear alkylbenzenesulfonate magnesium salt 7-15% by weight as a first surfactant; 1-7% by weight of alkyl ether sulfate as second surfactant; It provides a liquid detergent composition containing 0.01 to 0.2% by weight of cellulose gum as a thickener and having a neutral pH.

The main component of the dishwashing composition of the present invention comprises a first surfactant having a major cleaning function, a second surfactant for producing a synergistic cleaning effect, and a thickener for increasing the viscosity of the detergent. Solubilizers for solubilizing, pH adjusters for adjusting pH, and the like.

The content of the first surfactant used in the present invention is 7 to 15% by weight, preferably 8 to 11% by weight, and the content of the second surfactant is 1 to 7% by weight, preferably 4 to the composition. It is-7 weight%, and the content of a thickener is 0.01 to 0.2 weight%, Preferably it is 0.1 to 0.2 weight%. If the content of the surfactant is out of the content range, it is not preferable because it is difficult to expect sufficient washing power or the liquid composition becomes unstable, and if the content of the thickener is less than the content range, no thickening effect occurs and the content exceeds the content. The thickening effect is not increased accordingly.

In the liquid detergent composition of the present invention, the second surfactant may further contain 0.1 to 7 wt% of an alpha olefin sulfonate as an anionic surfactant, and 0.1 to 3 wt% of a higher aliphatic amide system which is a nonionic surfactant. It may contain.

In addition, the liquid detergent composition of the present invention may further contain a water-soluble organic thickener, a fluorescent brightener, an enzyme, a perfume, and the like, as necessary.

In order to prepare the liquid detergent composition of the present invention, neutralization is performed by adding magnesium hydroxide or magnesium oxide as a neutralizing agent to linear alkyl benzene sulfonate (LAS), which is a first surfactant, and then a short chain alcohol or hydrotrop is used as a solubilizing agent. After the solubilization by addition, the viscosity of the liquid was increased by using a surfactant such as alkyl ether sulfate, coconut fatty acid alkyl amide, and a thickener such as hydroxy ethyl cellulose, carboxymethyl cellulose, or sodium chloride or sodium sulfate. The liquid detergent composition of this invention can be manufactured by adjusting to 1500 cPs, and adjusting final PH to 6-8 using triethanolamine or sodium hydroxide solution.

In the neutralization process of the present invention, neutralization is performed using alkylbenzenesulfonic acid and magnesium oxide or magnesium hydroxide. The pH of the neutralizing agent is about 2 to 3, and in this neutralization process, since a considerable high heat is generated, a cooling device or a heat exchanger is used. do.

The present inventors prepared the liquid detergent composition which does not contain magnesium oxide or magnesium hydroxide as a counter ion of alkyl benzene sulfoic acid as the neutralizing agent, but compared the cleaning ability of the liquid detergent composition of the present invention with the cleaning power. As a result, it was confirmed that the liquid detergent composition of the present invention has more excellent cleaning power (see Table 2).

Hereinafter, the present invention will be described in more detail.

[Surfactants]

Alkylbenzenesulfonic acid, which is the first surfactant used as an essential surfactant among the components of the liquid detergent composition used in the present invention, is represented by the following general formula (I) and is based on 1 mole of the alkylbenzene sulfonic acid: Magnesium oxide or Magnesium Hydroxide contains 7 to 15% by weight of neutralized Magnesium Alkyl benzene sulfonate (Mg-ABS) at a ratio of 0.5 to 0.6 Mole.

_{R · C 6 H 4 SO 3} · H (I)

Wherein R in the alkyl group has a carbon distribution in which the carbon distribution is C ₁₂ to C ₁₈ , in particular C ₁₂ to C ₁₄ .

In addition to the magnesium alkylbenzenesulfonate, a second surfactant is used together to increase the cleaning effect. As an anionic surfactant that can be used as the second surfactant, a sulfuric acid ester salt of a higher alcohol and a higher alcohol may be used. Polyoxyethylene, Alkyl Ether Sulfate, and Alpha Olefin Sulfonate may be used in an amount of 1 to 7% by weight.

The higher sulfuric acid ester salt is a sulfuric acid ester by acting concentrated sulfuric acid or anhydrous sulfuric acid on the higher alcohol, and neutralizes the resulting sulfuric acid ester with alkali to form a sulfuric acid ester salt. The structural formula of the alkyl sulfate thus produced is represented by (R · OSO 3 · M) , wherein R is an alkyl group having a carbon distribution of C ₁₂ to C ₂₀ , and M is sodium, magnesium, ammonium, substituted ammonium, and the like. Alkyl sulfates are widely used in dishwashing liquid detergents due to their good water resistance and biodegradability.

Alkylethersulfate can be obtained by adding a few moles of oxyethylene to a higher alcohol and then making sulfuric acid ester with anhydrous sulfuric acid and neutralizing with alkali. The structural formula of the alkyl ether sulfate is represented by (R · En · OSO 3 · M) , wherein R is an alkyl group having a carbon distribution of C ₁₂ to C ₂₀ , E is ethylene oxide (CH ₂ CH ₂ O), and n is added. It is appropriate to use a mole number and n having a distribution of about 0 to 5 mole. M is sodium, magnesium, ammonium, substituted ammonium and the like. Alkyl ether sulphate is more water soluble than alkyl sulphate and has the best hard water resistance among surfactants, so when used in combination with alkyl benzene sulfonate, it is most used in liquid detergents.

In the alpha olefin sulfonate, a mixture of alkene sulfonic acid and sultone is obtained by sulfonating an alpha olefin synthesized in the petrochemical industry with sulfuric anhydride. Neutralizing this with alkali results in the alkene sulfonic acid being sodium alkene sulfonate, a part of the sultone being neutralized, the alkene sulfonic acid sodium being the remainder being the hydroxy alkane sulfonic acid sodium. Thus, among the final products, sodium alkene sulfonate 64-72%, sodium hydroxy alkane sulfonate

21 to 26%, and a mixture containing 7 to 11% of alkanesulfuric acid sodium and other byproducts

This is obtained, which is alpha olefin sulfonate. Of these, alkanesulfonate sulfonate is a poor cleaning material, and alkenesulfonic acid sodium salt has a slightly better cleaning power than hydroxy alkanesulfonate sodium, but a proper mixture of these two substances is better than when alone. . Compared with linear alkyl benzene sulfonate, it has been widely used as an active ingredient in detergents because of its cleaning effect, hard water resistance, biodegradability, and low skin irritation. Structure of the alpha olefin sulfonate is represented by _{(R · CH = CHCH 2 SO} 3 · Na + R · CHOHCH 2 CH 2 SO 3 · Na), the number of carbon atoms of R is C ₁₀ ~ C _18.

In addition to the above anionic surfactants, a fatty acid alkyl amide, which is a nonionic surfactant, may be used as the active ingredient of the detergent. Diethanol amide, which combines a higher fatty acid with diethanolamine 1: 1, is insoluble in water, but the 1: 2 combination of fatty acid and diethanolamine is 60-70% alkanolamide and 25-30% diethanolamine. It is used in combination with anionic surfactants in liquid detergents because it is a mixture of 3 to 5% of amine salts of fatty acids, so it is well soluble in water and increases foam stability, skin protection, and viscosity of liquid detergents along with detergency. In general, the most commonly used fatty acid alkyl amide is coconut fatty acid diethanol amide, and the structural formula is represented as follows.

The composition of the present invention contains a surfactant as a main active ingredient, and may contain 1 to 5% by weight of a solubilizer generally added to the liquid detergent composition to solubilize the surfactant, and the solubilizer is ethyl alcohol. Short chain alcohols having 1 to 5 carbon atoms such as (ROH: R = C2), ethylene glycol, propylene glycol, isopropanol, butanol, and hydrotropes such as sodium cumene sulfate, sodium xylenesulfonate, urea, and the like can be used. .

[Thickener]

The composition of the present invention maintains a viscosity of 900 to 1500 cPs by containing a thickener of about 0.01 to 0.2% by weight.

In general, thickeners used in the tax service industry have a relatively inexpensive inorganic builder such as sodium or ammonium to give a thickening effect. However, the problem with these weapon builders is that they cannot use a large amount, and in some cases, the viscosity of the liquid can be increased gradually with a small amount of salt, but sometimes the viscosity can drop sharply even with a small amount. The optimal amount of salt used depends on the formulation of the prescribed surfactant and how much salt it contains.

In addition to this salt, cellulose gum is commonly used as a thickener for taxpayers. The cellulosic black helps to stabilize the foam, to make it feel like a soap bubble, and to make it into a suspension. The addition of cellulose gum to the liquid detergent also enhances the cleaning effect and prevents reattachment of the separated contamination. This is because cellulose is adsorbed on the surface of the separated contaminant particles to carry the negative electric charge and thus prevents the access of the contaminants. Also, as a hydrophilic protective colloid, the cellulose is adsorbed on the surface of the hydrophobic contaminants to stabilize the dispersion to prevent recontamination. do. It also improves the stability of detergent foam. Therefore, in the present invention, cellulose gum can be used more preferably.

Commonly used cellulose gums in liquid detergents include hydroxy propyl methyl cellulose, hydroxy ethyl cellulose and carboxy methyl cellulose.

Cellulose gum is represented by the following general formula (II).

(Ⅱ)

Methyl cellulose is prepared by replacing the hydroxyl group of cellulose with a methyl group.

R-OH + NaOH → RONa + H2O, R-ONa + CH3Cl → R-O-CH3 + NaCl

At this time, it shows various properties depending on the degree of substitution by methyl group, and if it is almost not substituted by methyl group, it is only dissolved in alkaline aqueous solution, and the much substituted is dissolved in polar organic solvent. And the smaller the molecular weight, the higher the solubility. In addition to methoxyl groups, the introduction of other groups, such as ethoxyl, carboxyl, hydroxyethyl, hydroxypropyl, also affects the solubility or properties of cellulose. The viscosity of methyl cellulose is determined by the length of the polymer chain, and commercially available viscosity ranges from 10 to 19000 cPs for a 2% solution. And since these cellulose derivatives are non-ionic, they are stable in a wide pH range of 3-11.

Hydroxypropyl cellulose is achieved by the reaction of propylene oxide with methyl cellulose.

R-OH + CH2-CH-CH3O → R-O-CH2-CH-CH2OH

The rheological properties of these celluloses are Non Newtonian, and the viscosity is less than 500 cPs.

Has Newtonian characteristics. Most commercially available blacks increase in viscosity and increase in viscosity.

Hydroxy ethyl cellulose can be obtained by reaction of alkali treated cellulose with ethylene oxide.

R-OH + CH2CH2O → R-O-CH2CH2-OH

Hydroxy ethyl cellulose is a nonionic, hydrophilic colloid with good thickening effect. It is easily soluble in hot or cold water and is nonionic, so it shows excellent tolerance to dissolved electrolyte and is hardly affected by pH change.

In the composition of the present invention, hydroxy ethyl cellulose, a cellulose gum having the best solubility in water, was mainly used as a thickener.

Hereinafter, specific examples of the present invention will be described with reference to Examples, but the scope of the present invention is not limited to these Examples.

Example 1: Inventive Liquid Detergent for Cooking and Test of Cleaning Power

In this embodiment, according to the composition of Table 1 according to the neutralization process described above

Dishwashing liquid detergent 1 and liquid detergents 2 and 3 containing no comparable magnesium oxide were prepared and the cleaning power was tested. In the evaluation of cleaning power, the contamination used for the laboratory was applied for 3 hours by applying 1 ml of contaminant evenly to the center of the plate using a general flat plate (28 cm diameter) with artificial pollution consisting of 10% starch, 10% animal and vegetable oils, and pigments. Used after drying. The evaluation method takes 9g of the sample to be evaluated, receives a constant 8L in a container of about 15L (the temperature of the constant is set to 20 ° C), puts the sample into artificial bubbles, and then bubbles the coated dish. Wipe with a sponge until it disappears and count the number of dishes you have wiped.

Composition of the detergent of the present invention and the detergent containing no magnesium oxide ingredient Detergent 1 Detergent 2 Detergent 3 Alkylbenzenesulfonic acid 11.0 11.0 11.0 Magnesium oxide 0.69 0.00 0.00 Alkyl ether sulfate sodium salt (27%) 15.0 15.0 0.00 Alpha olefin sulfonate sodium salt (38%) 0.00 0.00 10.7 Ethyl alcohol 0.5 0.5 0.5 Coconut Fatty Acid Ethanolamide 2.0 2.0 2.0 Triethanolamine 0.5 0.5 0.5 Hydroxyethyl cellulose 0.05 0.05 0.05 Sodium Hydroxide (48%) to pH 7.0 D.I water balance Unit: weight%

Detergent power of the detergent of the present invention and detergent containing no magnesium oxide division Detergent 1 Detergent 2 Detergent 3 Dishwashed Chapter 14 Chapter ten Chapter 11

In Table 2, it can be seen that the detergent composition containing the alkyl benzene sulfonate magnesium salt is superior to the detergent composition containing the alkyl benzene sulfonate sodium salt.

Example 2: Detergency test according to the content of alkyl benzene sulfonate magnesium salt

In this embodiment, as shown in Table 3, the detergent was prepared in the same manner as in Example 1, but after preparing liquid detergents 4 to 9 having different amounts of alkyl benzene sulfonic acid magnesium salts, the contents of the alkyl benzene sulfonic acid magnesium salts The cleaning power change was investigated.

Detergent Composition with Different Magnesium Salts of Alkyl Benzene Sulfonate ingredient Detergent 4 Detergent 5 Detergent 6 Detergent 7 Detergent 8 Detergent 9 Alkylbenzenesulfonic acid 7.00 8.00 9.00 11.00 13.00 15.00 Magnesium oxide 0.50 0.53 0.56 0.63 0.83 0.86 Alkyl ether sulfate sodium salt (27%) 29.00 25.50 22.00 14.80 7.50 0.00 Element 2.00 2.00 2.00 2.00 2.00 2.00 Ethyl alcohol 0.50 0.50 0.50 0.50 0.50 0.50 Ethylene glycol 4.00 4.00 4.00 4.00 5.00 10.00 Coconut Fatty Acid Ethanolamide 2.00 2.00 2.00 2.00 2.00 2.00 Triethanolamine 0.50 0.50 0.50 0.50 0.50 0.50 Sodium chloride 0.20 0.20 0.20 0.20 0.20 0.20 Sodium Hydroxide (48%) to pH 7.0 D.I water balance Unit: weight%

Detergency according to the content of alkyl benzene sulfonic acid magnesium salt division Detergent 4 Detergent 5 Detergent 6 Detergent 7 Detergent 8 Detergent 9 Dishwashed Chapter 11 Chapter twelve Chapter thirteen Chapter thirteen Chapter 11 Chapter nine

As can be seen in Table 4, when the alkyl benzene sulfonate magnesium salt contains 8 to 11% by weight (detergent 5 to 7 of Table 3) and alkyl ether sulfate 4 to 7% by weight (detergent 5 to 7 of Table 3) It can be seen that the most effective, when only the alkyl benzene sulfonic acid magnesium salt alone is present, the cleaning power is less effective than when mixed with alkyl ether sulfate.

Example 3: Viscosity change and detergency test according to the type of thickener

In this embodiment, as shown in Table 5, but prepared in the same manner as in Example 1, but the liquid detergents 10 to 15 with different types of thickeners were prepared to measure the viscosity change of the liquid detergent for each type of thickener. Viscosity measurement was performed using a Brookfield LV type using a No. 3 spindle at 25 ° C.

Detergent composition according to the type of thickener ingredient Detergent 10 Detergent 11 Detergent 12 Detergent 13 Detergent 14 Detergent 15 Alkylbenzenesulfonic acid 11.00 11.00 11.00 11.00 11.00 11.00 Magnesium oxide 0.63 0.63 0.63 0.63 0.63 0.63 Alkyl ether sulfate sodium salt (27%) 17.00 17.00 17.00 17.00 17.00 17.00 Element 2.00 2.00 2.00 2.00 2.00 2.00 Ethyl alcohol 0.50 0.50 0.50 0.50 0.50 0.50 Ethylene glycol 3.00 3.00 3.00 3.00 3.00 3.00 Sodium chloride 0.20 0.40 0.60 0.80 Hydroxyethyl cellulose 0.10 Carboxy Methyl Cellulose 0.10 Coconut Fatty Acid Ethanolamide 2.00 2.00 2.00 2.00 2.00 2.00 Triethanolamine 0.50 0.50 0.50 0.50 0.50 0.50 Sodium Hydroxide (48%) to pH 7.0 D.I water balance Unit: weight%

Viscosity by Type of Thickener division Detergent 10 Detergent 11 Detergent 12 Detergent 13 Detergent 14 Detergent 15 Viscosity (25 ℃) 770cps 800 cps 830cps 780cps 1200cps 1000 cps

In Table 6, as a result of measuring the viscosity of the liquid detergent for each type of thickener, it can be seen that depending on the content of the salt, the viscosity drops when the concentration exceeds a certain amount. It can be seen that it is effective for thickening.

Detergency according to the type of thickener division Detergent 10 Detergent 11 Detergent 14 Detergent 15 Dishwashed Chapter twelve Chapter twelve Chapter thirteen Chapter 14

Table 7 above is to evaluate the cleaning power of the composition using the cellulose gum and the composition not used, it can be seen that the composition using the cellulose gum is better than the composition using the salt.

As described through the above examples, the present invention contains 7 to 15% by weight of the alkyl benzene sulfonate magnesium salt neutralized with magnesium salt and 1 to 7% by weight of the alkyl ether sulfate, and the pH of the liquid is neutral in viscosity. It exhibits a viscosity of 900 ~ 1500 cPs, has a good foaming ability and excellent foaming ability and excellent cleaning ability, so it is an industrially useful invention as a liquid detergent composition.

Claims (9)

8-11 wt% of linear alkylbenzenesulfonate magnesium salt as a first surfactant; 4-7% by weight of alkyl ether sulfate as second surfactant; 0.01 to 0.2% by weight of cellulose gum as a thickener; A dishwashing liquid detergent composition comprising 0.1 to 5% by weight of a solubilizer and a neutral pH (pH 6-8). The liquid detergent composition according to claim 1, which contains an alkylbenzensulfonic acid magnesium salt and wherein said alkylbenzenesulfonic acid is represented by the following general formula: R, C ₆ H ₄ SO ₃ H In the above formula, R of the alkyl group has a C distribution of C12 to C18, especially C12 to C14 Has a C distribution. The liquid detergent composition according to claim 1, which contains an alkyl ether sulfate, wherein the alkyl ether sulfate is represented by the following general formula: R, En, OSO3, M In the formula, R is an alkyl group having a carbon distribution of C ₁₂ ~ C ₂₀ , E is ethylene oxide (CH ₂ CH ₂ O), n is the addition mole number of 0 to 5 mol distribution, M is sodium, Magnesium, ammonium, substituted ammonium and the like. The liquid detergent composition according to claim 1, wherein the cellulose gum is used and the cellulose gum is represented by the following general formula: The liquid detergent composition according to claim 1, wherein the pH of the composition is 6-8. The liquid detergent composition according to claim 1, further comprising 0.1 to 3% by weight of ethyl alcohol (ROH: R = C ₂ ) as a solubilizer. The ethylene glycol, propylene glycol and urea according to claim 1 as solubilizers. Liquid detergent composition characterized in that it further contains 0.1 to 5% by weight of any one or more selected from. The liquid detergent composition according to claim 1, further comprising 0.1 to 7% by weight of an alpha olefin sulfonate which is an anionic surfactant as a second surfactant, and the structural formula is represented by the following general formula: R, CH = CHCH ₂ SO ₃ Na + R CHOHCH ₂ CH ₂ SO ₃ Na In the formula, the carbon number of R is C ₁₀ ~ C ₁₈ . The liquid detergent composition according to claim 1, further comprising 0.1 to 3% by weight of a higher aliphatic amide system, which is a nonionic surfactant, as a second surfactant, and the structural formula is represented by the following general formula: