KR100345997B1 - Alkalic liquid detergent composition containing magnesium alkylbenzene sulfonate - Google Patents

Abstract

The present invention is characterized by a liquid detergent composition containing magnesium salt, contaminase, and arylboronic acid in a linear alkylbenzenesulfonic acid, the pH of which is alkaline. In particular, the composition of the present invention can maintain excellent enzyme stability even in the alkaline detergent composition using the aryl boronic acid and has an excellent effect in showing an excellent washing power using the alkylbenzenesulfonic acid magnesium salt.

Description

Alkalic liquid detergent composition containing magnesium alkylbenzene sulfonate

The present invention relates to an alkaline liquid detergent composition. More specifically, the present invention relates to a liquid detergent composition containing an alkylbenzenesulfonic acid magnesium salt neutralized with magnesium salts and having an excellent washing ability.

Liquid detergents are more convenient to use than powder detergents, and have the advantages of superior solubility in cold water, but are disadvantages in that the manufacturing cost is high and the cleaning power is lower than powder detergents. This is because, unlike powder detergent, the use of builders, etc., which can increase washing power, is limited to use only a small amount, and maintaining a high alkali state is limited in order to maintain stability of enzyme activity.

Therefore, the present inventors have tried to develop a liquid detergent product that can increase the cleaning power significantly compared to the conventional liquid detergent, while maintaining the same level as the washing performance of the powder type, and the manufacturing cost is low, and can maintain the excellent enzyme stability in the alkaline liquid. The present invention has been completed by preparing a liquid detergent composition that is stable under excellent washing power. As the main components used as the liquid washing detergent of the present invention, surfactants, water softeners, solubilizers, fluorescent brighteners, enzymes, alkali agents, enzyme stabilizers and the like are largely used. For example, as surfactant, anionic surfactants, such as linear alkylbenzene sulfonate, fatty acid soap, lauryl sulfate, alpha olefin sulfonate, and lauryl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid Nonionic surfactants such as alkanolamide were mainly used, and trisodium nitrilotriacetate (NTA 3Na), EDTA 4Na, EDTA 2Na, sodium citrate, etc. were mainly used as the softener, and protease was used as the enzyme.

In recent liquid detergent compositions, one of the important components together with the surfactant is an enzyme. As enzymes used in detergents, proteases, which are proteolytic enzymes, amylases, which are starches, and lipases, which are lipolytic enzymes, are mainly used. Recently, protease, an alkaline protease, has been used in large amounts in enzyme cleaners and hair removal processes in leather industry, and enzyme cleaners have the advantage of reducing the risk of environmental pollution, unlike synthetic detergents known as important factors for river pollution. In order to use this protease for alkaline detergents, an alkaline and surfactant-resistant protease must be mass-produced, and in the development of a product, a special enzyme stabilization system is required to stabilize the enzyme so that the enzyme is not degraded in the product. . To this end, enzyme stabilization may be maintained in a product by appropriately using enzyme activity inhibitors and stabilizers.

As a solubilizer, ethanol, propylene glycol, isopropanol, butanol, sodium cumene sulfonate, sodium xylene sulfonate, urea and the like were used.

To date, liquid detergents containing surfactants neutralized with magnesium salt have been made only at pH neutral and have been confined to kitchen and hard detergents. The reason is that in the mixture with magnesium salt in alkyl benzene sulfonic acid, when the liquidity is alkali, the magnesium ion of the magnesium benzene sulfonate salt is substituted with other alkali ions and separated into molecules such as magnesium hydroxide to change the solution into a turbidity. This is because liquid phase separation occurs after that. In addition, there have been no reports of maintaining the activity stability of enzymes in alkaline liquid detergents using alkylbenzenesulfonate magnesium salts.

Therefore, an object of the present invention is a liquid detergent composition containing an alkylbenzenesulfonic acid magnesium salt neutralized with magnesium salts and having an alkaline pH of 8 or more, maintaining a stable enzyme stability and at the same time maintaining a stable phase and excellent cleaning power In providing a detergent composition.

The object of the present invention is to neutralize by adding magnesium hydroxide or magnesium oxide as a neutralizing agent to linear alkylbenzenesulfonate (LAS) as a surfactant, and then to adjust the viscosity by adding short chain alcohol or hydrotropes, A liquid detergent composition of the present invention having a final pH of 8 or more is prepared by adding a surfactant and other additives including ethanol and using monoethanolamine (MEA) as an alkaline agent. To prepare a conventional liquid detergent that does not contain hydroxide or magnesium oxide to investigate the cleaning power according to the liquid detergent and the type of contamination of the present invention prepared by changing the pH of the prepared liquid detergent or the composition of the liquid detergent composition Achievement was by examining post wash. In addition, by measuring the enzyme storage stability according to the content of the boron compound which is an enzyme activity inhibitor, the object of the present invention was achieved.

Hereinafter, the configuration and operation of the present invention.

The present invention comprises (1) preparing a liquid detergent composition of the present invention containing a magnesium oxide as a neutralizing agent and a monoethanolamine as an alkaline agent in which the pH is alkaline, and washing the contaminated cloth to investigate the washing power; (2) preparing a liquid detergent having a lower pH than the liquid detergent of the present invention and then irradiating the washing power in the same manner as above; (3) preparing a liquid detergent composition having a high content of linear alkylbenzenesulfonate salt (LAS Mg) obtained by treating magnesium salt with alkylbenzenesulfonate and examining the washing power in the same manner as above; (4) preparing a liquid detergent composition with varying molar ratios of magnesium oxide and alkylbenzenesulfonic acid and examining the washing power in the same manner as above; And (5) preparing a liquid detergent composition of the present invention and investigating enzyme storage stability according to the type and content of enzyme activity inhibitor.

Surfactants

Alkylbenzenesulfonic acid 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 magnesium oxide (Magnesium) per 1 mol of the alkylbenzene sulfonic acid oxide) or magnesium hydroxide in an amount of 0.2 to 0.7 molar ratio and containing 5 to 40% by weight of magnesium alkylbenzene sulfonate (Mg-ABS).

_{R · C 6 H 4 SO 3} · H

(I)

Wherein R is an alkyl group having ₁₂ to ₁₈ carbon atoms, preferably a linear alkyl group having ₁₂ to ₁₄ carbon atoms.

In addition to the magnesium alkylbenzenesulfonate, it may further contain a cleaning surfactant consisting of 1 to 40% by weight of other anionic surfactants, nonionic surfactants, amphoteric surfactants or mixtures thereof.

In addition to the magnesium alkylbenzene sulfonate, other anionic surfactants may include alkyl sulfate (R · SO 4 · M) and alkyl ether sulfate (R · En SO 4 · M). Wherein R is an alkyl group having C ₁₂ to C ₂₀ carbon atoms, E is ethylene oxide (CH ₂ CH ₂ O), n is an additional mole number and 0 to 5 mol is preferably used, and M is sodium, magnesium, ammonium Or substituted ammonium and the like.

In addition, other anionic surfactants that may be used include alpha olefin sulfonate sodium salts (R CH CH ₂ SO ₃ Na + R CHOHCH ₂ CH ₂ SO ₃ Na). Wherein R has C ₁₀ to C ₁₈ .

With other anionic surface active agent in addition to be used is a SOAP (COO and R and M), where R is a C ₁₂ to C _20, M is sodium, magnesium, ammonium or substituted ammonium.

Non-ionic surfactants that may also be used are materials having groups that are not ionized, such as hydroxyl groups (OH) and carbonyl groups (O) bonds of hydrophilic molecules. Nonionic surfactants are classified into surfactants of polyethylene glycol type and polyalcohol type according to the type of hydrophilic group, and nonionic surfactants of polyhydric alcohol type are not used as cleaning agent and penetrating agent. Zero is used.

The polyethyleneglycol type is prepared by adding hydrophilic ethylene oxide (CH ₂ CH ₂ O) to a hydrophobic raw material having a reactive hydrogen atom. Wherein said hydrogen atoms in the reactive hydrogen atom is a hydroxyl group (OH), carboxyl (COOH), amine groups (NH _2), amide (CONH _2).

Examples of the polyethylene glycol type that can be used include the following.

Higher alcohol type;

RO- (CH ₂ CH ₂ O) nH R = C _12- C ₁₄ n = 3-12

Alkyl phenyl type;

R = C12-C14 n = 3-12

May be used representatively, and other types that may be used include

Fatty acid system;

R = C ₁₀ -C ₁₈ n = 1-3

Higher aliphatic amines;

R = C ₁₀ -C ₁₈ n = 1-3

Aliphatic amides;

R = C ₁₀ -C ₁₈ n = 1-3

Etc. can be used.

In addition to playing polyimide Al: R1 and COON (R2OH) 2 (. And where R1 is a C ₁₂ to C _20, R2 is a C ₁ to C ₂₎ it can use.

The composition of the present invention contains a surfactant as a main component and contains 1 to 15% by weight of a solubilizing agent, and the solubilizing agent may be a short chain alcohol such as ethyl alcohol, ethylene glycol, propylene glycol, or hydrotropes (sodium cumene sulfate, sodium Xylenesulfonate, urea) and the like.

Proteolytic Enzyme

The composition of the present invention contains about 0 to 5% by weight of the protease enzyme. Most preferably, it contains 0.01 to 4.0% by weight of active protease. This active protease can be obtained from animals, plants or microorganisms. More preferably, an active protease purified from a serine protease originating from a microorganism or an active protease in an unpurified form may be used. This active protease includes those produced by modifying chemically or genetically mutated species. More preferably, it is a bacterial serine proteolytic enzyme obtained from Bacillus subtillis and / or Licheniformis. Suitable active proteases that are commercially available include Alcalase, Esperase, Savinase, Maxatase, and Maxacal from NOVO. ) And Maxapem (Protein engineered Maxacal) can be used. More preferably, savinase or maxaxal may be used.

Enzyme Inhibitor

In general, boron compounds (boric acid, boronic acid, borate, boron oxide) are widely known as active inhibitors of active proteases. In particular, boron compounds such as boric acid and boric acid are known to bind to the proteolytic enzyme active site to inhibit the activity of the enzyme. These boron compounds inhibit the active part of the protease through covalent bond formation with serine groups and hydrogen bond formation with histadine groups. In particular, boron compounds with aryl groups such as phenylboronic acid form stronger covalent bonds in the serine group, which has a more potent inhibitory activity of the enzyme.

In the present invention, 0.001 to 1.0% by weight of arylboronic acid was used as an enzyme activity inhibitor among the components of the liquid detergent composition, and arylboronic acid is represented by the general formula (II).

(Ⅱ)

In the above formula,

X is hydrogen or alkyl of C1 to C6, aryl, alkyl of substituted C1 to C6, substituted aryl, hydroxy, hydroxy derivative, amine, alkylated amine of C1 to C6, amine derivative, halogen, nitro, Thiols, thiol derivatives, aldehydes, acids, acid salts, esters, sulfonates or phosphates,

Y is hydrogen or alkyl having 1 to 6 carbon atoms, aryl, alkyl having 1 to 6 carbon atoms, substituted aryl, hydroxy, hydroxy derivative, amine, alkylated amine having 1 to 6 carbon atoms, amine derivative, halogen, nitro, Thiols, thiol derivatives, aldehydes, acids, acid salts, esters, sulfonates or phosphates. Preferably X is hydrogen, nitro, acetamino or butyl and Y is hydrogen.

In the neutralization process used in the present invention, magnesium hydroxide or magnesium oxide was used as the neutralizing agent, and monoethanolamine (MEA) was used as the alkaline agent. First, neutralization was performed using alkylbenzene sulfonic acid and magnesium oxide or magnesium hydroxide. At this time, the pH of the first neutralized product was about 3 to 4, which is appropriate. In this neutralization process, since a considerable high heat is generated, a cooling device or a heat exchanger is used. And if the viscosity needs to be adjusted by using the materials generally used in liquid detergent compositions such as short-chain alcohol or hydrotropes. Herein, short-chain alcohols are alcohols having 1 to 5 carbon atoms, such as ethyl alcohol, propylene glycol, isopropanol and butanol, and hydrotrope is a material commonly used for viscosity adjustment or stability in detergent compositions. Nate (Sodium cumene sulfonate), xylene sulfonate (Xylene sulfonate) or urea was used, and the product was alkalinized by secondary neutralization with ethanol, other additives and monoethanolamine (MEA). At this time, the pH of the composition in the state of the final neutralization was about 9 to 10 was appropriate.

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 Preparation of the Liquid Detergent of the Present Invention and Detergency

In this example, according to the neutralization process described above, according to the composition of Table 1, liquid detergent 1 of the present invention and another detergent 2 and 3 comparable thereto were prepared, and then washing power was tested. The cleaning power was evaluated using a turgotometer manufactured by US testing company, which is mainly used for laboratory use. The laundry measurement temperature was operated at 25 ° C. with a turgotomometer rotation RPM 120. The sample volume was 0.67 g of the sample in 1 L of water, and the washing time was 10 minutes and rinsing was performed twice for 3 minutes each. AS12 and EMPA104 were used as the contaminated cloth used for the measurement. In other words, EMPA 104 was cut down to 7 x 7cm in width and used 7 sheets for each sample. Contamination was composed of Indian ink and olive oil, and AS 12 was 7 x 7cm in width. Seven pieces were used for each sample, and contamination was 15.84% by weight of Carboxy methyl carubin, 1.94% by weight of Indian ink, 36.25% by weight of peanut oil, 3.70% by weight of milk powder (38% casein). , 18.18% by weight of the filtrate (silica), 21.80% by weight of Emulgater'D (Surfantant), and 2.29% by weight of yellow iron oxide. The cleaning effect was measured by using a color difference meter to measure the color difference of the contaminated cloth before and after washing. And calculated according to the following formula and the results are shown in Table 2 and the detergent power of the present invention detergent 1 and the product sold in the overseas market was measured in the same manner as above and the results are shown in Table 3. As a result of the experiment, the detergent 1 of the present invention using magnesium oxide as the first neutralizing agent showed an excellent washing effect in both EMPA 104 and AS 12 staining cloths compared to detergent 2 and detergent 3 (Table 2), and also sold to overseas markets. The washing power was superior to the detergent products in use (Table 3).

Cleaning effect (%) = (C-B) / (A-B) × 100

* A: whiteness of white cloth

* B: Pollutant whiteness before washing

* C: Pollutant white after washing

Composition of the detergent of the present invention and the detergent containing no magnesium oxide ingredient Detergent 1 Detergent 2 Detergent 3 Alkylbenzenesulfonic acid 17.0 17.0 19.0 Ⓑ magnesium oxide 0.75 0.00 0.00 Alkyl ether sulfate sodium salt (70%) 24.0 24.0 26.0 Alpha olefin sulfonate sodium salt (38%) 30.0 30.0 27.0 Ethyl alcohol 6.0 6.0 7.2 Monoethanolamine 5.0 5.0 6.5 Protease 2.0 2.0 2.0 Sodium Hydroxide (48%) to pH 10.5 Other additives 0 to 15 D.I water balance ※ ⓐ: ⓑ molar ratio 1: 0.36 1: 0 1: 0 Unit: weight%

Cleaning power of the detergent of the present invention and detergent containing no magnesium oxide division Detergent 1 Detergent 2 Detergent 3 % Wash rate for EMPA104 27.9 25.1 25.8 % Cleans to AS12 45.1 37.2 39.2

Investigation of cleaning power of the present invention detergent and foreign detergent product Detergent 1 Japan P company product Japan L company product % Wash rate for EMPA104 27.9 20.8 25.3 % Cleans to AS12 45.1 39.2 36.2

Example 2 Investigation of Liquid Detergent Preparation and Cleaning Power with Different pH

In this example, as shown in Table 4, detergent was prepared in the same manner as in Example 1, but pH 4 was adjusted with sodium hydroxide to prepare detergent 4 of the present invention showing alkalinity and comparative detergents 5 and 6 showing neutrality. After the washing power was also tested in the same manner as in Example 1. As shown in Table 5, when the pH of the product was less than 8.0, it was found that there was no difference in the detergent using magnesium, the detergent using general alkali, or the washing power.

Detergent composition with pH difference ingredient Detergent 4 Detergent 5 Detergent 6 Alkylbenzenesulfonic acid 17.0 17.0 17.0 Ⓑ magnesium oxide 0.75 0.00 0.75 Alkyl ether sulfate sodium salt (70%) 24.0 24.0 24.0 Alpha olefin sulfonate sodium salt (38%) 30.0 30.0 30.0 Ethyl alcohol 6.0 6.0 6.0 Monoethanolamine 2.0 2.0 2.0 Protease 2.0 2.0 2.0 Sodium Hydroxide (48%) to pH 8.5 to pH 7.5 to pH 7.5 Other additives 0 to 15 D.I water balance ※ ⓐ: ⓑ molar ratio 1: 0.36 1: 0 1: 0.36 [Note] Unit: wt%

Cleaning power of the present invention alkaline detergent and neutral detergent division Detergent 4 Detergent 5 Detergent 6 Contaminated cloth AS12 cleaning rate (%) 39.7 34.5 35.1 Contaminated cloth EMPA104 cleaning rate (%) 25.9 22.3 22.8

Example 3: Investigation of detergent preparation and cleaning power with different LAS Mg content

In this embodiment, as shown in Table 6, a detergent was prepared in the same manner as in Example 1, but the magnesium alkyl-treated linear alkylbenzenesulfonate magnesium benzene sulfonate magnesium salt (LAS Mg) content was controlled. After preparing the detergents 9, 10, 11, 12 and 13 of the present invention, the washing power was also tested in the same manner as in Example 1. As a result, as shown in Table 7, contaminated cloth AS12 showed the most effective cleaning power when the content of LAS Mg was 15 to 20% by weight. As the amount of LAS Mg was increased, the ratio of AES and AOS decreased so that LAS Mg increased The lower the cleaning power was.

Detergent composition with different LAS Mg content ingredient Detergent 9 Detergent 10 Detergent 11 Detergent 12 Detergent 13 Alkylbenzenesulfonic acid 15.0 20.0 25.0 30.0 35.0 Ⓑ magnesium oxide 0.65 0.93 1.16 1.39 1.62 Alkyl ether sulfate sodium salt (70%) 27.0 22.0 15.0 15.0 13.0 Alpha olefin sulfonate sodium salt (38%) 30.0 30.0 20.0 17.0 13.0 Ethyl alcohol 6.0 6.0 6.0 6.0 6.0 Monoethanolamine 5.0 5.0 5.0 5.0 5.0 Protease 2.0 2.0 2.0 2.0 2.0 Sodium Hydroxide (48%) to pH 10.5 Other additives 0 to 15 D.I water balance [Note] Unit: wt%

Detergency of detergents with different LAS Mg content division Detergent 9 Detergent 10 Detergent 11 Detergent 12 Detergent 13 % Cleaning rate 42.5 43.6 41.81 41.0 40.7 NOTE The cleaning rate is the result of using the contaminated cloth AS12.

Example 4 Detergent Preparation and Detergent Investigation of Molar Ratios of Various Magnesium Oxides and Alkyl Benzene Sulphonic Acids

In the present embodiment, as shown in Table 8, the detergent was prepared in the same manner as in Example 1, but the detergent 14, 15, 16 and 17 of the present invention was also prepared by changing the molar ratio of magnesium oxide and alkyl benzene sulfonic acid. Washing power was tested in the same manner as in Example 1. As a result, as shown in Table 9, when the ratio of alkylbenzenesulfonic acid to magnesium oxide is lower than 1: 0.2, the cleaning power was lowered, and when the ratio is more than 1: 0.7, the cleaning power was excellent, but formulation was difficult due to problems in formulation.

Detergent Composition of Molar Ratios of Various Magnesium Oxides and AlkylbenzeneSulfonic Acids ingredient Detergent 14 Detergent 15 Detergent 16 Detergent 17 Alkylbenzenesulfonic acid 17.0 17.0 17.0 17.0 Ⓑ magnesium oxide 0.5 1.35 0.4 1.65 Alkyl ether sulfate sodium salt (70%) 24.0 24.0 24.0 24.0 Alpha olefin sulfonate sodium salt (38%) 30.0 30.0 30.0 30.0 Ethyl alcohol 6.0 6.0 6.0 6.0 Monoethanolamine 5.0 5.0 5.0 5.0 Protease 2.0 2.0 2.0 2.0 Sodium Hydroxide (48%) up to pH 10.5 Other additives 0 to 15 D.I water balance ※ ⓐ: ⓑ molar ratio 1: 0.23 1: 0.65 1: 0.19 1: 0.79 Unit: weight%

Detergent cleaning power of various ratios of magnesium oxide and alkylbenzene sulfonic acid division Detergent 14 Detergent 15 Detergent 16 Detergent 17 Contaminated cloth AS12 cleaning rate (%) 40.01 41.90 34.69 42.02

Example 5 Enzyme Storage Stability Test 1

In this example, the liquid detergent of the present invention was prepared according to the composition of Table 10 according to the neutralization process described above, and the enzyme activity retention stability of each boron compound was measured. The protein used to measure the activity of the enzyme (protease) was used AZO casein (SIGMA), and the reaction conditions were measured for 20 minutes at 40 ℃ UV spectrophotometer, absorbance was measured at 390nm. Sample storage conditions were stored for about 4 weeks in a 40 ℃ incubator and the activity was initially set to 100 to measure the activity of the enzyme (protease) every week. The pH of the sample was maintained at 9.7 to 10.20 (at 25 ° C of the stock solution).

Detergent Composition by Type of Boron Compound ingredient Detergent 18 Detergent 19 Detergent 20 Detergent 21 Detergent 22 Alkylbenzenesulfonic acid 11.90 11.90 11.90 11.90 11.90 Magnesium oxide 0.74 0.74 0.74 0.74 0.74 Alkyl ether sulfate sodium salt (70%) 16.45 16.45 16.45 16.45 16.45 Alpha olefin sulfonite sodium salt (38%) 19.25 19.25 19.25 19.25 19.25 Ethyl alcohol 4.50 4.50 4.50 4.50 4.50 Monoethanolamine 2.87 2.87 2.87 2.87 2.87 Propylene glycol 8.00 8.00 8.00 8.00 8.00 Sodium Formate 1.40 1.40 1.40 1.40 1.40 Boric acid 1.00 0.42 0.42 0.42 0.42 3 nitrophenylboronic acid 0.5 Butylboronic Acid 0.5 Acetamidophenylboronic acid 0.5 Phenylboronic Acid 0.5 Calcium chloride 0.01 0.01 0.01 0.01 0.01 Trisodium nitriloacetate 0.10 0.10 0.10 0.10 0.10 Active protease 1.40 1.40 1.40 1.40 1.40 Fluorescent Whitening Agent 0.10 0.10 0.10 0.10 0.10 water balance balance balance balance balance sum 100.00 100.00 100.00 100.00 100.00 Unit weight%

Enzyme activity maintenance stability measurement result by type of boron compound 1 week 3 weeks 4 Weeks Detergent 18 73.73 30.70 19.94 Detergent 19 100.00 84.00 77.30 Detergent 20 89.80 52.70 40.90 Detergent 21 99.00 91.35 84.37 Detergent 22 88.40 47.33 40.17

In this embodiment, as a result of measuring the activity maintenance stability of proteolytic enzymes of each type of boron compound, the composition used by mixing two substances was superior to the composition using the boron compound alone. The mixture used with was especially excellent in stability.

Example 6: Enzyme Storage Stability Test 2

In this example, according to the neutralization process described above, the liquid detergent of the present invention was prepared according to the composition of Table 12, and the enzyme activity retention stability according to the concentration of phenylboronic acid was measured in the same manner as in Example 5.

ingredient Detergent 23 Detergent 24 Detergent 25 Detergent 26 Alkylbenzenesulfonic acid 11.90 11.90 11.90 11.90 Magnesium oxide 0.74 0.74 0.74 0.74 Alkyl ether sulfate sodium salt (70%) 16.45 16.45 16.45 16.45 Alpha olefin sulfonite sodium salt (38%) 19.25 19.25 19.25 19.25 Ethyl alcohol 4.50 4.50 4.50 4.50 Monoethanolamine 2.00 2.00 2.00 2.00 Propylene glycol 8.00 8.00 8.00 8.00 Sodium Formate 1.40 1.40 1.40 1.40 Boric acid 0.42 0.42 0.42 0.42 Tetrasodium Ethyleneamine Acetate 0.10 0.10 0.10 0.10 Phenyl Boronic Acid 0.01 0.05 0.1 1.0 Calcium chloride 0.01 0.01 0.01 0.01 Active protease 1.40 1.40 1.40 1.40 Fluorescent Whitening Agent 0.10 0.10 0.10 0.10 water balance balance balance balance sum 100.00 100.00 100.00 100.00

Enzyme activity maintenance stability measurement result by concentration of phenylboronic acid 1 week 2 weeks 3 weeks 4 Weeks Detergent 23 85.85 79.79 63.23 49.00 Detergent 24 90.20 90.95 80.51 77.32 Detergent 25 90.98 90.98 84.39 81.85 Detergent 26 96.35 93.26 93.00 90.22

Example 7 Enzyme Storage Stability Test 3

In this example, according to the neutralization process described above, the liquid detergent of the present invention was prepared according to the composition of Table 14, and the enzyme activity retention stability according to the concentration of 3 nitrophenylboronic acid was measured in the same manner as in Example 6.

ingredient Detergent 27 Detergent 28 Detergent 29 Detergent 30 Alkylbenzenesulfonic acid 11.90 11.90 11.90 11.90 Magnesium oxide 0.74 0.74 0.74 0.74 Alkyl ether sulfate sodium salt (70%) 16.45 16.45 16.45 16.45 Alpha olefin sulfonite sodium salt (38%) 19.25 19.25 19.25 19.25 Ethyl alcohol 4.50 4.50 4.50 4.50 Monoethanolamine 2.00 2.00 2.00 2.00 Propylene glycol 8.00 8.00 8.00 8.00 Sodium Formate 1.40 1.40 1.40 1.40 Boric acid 0.42 0.42 0.42 0.42 3 nitrophenylboronic acid 0.01 0.05 0.10 1.00 Tetrasodium Ethyleneamine Acetate 0.10 0.10 0.10 0.10 Calcium chloride 0.01 0.01 0.01 0.01 Active protease 1.40 1.40 1.40 1.40 Fluorescent Whitening Agent 0.10 0.10 0.10 0.10 water Balance Balance Balance Balance sum 100.00 100.00 100.00 100.00

Enzyme activity maintenance stability measurement result by concentration of nitrophenylboronic acid 1 week 2 weeks 3 weeks 4 Weeks Detergent 27 80.32 71.22 55.34 41.11 Detergent 28 81.33 75.27 63.57 56.43 Detergent 29 89.26 80.48 77.22 70.00 Detergent 30 98.77 95.33 84.58 80.26

Example 8 Enzyme Storage Stability Test 4

In this Example, according to the neutralization process described above, the liquid detergent of the present invention was prepared according to the composition of Table 16, and the enzyme activity retention stability according to the concentration of acetamidophenylboronic acid was measured in the same manner as in Example 6.

ingredient Detergent 31 Detergent 32 Detergents 33 Detergent 34 Alkylbenzenesulfonic acid 11.90 11.90 11.90 11.90 Magnesium oxide 0.74 0.74 0.74 0.74 Alkyl ether sulfate sodium salt (70%) 16.45 16.45 16.45 16.45 Alpha olefin sulfonite sodium salt (38%) 19.25 19.25 19.25 19.25 Ethyl alcohol 4.50 4.50 4.50 4.50 Monoethanolamine 2.00 2.00 2.00 2.00 Propylene glycol 8.00 8.00 8.00 8.00 Sodium Formate 1.40 1.40 1.40 1.40 Boric acid 0.42 0.42 0.42 0.42 Acetamidophenyl boronic acid 0.01 0.05 0.10 1.00 Tetrasodium Ethyleneamine Acetate 0.10 0.10 0.10 0.10 Calcium chloride 0.01 0.01 0.01 0.01 Active protease 1.40 1.40 1.40 1.40 Fluorescent Whitening Agent 0.10 0.10 0.10 0.10 water Balance Balance Balance Balance sum 100.00 100.00 100.00 100.00

Enzyme activity maintenance stability measurement result of acetamidophenylboronic acid by concentration 1 week 2 weeks 3 weeks 4 Weeks Detergent 31 80.70 75.16 52.70 45.77 Detergent 32 86.06 77.20 55.33 50.10 Detergents 33 90.45 85.67 79.20 75.11 Detergent 34 95.30 88.43 85.27 79.00

As described through the above examples of the present invention, the linear alkylbenzenesulfonic acid containing 5 to 40% by weight of the alkylbenzenesulfonic acid magnesium salt treated with magnesium salt in a molar ratio of 1: 0.2 to 1: 0.7. The liquid detergent composition was prepared, and the prepared liquid detergent exhibits alkalinity in the pH range of 8 to 11, and has an excellent effect of excellent washing power, which is a very useful invention in the detergent industry.

Claims (5)

5 to 40% by weight of an alkylbenzenesulfonate magnesium salt neutralized at a ratio of 0.2 to 0.7 mol of magnesium oxide or magnesium hydroxide to 1 mol of alkylbenzene sulfonic acid composed of the following general formula (I), consisting of the following general formula (II) A liquid detergent composition comprising 0.001 to 1.0% by weight of arylboronic acid, 0.01 to 4.0% by weight of a contaminating enzyme, 1 to 15% by weight of a solubilizer and 40 to 75% by weight of water, and has a pH of 8 to 11. _{R · C 6 H 4 SO 3} · H (Ⅰ) (Ⅱ) Wherein R is an alkyl group of C12 to C18, X is hydrogen or alkyl of C1 to C6, aryl, alkyl of substituted C1 to C6, substituted aryl, hydroxy, hydroxy derivative, amine, Alkylated amines, amine derivatives, halogens, nitros, thiols, thiol derivatives, aldehydes, acids, acid salts, esters, sulfonates or phosphates which are C1 to C6, and Y is hydrogen or alkyl, aryl, substituted C1 to C6 Alkyl, substituted aryl, hydroxy, hydroxy derivative, amine, C1 to C6 alkylated amine, amine derivative, halogen, nitro, thiol, thiol derivative, aldehyde, acid, acid salt, ester, sulfonate or It is a phosphate. The liquid detergent composition according to claim 1, wherein the arylboronic acid is phenylboronic acid, trinitrophenylboronic acid or acetamidophenylboronic acid. The liquid detergent composition according to claim 1, wherein the contaminase is an active protease, a lipolytic enzyme, a starch enzyme or a cellulase. The liquid detergent composition according to claim 1, wherein the solubilizer is ethyl alcohol, ethylene glycol, propylene glycol or a mixture thereof. The liquid detergent composition according to claim 1, further comprising a cleaning surfactant comprising 1 to 40% by weight of an anionic surfactant, nonionic surfactant, amphoteric surfactant or a mixture thereof.