KR100420467B1 - a alkaline composition of liquid type cleanser containing nonionic surfactant - Google Patents

Abstract

The present invention relates to an alkaline liquid detergent composition, and more particularly, polyoxyethylene lauryl ether (nonionic surfactant), alphaolefin sulfonate (anionic surfactant), and separated from Korean soil. By containing six kinds of alkaline active protein contaminating enzymes secreted extracellularly from Vibrio mechnicoco species RH 530 (Vibrio metschnikovii sp. RH 530), which are basophilic strains, and monoethanolamine, sodium carbonate, and sodium carbonate as alkali agents. It relates to an alkaline liquid detergent composition which has a good cleaning power.

Description

Alkaline composition of liquid type cleanser containing nonionic surfactant

The present invention relates to an alkaline liquid detergent composition, and more particularly, polyoxyethylene lauryl ether (nonionic surfactant), alphaolefin sulfonate (anionic surfactant), and separated from Korean soil. By containing six kinds of alkaline active protein contaminating enzymes secreted extracellularly from Vibrio mechnicoco species RH 530 (Vibrio metschnikovii sp. RH 530), which are basophilic strains, and monoethanolamine, sodium carbonate, and sodium carbonate as alkali agents. It relates to an alkaline liquid detergent composition which has a good cleaning power.

Liquid detergents have the advantage of being easier to use than powder detergents and excellent in solubility in cold water, but are disadvantageous in that the manufacturing cost is high and the washing power is poor compared to powder detergents. This is because liquid detergents, unlike powder detergents, have limited use of additives such as alkali agents and metal ion sequestrants, which are builders that can increase cleaning power.

Meanwhile, in the recent liquid detergent composition, one of the important components together with the surfactant is an enzyme. The main enzymes used in the detergent include protease, a protease, amylase, and lipase, a lipolytic enzyme. Can be. Among these, protease, an alkaline protease, is used in large quantities in enzyme cleaners and hair removal processes in leather industry, and enzyme detergents can reduce the risk of environmental pollution, unlike synthetic detergents, which are known to be important factors for river pollution. . However, in order to use this protease for alkaline detergents, an alkaline and surfactant-resistant protease must be mass-produced, and a special enzyme stabilization system can be developed to stabilize the enzyme so that the enzyme is not degraded in the product. need.

An object of the present invention is to solve the above problems by appropriately adjusting the composition components and to provide an alkaline liquid detergent composition having excellent washing power and stabilized enzyme.

The present inventors have solved the above problems and tried to develop a liquid product that is superior to the conventional liquid detergent, and as a result, polyoxyethylene lauryl ether as a nonionic surfactant, alphaolefin sulfonate as an anionic surfactant, and Korean soil Vibrio meschnicoco species RH 530, a basophilic strain isolated from the virus, which was deposited with the Gene Bank of the Institute of Genetic Engineering, Korea Advanced Institute of Science and Technology on October 18, 1993, and can be distributed under accession number KCTC 0088BP. 6 kinds of alkaline active protein contaminase enzymes (prt 1 to 6. hereinafter referred to as 'Vaps' disclosed in Table 1 in the specification of Korean Patent No. 145277) secreted out of the cells from The liquid detergent composition excellent in the alkaline washing power which shows 8 or more was developed.

In the present invention, an enzyme activity inhibitor and an enzyme stabilizer were used to prevent the enzyme from being stabilized and decomposed in the product in addition to the surfactant and the enzyme, and other hard water softeners, solubilizers, alkali agents, fluorescent brighteners, and the like. In the liquid detergent composition according to the present invention, pH is alkaline by containing monoethanolamine or sodium carbonate, which is an alkaline agent, in the surfactant, and enzyme stabilization can be maintained in a product by appropriately using an enzyme stabilizer or the like.

Hereinafter, each composition constituting the present invention will be described.

[Surfactants]

The nonionic surfactant used as an essential surfactant among the components of the liquid detergent composition used in the present invention is a surfactant which shows the next consumption in an after-treatment industry as the anionic surfactant, and the hydroxyl group (OH) and the carboxyl group of the hydrophilic group molecule. A substance with a group that is not ionized, such as a (COOH) bond. Nonionic surfactants are classified into polyethylene glycol type and polyhydric alcohol type according to the type of hydrophilic group, and polyethylene glycol type is mainly used as a detergent and a penetrating agent than nonionic surfactants of polyhydric alcohol type. do.

The polyethylene glycol type is prepared by adding hydrophilic ethylene oxide (CH _₂ CH _₂ O) to a hydrophobic raw material having a reactive hydrogen atom. The reactive hydrogen atom herein refers to a hydrogen atom in a hydroxyl group (OH), a carboxyl group (COOH), an amine group (NH _₂ ) group, and an amide group (CONH _₂ ).

In the kind of the polyethylene glycol type,

Higher alcohol type;

Alkylphenyl system;

Is typically used,

In addition to fatty acids;

Higher aliphatic amines;

Aliphatic amides;

Or an alkanol amide: R 1 · COON (R 2 OH) 2 (R 1 is C ₁₂ to C _{20, and} R ₂ is C ₁ to C ₂ ).

In the liquid detergent of the present invention, 1 to 40% by weight, more preferably 10 to 33% by weight of polyoxyethylene lauryl ether, a polyethylene glycol type higher alcohol, is represented by the following general formula (I). .

RO- (CH ₂ CH ₂ O) nH ------ General formula (Ⅰ)

(R = C ₁₂ ~ C ₁₄ , n = 9mole)

Meanwhile, the anionic surfactants include linear alkylbenzene sulfonates, fatty acid soaps, alkyl sulfates, alpha olephine sulfonates, and alkyl ether sulfates. May be used, but in the present invention, alpha olefin sulfonate sodium salt represented by the following general formula (II) (R · CH = CHCH ₂ SO ₃ · Na + R · CHOHCH ₂ CH ₂ SO ₃ · Na) , R is C ₁₀ -C ₁₈ ) to 1 to 20% by weight, more preferably about 3 to 15%.

_{R · CH = CHCH 2 SO 3} · Na + R · CHOHCH 2 CH 2 SO 3 · Na ------ formula (Ⅱ)

(The carbon number of R in the structural formula is C ₁₀ ~ C ₁₈ )

This alpha olefin sulfonate is an economical raw material that has biodegradability in the natural state and excellent cleaning power and low raw material price compared to alkyl sulfate or alkyl ether sulfate compared to the linear alkylbenzene sulfonate commonly used as anionic surfactant. It is the most frequently used raw material with linear alkylbenzene sulfonate in laundry detergent.

[Water Softener]

Trisodium nitrilo acetate (Tri sodium Nitrilo Acetate), EDTA 4Na (Tetra Sodium Ethylene Di Amine Tetra Acetate), EDTA 2Na (Di Sodium Ethylene Di Amine Tetra Acetate), Sodium Citrate can do.

[Solubilizer]

The composition of the present invention may contain 1 to 15% by weight of a solubilizing agent based on the above-described surfactant, solubilizing agents such as ethyl alcohol (ROH: R = C ₂ ) or short chains such as ethylene glycol, propylene glycol Alcohol or hydrotrope such as sodium cumene sulfonate, sodium xylene sulfonate, urea, or the like may be used.

[Builder]

Builders are one of the important components of detergents in cleaning detergents. In general, builders are generally referred to as alkali agents and metal ion sequestrants, and the liquid detergent composition is limited in use due to formulation and stability problems.Alkali agents commonly used in liquid detergent compositions include monoethanolamine (MonoEthanolAmine), Liquid alkali agents such as diethanolamine (DiEthanolAmine), triethanolamine (TriEthanolAmine), and the like are often used, and powdered alkali agents such as sodium silicate and sodium carbonate (Sodium Carbonate) are limitedly used. In the present invention, sodium carbonate (Sodium Carbonate) as an alkali agent to contain 1 to 5% by weight, more preferably 1 to 3% by weight, and other monoethanolamine (MEA) that is used as a general alkali in the liquid detergent composition Was used.

[Proteolytic Enzyme]

As an enzyme, protease, which is a protease, was used. The composition of the present invention contains about 0.1 to 5% by weight of alkaline protease, more preferably about 0.1 to 4.0% by weight of active protease.

These proteases can be obtained from animals, plants and microorganisms. Commercially available suitable proteases include Alcalase, Esperase, Savinase from "NOVO" and Maxatase, Maxacal and Maxapem (Protein from "Genenco"). engineered Maxacal), but preferably 6 types of alkaline active protein contaminants that are secreted extracellularly from Vibrio meschnicoco species RH 530 (Vibrio metschnikovii sp. RH 530), a basophilic strain isolated from Korean soil. It is preferable to contain Vaps (prt 1 to 6 disclosed in Table 1 of the specification of Korean Patent No. 145277).

[Enzyme Stabilizer]

The composition of the present invention contains about 1 to 15% by weight of an enzyme stabilizer. More preferably, about 6-12 weight% of enzyme stabilizers are contained. Enzymes used in liquid detergents have a sensitization (Denaturation) action in which the enzyme loses activity due to attack by a surfactant in the composition over time. In particular, the activator uses a stabilizer to mitigate the effects of anionic surfactants rather than nonionic surfactants. As representative stabilizers, propylene glycol, ethylene glycol, and poly Oxyethylene glycol (Polyoxyethylene Glycol) and the like. The composition of the present invention was used in combination with propylene glycol and ethylene glycol.

[Enzyme Inhibitor]

Generally, boron compounds (boric acid, boric acid, boronic acid, borate, boric oxide) are widely known as inhibitors of active protease. In particular, compounds such as boronic acid and boric acid are known to bind to the proteolytic enzyme activity 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 histidine groups. In particular, boron compounds having an aryl group, such as phenyl boronic 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 aryl boronic acid (Aryl Boron acid) was used as an enzyme activity inhibitor among the components of the liquid detergent composition, and aryl boronic acid is represented by the general formula (III).

(Where X is Hydrogen or C1 to C6 Alkyl, Aryl, substituted C1 to C6 Alkyl, substituted Aryl, Hydroxyl, Hydroxyl derivative, Amine, C1 to C6 Alkylated Amine, Amine derivative, Halogen, Nitro, Thiol, Thiol derivative, Aldehyde , Acid, Acid salt, Ester, Sulfonate or Phophonate, etc.

Y is Hydrogen or C1 to C6 Alkyl, Aryl, substituted C1 to C6 Alkyl, substituted Aryl, Hydroxyl, Hydroxyl derivative, Amine, C1 to C6 Alkylated Amine, Amine derivative, Halogen, Nitro, Thiol, Thiol derivative, Aldehyde, Acid , Acid salt, Ester, Sulfonate or Phosphonate.)

The liquid detergent composition according to the present invention containing the above-described components first dissolves polyoxy ethylene lauryl ether, which is a nonionic surfactant, in ethylene glycol and propylene glycol, which are enzyme stabilizers, and alpha olefin selphonate and ionic water, which are anionic surfactants. To prepare a surfactant base, add aryl boronic acid as an enzyme activity inhibitor, add monoethanol amine or sodium carbonate as an alkali, and adjust the liquidity to alkali. (The pH of the composition in the finished state is about 9 to 10 It was prepared by adding protease). And if the viscosity needs to be adjusted at this time, it is adjusted using materials used in liquid detergent compositions such as short-chain alcohol or hydrotrope (Hydrotrope). Here, short-chain alcohols are alcohols having 1 to 5 carbon atoms, such as ethyl alcohol, propylene glycol, isopropanol, butanol, etc., and hydrotrope is a material commonly used for adjusting viscosity or stability in detergent composition. Sodium cumene sulfonate, xylene sulfonate, or urea.

Hereinafter, specific experimental examples of the present invention will be described.

Example 1 Liquid Detergent Preparation and Washing Power Investigation

In this embodiment, according to the composition described in Table 1 according to the composition of the liquid detergent of the present invention was prepared by changing the composition for each type of surfactant and then the washing power was tested.

Detergency evaluation was performed using a turgotometer manufactured by the US testing company mainly used for laboratory use. Washing temperature was operated at 120 ° C tagotometer rotation RPM, the sample volume was used 1g of water in 1L of sample, the washing time was 10 minutes, rinsing three minutes each.

AS12 and EMPA104 were used as the contaminated cloth used for the measurement. EMPA 104 and AS 12 were cut to 7 x 7 cm in width and used 7 sheets for each sample. Contamination was 15.84% by weight of Carboxy methyl carubin, 1.94% by Indian ink, peanut oil. 36.25% by weight, milk powder (38% casein) 3.70% by weight, filtrate (silica) 18.18% by weight, Emulgater D (Emulgater'D; Surfatant) 21.80%, yellow iron oxide 2.29% by weight.

The cleaning effect was measured using a color difference meter before and after washing, and the results were calculated according to the following formula, and the results are shown in Table 2. The composition containing a large amount of nonionic surfactants rather than the composition consisting only of anionic surfactants showed the washing power. It can be seen that better.

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

* A: whiteness of white cloth

* B: Pollutant whiteness before washing

* C: Pollutant whiteness after washing

<Table 1> Composition of detergent containing proteolytic enzyme by base according to type of surfactant (unit: weight%)

ingredient Detergent 1 Detergent 2 Detergent 3 Alkylbenzenesulfonic acid 12.0 6.1 Sodium hydroxide 1.3 0.65 Alkyl ether sulfate sodium salt 11.5 5.7 1.0 Alphaolefin Sulfonate Sodium Salt 7.1 3.6 2.0 Ethyl alcohol 5.0 5.0 5.0 Monoethanolamine 3.0 3.0 3.0 Polyoxyethylene lauryl ether 15.2 28.0 Propylene glycol 6.0 6.0 6.0 Ethylene glycol 6.0 6.0 6.0 Sodium formate 0.8 0.8 0.8 Boric acid 0.6 0.6 0.6 Phenyl boronic acid 0.1 0.1 0.1 Sodium xylenesulfonate 1.2 1.2 1.2 Protease 0.6 0.6 0.6 Ionized water balance balance balance TOTAL 100 100 100

<Table 2> Detergency of Detergent Composition Containing Proteolytic Enzymes by BASE According to Type of Surfactant

division Detergent 1 Detergent 2 Detergent 3 % Wash rate for EMPA104 27.9 27.1 27.8 % Cleans to AS12 31.1 33.2 35.2

As described above, in the detergent composition containing proteases (Vaps), a detergent composition containing a large amount of nonionic surfactants is used rather than a detergent composition containing a large amount of alkylbenzene sulfonic acid, which is generally used in detergents. It can be seen that better cleaning power.

Example 2 Preparation of Liquid Detergent and Detergency Determination with Different Composition Ratios of Polyoxyethylene Lauryl Ether as Nonionic Surfactant and Alphaolefin Sulfonate as Anionic Surfactant

<Table 3> Detergent composition with difference in composition ratio of polyoxyethylene lauryl ether and alpha olefin sulfonate

ingredient Detergent 4 Detergent 5 Detergent 6 Detergent 7 Detergent 8 Detergent 9 Alkyl ether sulfate sodium salt 14.0 Alphaolefin Sulfonate Sodium Salt 5.55 11.1 16.65 22.2 18.22 Ethyl alcohol 5.0 5.0 5.0 5.0 5.0 5.0 Monoethanolamine 3.0 3.0 3.0 3.0 3.0 3.0 Polyoxyethylene lauryl ether 33.0 27.0 21.7 16.0 11.0 Propylene glycol 6.0 6.0 6.0 6.0 6.0 6.0 Ethylene glycol 6.0 6.0 6.0 6.0 6.0 6.0 Sodium formate 0.8 0.8 0.8 0.8 0.8 0.8 Boric acid 0.6 0.6 0.6 0.6 0.6 0.6 Phenyl boronic acid 0.1 0.1 0.1 0.1 0.1 0.1 Sodium xylenesulfonate 1.2 1.2 1.2 1.2 1.2 1.2 Protease 0.6 0.6 0.6 0.6 0.6 0.6 Ionized water balance balance balance balance balance balance TOTAL 100 100 100 100 100 100

<Table 4> Detergency of detergent composition with difference in composition ratio of polyoxyethylene lauryl ether and alpha olefin sulfonate

division Detergent 4 Detergent 5 Detergent 6 Detergent 7 Detergent 8 Detergent 9 Contaminated cloth AS12 cleaning rate (%) 37.9 35.8 34.3 32.1 30.5 32.7

The results of the above washing power test result shows that the composition of the detergent 4 having a high content of non-ion shows the best washing power, and the composition of the detergents 5 and 6 containing some of the anions is good. However, the composition of detergent 4 showed good cleaning power, but the liquid phase showed instability that separated from weak alkali to white turbidity.

Example 3: Na ₂ CO ₃ Detergent preparation and cleaning power investigation

<Table 5> Detergent composition according to use of Na ₂ CO ₃

ingredient Detergent 9 Detergent 10 Alphaolefin Sulfonate Sodium Salt 5.55 5.55 Ethyl alcohol 5.0 5.0 Monoethanolamine 5.0 3.0 Polyoxyethylene lauryl ether 27.0 27.0 Propylene glycol 6.0 6.0 Ethylene glycol 6.0 6.0 Sodium formate 0.8 0.8 Boric acid 0.6 0.6 Phenyl boronic acid 0.1 0.1 Sodium xylenesulfonate 1.2 1.2 Sodium carbonate 3.0 Protease 0.6 0.6 Ionized water balance balance TOTAL 100 100

<Table 6> Detergency of the detergent composition according to the use of Na ₂ CO ₃

※ The cleaning rate is the result of using the AS12 cloth.

division Detergent 10 Detergent 11 % Cleaning rate 42.5 43.6

Alkali agents used in liquid detergents generally use mono ethanol amine to maintain the liquidity in an alkaline state. In the above experiment, it can be seen that the washing power of the detergent is increased by using sodium carbonate as the alkali agent in addition to the monoethanol as the alkali agent.

Example 4: Detergent preparation and cleaning power investigation according to enzyme concentration

<Table 7> Detergent composition according to enzyme concentration

ingredient Detergent 12 Detergent 13 Detergent 14 Detergent 15 Alphaolefin Sulfonate Sodium Salt 5.55 5.55 5.55 5.55 Ethyl alcohol 5.0 5.0 5.0 5.0 Monoethanolamine 3.0 3.0 3.0 3.0 Polyoxyethylene lauryl ether 27.0 27.0 27.0 27.0 Propylene glycol 6.0 6.0 6.0 6.0 Ethylene glycol 6.0 6.0 6.0 6.0 Sodium formate 0.8 0.8 0.8 0.8 Boric acid 0.6 0.6 0.6 0.6 Phenyl boronic acid 0.05 0.08 0.15 0.23 Sodium xylenesulfonate 1.2 1.2 1.2 1.2 Sodium carbonate 3.0 3.0 3.0 3.0 Protease 0.3 0.6 1.2 2.5 Ionized water balance balance balance balance TOTAL 100 100 100 100

<Table 8> Detergency of detergent composition according to enzyme concentration

※ The cleaning rate is the result of using the AS12 cloth.

division Detergent 12 Detergent 13 Detergent 14 Detergent 15 % Cleaning rate 41.8 43.7 44.8 45.3

Example 5: Detergent preparation and cleaning power according to the type of enzyme

<Table 9> Detergent composition according to enzyme type

ingredient Detergent 16 Detergent 17 Alphaolefin Sulfonate Sodium Salt 5.55 5.55 Ethyl alcohol 5.0 5.0 Monoethanolamine 3.0 3.0 Polyoxyethylene lauryl ether 27.0 27.0 Propylene glycol 6.0 6.0 Ethylene glycol 6.0 6.0 Sodium formate 0.8 0.8 Boric acid 0.6 0.6 Phenyl boronic acid 0.1 0.1 Sodium xylenesulfonate 1.2 1.2 Sodium carbonate 3.0 3.0 Proteases (Vaps) 0.6 Protease (Savinase) 0.6 Ionized water balance balance TOTAL 100 100

※ Savinase: Commercial PROTEASE from Denmark NOVO NORDISK

<Table 10> Detergency of detergent composition according to enzyme type

※ The cleaning rate is the result of using the AS12 cloth.

division Detergent 16 Detergent 17 % Cleaning rate 43.5 41.7

The experimental result is a result of comparing the general proteinase and Vaps which is widely used in the composition of the present invention, it can be seen that using the Vaps is more effective in the detergent composition of the present invention than using the general proteinase. .

According to the present invention as described above, it is possible to provide an alkaline liquid detergent excellent in washing power while using the proteolytic enzyme that does not cause contamination and takes advantage of the liquid detergent that is easy to use and excellent in solubility in cold water.

Claims (6)

In a liquid detergent composition for laundry comprising a surfactant, a water softener, a solubilizer, a fluorescent brightener, an enzyme, an alkaline agent and an enzyme stabilizer, 10 to 33% by weight of polyoxyethylene lauryl ether represented by the following general formula (I) as a nonionic surfactant, 3 to 15% by weight of an alpha olefin sulfonate represented by the following general formula (II) as an anionic surfactant A liquid detergent composition for laundry, characterized in that it contains. RO- (CH ₂ CH ₂ O) nH ------ General formula (Ⅰ) (In the above formula, R = C ₁₂ ~ C ₁₄ , n (ethylene oxide) is an additional mole of 9 mole) _{R · CH = CHCH 2 SO 3} · Na + R · CHOHCH 2 CH 2 SO 3 · Na ------ formula (Ⅱ) (The carbon number of R in the structural formula is C ₁₀ ~ C ₁₈ ) The method of claim 1, Washing liquid detergent composition, characterized in that it further comprises 0.1 to 4% by weight of alkaline active protease. The method of claim 2, The alkaline active proteases are six kinds of alkaline active protein contaminants which are secreted extracellularly from Vibrio meschnicoco species RH 530, a basophilic strain isolated from Korean soil. Liquid detergent composition for washing. The method according to claim 1 or 2, A liquid detergent composition comprising 1 to 3% by weight of sodium carbonate as an alkali builder. The method according to claim 1 or 2, Liquid detergent composition comprising 1 to 5% by weight of sodium carbonate (alkaline) as an alkali agent. The method according to claim 1 or 2, A liquid detergent composition further comprising 0.001 to 0.5% by weight of aryl boronic acid represented by the following general formula (III) as an enzyme stabilizer. (Where X is Hydrogen or C1 to C6 Alkyl, Aryl, substituted C1 to C6 Alkyl, substituted Aryl, Hydroxyl, Hydroxyl derivative, Amine, C1 to C6 Alkylated Amine, Amine derivative, Halogen, Nitro, Thiol, Thiol derivative, Aldehyde , Acid, Acid salt, Ester, Sulfonate or Phophonate, Y is Hydrogen or C1 to C6 Alkyl, Aryl, substituted C1 to C6 Alkyl, substituted Aryl, Hydroxyl, Hydroxyl derivative, Amine, C1 to C6 Alkylated Amine, Amine derivative, Halogen, Nitro, Thiol, Thiol derivative, Aldehyde, Acid , Acid salt, Ester, Sulfonate or Phosphonate.)