JPH0788517B2 - Enzyme-containing detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an enzyme-containing general household and commercial liquid or gel detergent, specifically, laundry washing,
The present invention relates to a so-called house hold detergent, shampoo and body washing detergent for washing dishes, washing furniture or houses.

[Prior Art and Problems Thereof] Addition of an enzyme to a detergent gives favorable results for washing such as improvement of washing rate, and various enzymes have been used or proposed.

For example, protease improves the cleaning rate by hydrolyzing protein components contained in human body dirt (Takao Ono, Bioindustry 3 , 181, (1986)).
etc). Lipase improves the cleaning rate by changing the triglyceride in human body lipids, which are difficult to remove with surfactants, to diglyceride or monoglyceride (M. Minagawa
J. Am. Oil Chem., 62 1053-1058 (1985) etc.). Amylase hydrolyzes the starch contained in stains of foods to facilitate the removal of stains, and cellulase is effective in removing dust stains, and improves the color of the washing finish of cotton cloth (Patent Document 1) (Sho 59-1598, No. 57-108199). Lysozyme is added in anticipation of a decrease in the number of viable bacteria due to the bacteriolytic action and an anti-inflammatory effect during body washing.

These enzymes are generally relatively stable in the dry state, and when the powder detergent is mixed with the enzyme, the dry state is maintained, so that the storage stability of the enzyme is good.

On the other hand, the enzyme easily changes its higher-order structure in the dissolved state and is easily inactivated. Many anionic surfactants that are widely used as the main component of detergents deactivate the enzyme in the presence of water. So there is a problem with liquid cleaners,
As a countermeasure, various proposals have been conventionally made.

For example, a method in which an alkyl ethoxylate having a large ethylene oxide addition number is used as a surfactant and the pH is adjusted to 8 to 10.5 to form a calcium salt (JP-A-58-80397).
No.), a method of adding propylene glycol or the like with an antioxidant such as sodium sulfite (JP-A-55-27378), a method of adding an alkoxylated alkylamine (JP-A-53-16012), polyhydroxy Method of adding compound and boric acid (JP-A-53-57209), method of adding free calcium ion and polyacid such as citric acid (JP-A-52-128904), nitrogen compound and lower carboxylic acid A method of adding salt and the like (JP-A-47-3733) has been proposed.

However, in spite of many of these proposals, it is a reality that the storage stability of the enzyme incorporated in the liquid or gel detergent is not sufficient (CAStarace, JA
M. Oil Chem. Soc., 60 1025 (1983) etc.).

[Object of the Invention] Accordingly, an object of the present invention is to provide a liquid or gel detergent composition containing an enzyme in a state of good storage stability.

[Summary of the Invention] The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, it is insoluble in a commonly used liquid or gel detergent, but when mixed with water together with the detergent. Is an easily soluble polyvinyl alcohol, coated with an enzyme dissolved or dispersed in a water-containing polyhydroxy compound to form a microcapsule, and when the microcapsule is blended with a detergent, the enzyme activity is stably maintained for a long period of time. This has led to the completion of the present invention.

That is, the present invention uniformly coats microencapsule coated with an enzyme with a saponification rate of 80 to 99% and an average degree of polymerization of 200 to 4,000 with polyvinyl alcohol or a crosslinked product thereof in a liquid or gel detergent having a water content of 5 to 70%. The liquid detergent composition is characterized in that the microcapsules dispersed in are soluble in water but insoluble in the detergent.

[Related Art of the Invention] The present invention is the first method for encapsulating an enzyme into a liquid detergent and encapsulating the enzyme in a liquid detergent. But,
There have been many proposals for encapsulation of enzymes in the past, and some proposals have been made for the purpose of blending detergents, but these are all intended for powdered and dry detergents.

For example, a dispersion liquid in which an enzyme and swellable particles coexist in a binder liquid is microencapsulated by a spray drying method to protect the enzyme in a dry state, but the enzyme is eluted in water (enzyme-containing capsule (Japanese Patent Publication No. 46). -42594),
Enzyme granules for detergents (Japanese Patent Publication No. 61-44471) consisting of modified cellulose that is neutral to acidic, water-insoluble, alkaline and water-soluble, coexists enzyme and inorganic salt in water-soluble binder solution There is an enzyme-containing capsule (Japanese Examined Patent Publication No. 50-22506) that microcapsules the solution prepared by spray drying, protects the enzyme in the dry state, and elutes the enzyme in water.

All of these proposals are directed to the formulation in a dry detergent, and do not consider the formulation to a system where water is present such as a liquid detergent.

As the enzyme-containing microcapsules, those which are encapsulated with a water-insoluble and semipermeable membrane for the purpose of other immobilized enzymes (for example, Japanese Patent Publication No. 52-18271) or have been developed for medicinal purposes. There are many enzyme enteric capsules (for example, JP-A-58-55413 and JP-A-58-67166), but it is difficult to use them for the same purpose as in the present invention.

On the other hand, it has been proposed to microencapsulate a drug other than an enzyme into a detergent.

For example, there is a composition in which a cationic agent is microencapsulated with dextrin or the like and blended with anhydrous anionic shampoo (Japanese Patent Laid-Open No. 50-3105). In this case, the shampoo is anhydrous and the microcapsule is anhydrous. Otherwise it will collapse.

Further, microcapsules coated with a special copolymer which is insoluble in alkaline water and soluble in neutral or acidic water have also been proposed (JP-A-61-28440 and 61-28441).
No.), it is described that if a laundry aid such as a softening finish is applied to the core substance, it can be used for blending a detergent. Also in this case, the purpose of the present invention is to release the softening agent at the time of rinsing by changing the pH of the washing liquid such as washing, dehydration and rinsing in the washing process, which is different from the object of the present invention.

The microcapsule used in the present invention has a water-soluble water-soluble substance as a core substance, which does not dissolve in a water-containing mixture such as a liquid detergent, but has a very special property of dissolving in water,
Never seen an example in the past.

[Structure of the Invention] Enzyme The enzyme applied to the detergent composition of the present invention is an enzyme that is active under neutral or alkaline conditions and contributes to improvement of detergency, and is significantly deactivated by the presence of detergent. Those that do not occur are desirable.

Examples of such an enzyme include Bacillus Licheniformis (Bacillus licheniformis), Bacillus Subtilis (Bacillus subtilis), Bacillus firmus (Bacillus pharmus), Bacillus SP.FERM.BP-93 (JP-A-58-134990), and Bacillus alcalophilus ( Proteases produced by strains such as Bacillus alcalophilus; Bacillus subtilis (bacillus subtilis), Bacillus licheniformis (bacillus licheniformis), amylase produced by strains such as Aspergillus oryzae (mucor lipolyticus) (mucor lipolyticus) , Candinda cylindracea, Pseudomouns nitroreducens, Pseudomonus fragi, Chromodbacterium viscosum, Rhizopus delemer Produced by a strain of Bacillus, and a lipase isolated by arterial pancreas of pigs; cellulase or hemicellulase produced by a strain of Bacillus Pasteri, Trichoderma viride, Aspergillus niger, etc. Hen egg white lysozyme and Bacillus subtilis
And lysozyme produced by such strains.

Enzyme support material In microencapsulation, the enzyme is handled in a state of being dissolved or dispersed in the support material. The enzyme support material is desirable for perfecting the capsule coating and also serves to enhance the storage stability of the enzyme.

A desirable substance as a supporting substance is a water-soluble polyhydroxy compound, that is, having 2 or more hydroxyl groups and 2 carbon atoms.
~ 6 compounds and their low polymers.

Specific examples include ethylene glycol, propylene glycol, butanediol, butanetriol, glycerin, mannitol, sorbitol, glucose, fructose, diethylene glycol, triethylene glycol, polypropylene glycol, dextrin, pectin, and alginic acid.

Coating Material The coating material for the microcapsules is one of the most important constituent elements of the present invention. The inventors of the present invention have found that a specific polyvinyl alcohol is optimal as a result of repeating various studies on a coating material which does not dissolve in a detergent having a water content of 70% or less but dissolves in water.

That is, the polyvinyl alcohol used as the microcapsule coating material in the present invention has (i) an average degree of polymerization of 200 to 4,000, preferably 500 to 2,500, and (ii) a saponification rate of 80 to 99%, preferably 87 to 99%. Is.

If the degree of polymerization is too high, there is a problem in terms of handling such as viscosity, and if the degree of saponification is low, there is a problem in coating strength in a liquid detergent.

In addition, in order to improve the strength of the capsule, it may be effective to treat the capsule with a crosslinking agent such as boric acid or a boric acid derivative.

Alkaline earth metal salt and enzyme stabilizer In order to further improve the storage stability of the enzyme, it is effective to add an alkaline earth metal salt to the enzyme support material.

The enzyme stabilizing effect of the alkaline earth metal salt varies depending on each enzyme, but it is desirable to add the alkaline earth metal salt in a ratio of 5 ppm or more with respect to the bulk enzyme powder in the capsule.

If calcium or the like is already present in the enzyme bulk powder in a sufficient amount, it is not necessary to add it during capsule formation, but if it is insufficient, it is water-soluble or at least partly soluble in alkaline earth metal salts. For example, calcium acetate, calcium chloride, calcium nitrate, magnesium acetate, magnesium chloride, magnesium nitrate, etc. are added.

In order to stabilize the enzyme, in addition to the above alkaline earth metal salts, antioxidants such as ascorbic acid and its derivatives, amino acids, polypeptides and their derivatives,
Addition of substances that form protective colloids such as gums is also effective, and these are applied as necessary.

Furthermore, the enzyme has a stable pH range, and the pH inside the capsule is
In order to maintain C. in a stable region, addition of salts or the like that form a buffering action is applied as necessary.

Microencapsulation Method The above-mentioned enzyme such as protease and polyvinyl alcohol are dissolved in a mixture of a polyhydroxy compound such as propylene glycol and water. If the amount of calcium in this solution is 5 ppm or less with respect to the enzyme, a calcium salt or the like is added, and further another enzyme stabilizer is added if necessary.

The microcapsules containing polyvinyl alcohol as a coating material can be prepared from this solution by, for example, the following method.

(I) A method of forming microcapsules by dropping the above enzyme solution into water and / or alcohol (ethanol, ethylene glycol, propylene glycol, glycerin, etc.) in which boric acid is dissolved as minute droplets.

(Ii) A method in which the enzyme solution is sprayed with a spray dryer to form microcapsules. In this case, the temperature of the hot air is 200 ° C. or lower at the inlet, and preferably 80 to 120 ° C. is applied in order to avoid the inactivation of the enzyme due to the rise in the product temperature.

iii) A method in which the enzyme solution is dispersed in a hydrophobic solvent (benzene, hexane, liquid paraffin, etc.) as fine droplets, and water is removed by heating or depressurization to obtain microcapsules.

Surfactant In the detergent composition of the present invention, a surfactant for general detergents, which also includes an anionic surfactant and a cationic surfactant, which have conventionally been limited in use in enzyme-containing liquid detergents for deactivating enzymes, is used. The agent can be widely used.

For example, as the anionic surfactant, sodium linear alkylbenzene sulfonate (alkyl: C _{10 to} C ₁₆ ) (LAS), sodium α-olefin sulfonate (olefin: C ₆
~C ₂₂₎ (AOS), sodium alkyl sulfate _{(alkyl: C 9 ~C 17) (AS} ), sodium polyoxyethylene alkyl ether sulfate _{(alkyl: C 9 ~C 17, EO =} 1~20) (AES), 2-Sulfo fatty acid ester sodium (fatty acid: C _{11 to} C
₁₇ , alcohol: C ₁ ~ C ₆ ) (SFE), sodium secondary alkane sulfonate (alkane: C ₁₂ ~ C)
₁₈ ) (SAS), soap (fatty acid: C _{12 to} C ₁₈ ), sodium alkyl phosphate (alkyl: C _{9 to} C ₁₇ ), and the like, and nonionic surfactants include polyoxyethylene alkyl ether (alkyl). : C _{5 to} C ₁₇ , EO = 4 to 20 (A
E), polyoxyethylene alkyl phenyl ether (alkyl: C _{6 to} C ₁₂ , EO: 4 to 20) (APE), and the like. Cationic surfactants include cetyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, Examples thereof include distearyldimethylammonium chloride, and examples of the zwitterionic surfactant include lauryl betaine and stearyl betaine.

Composition of Detergent Composition The basic composition of the detergent according to the present invention is as follows.

Enzyme-containing capsule 0.01-10% (wt%) Surfactant 3-70% Water 5-70% The enzyme-containing capsule to be mixed is not limited to one type. Conventionally, it has been difficult to mix several kinds of enzymes in a system in which water such as a liquid detergent is present. However, according to the present invention, for example, protease, amylase, etc. are separately microencapsulated to prepare a plurality of enzymes. Even if the microcapsules of the seeds are mixed at the same time, the storage stability can be maintained in a good state.

In the detergent composition of the present invention, in addition to the above basic composition,
Builders commonly used in detergents such as propylene glycol, ethanol, fluorescent dyes, and citric acid are added as needed.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In the following examples, as the enzyme titer unit, a protease is a unit described in JP-A-58-134990, an amylase is a unit described in Japanese Industrial Standard JIS-K7001 (1972), and a cellulase is “Enzyme Utilization Handbook”. (Jijijinkan, Showa 55
Michio Ozaki, pp. 298, units of lysozyme described in "Enzyme Utilization Handbook", page 422, and lipases described in "Enzyme Utilization Handbook", page 230.

Example 1 Bacillus SP.FERM BP-93 described in JP-A-58-134990
Cultured, and a protease with a titer of 105 nkat / mg (API-21)
A bulk powder was obtained (the titer was measured according to the method described in JP-A-58-134990).

This protease was prepared into a solution containing the following mixture.

Protease (API-21) Bulk powder 70g Calcium acetate 8g Propylene glycol 480g Polyvinyl alcohol (Average degree of polymerization 2,000, Saponification rate 95%)
55 g Distilled water 387 g After filtering this solution through a filter, it was dropped into a saturated aqueous solution of boric acid through a thin nozzle to form microcapsules.
The microcapsules were separated by filtration and stored in propylene glycol containing 25% water.

The size of the microcapsules was about 150-800μ in diameter.

Next, a liquid detergent composition having the following composition containing propylene glycol in which the above microcapsules were dispersed was prepared. Composition weight% of composition Polyoxyethylene alkyl ether sodium sulfate (C _14-15 , EO = 15) 15 Polyoxyethylene alkyl ether C _12-15 , EO = 10 18 Carboxymethyl cellulose 1 Polyethylene glycol (MW6,000) 1 ethanol 10 sodium citrate dihydrate 8 microcapsule propylene glycol dispersion (average protease titer 4,000 nkat / ml) 5 distilled water 42 Comparative Example 1 Protease (API-21) and calcium acetate 25%
Example 1 except that the solution was dissolved in propylene glycol containing water, the protease titer was 4,000 nkat / ml, and a solution containing 50 mM of calcium ions was used, and this solution was used instead of the propylene glycol dispersion of the microcapsules. A composition having exactly the same composition as that of the liquid detergent of Example 1 was prepared.

The liquid detergent compositions of Example 1 and Comparative Example 1 were treated at 38 ° C (100
After 10 intermediate storage at ° F), the activity of the enzyme was measured.
In the case of Comparative Example 1 was 80-85%, but in the case of Comparative Example 1 containing the protease propylene glycol, it was 3% (detection limit) or less.

Example 2 Commercial lipase isolated from swine pancreas (Amano Pharmaceutical Co., Pancreatin TA, lipase titer 5,000 U / g), (Bacillus subt
Amylase obtained by culturing ilis (Yamato Kasei, Krystase M20, titer 220,000 U / g) and Bacillus subtili
Using the protease (Daiwa Kasei, Protin AS, titer 600,000 PU / g) obtained by culturing s, the following composition was prepared as solution A,
B and C were created.

Next, the solutions A, B and C were dropped from boric acid saturated Wednesday containing 50% ethanol each through a fine nozzle to form microcapsules, and treated in the same manner as in Example 1 to contain 25% water. Stored in propylene glycol.

Next, a liquid detergent composition having the following composition containing the above three types of microcapsules was prepared. Composition Weight% Polyoxyethylene alkyl ether Sodium sulfate (C _14-15 , EO = 5) 10 Polyoxyethylene alkyl ether C _13-15 , EO = 12 25 Mashi fatty acid sodium salt 5 Carboxymethyl cellulose 1 Lipase micro Capsule-Propylene dispersion (Average lipase titer, 3,300U / ml) 3 Amylase microcapsule-Propylene dispersion (Average lipase titer, 3,300U / ml) 3 Protease microcapsule-Propylene dispersion (Average protease titer, 1,800 nkat / ml) 10 Diethylene glycol 7 Distilled water 36 Comparative Example 2 Lipase bulk powder, amylase bulk powder, and protease bulk powder were dissolved in propylene glycol (containing 25% water) containing 60 mM of calcium ion, and the average lipase titer was 100 U / ml propylene glycol solution, average amylase force 3,300U
/ ml propylene glycol solution and an average protease titer of 1,800 nkat / ml propylene glycol solution were prepared and used in place of the microcapsule dispersions of Example 2 respectively, corresponding to detergent compositions A, B, C. A composition was made.

The liquid detergent compositions of Example 2 and Comparative Example 2 were treated at 38 ° C (100
In the case of Example 2 in which the enzyme was incorporated as microcapsules, the residual enzyme activity after storage at 8 ° F) for 8 weeks was lipase 75-80, amylase 80-85%, protease 80-
Although it was 85%, it was 3% (detection limit) or less in the case of Comparative Example 2 in which the enzyme was blended as a propylene glycol solution.

Example 3 A solution containing the following mixture was prepared using an alkaline protease obtained by culturing Bacillus licheniformis (manufactured by Sigma, product number p5380).

Alkaline protease 50g Magnesium chloride 3g Calcium chloride 3g Sodium ascorbyl monophosphate 4g Propylene glycol 450g Polyvinyl alcohol (average degree of polymerization 1,000, saponification rate 99%)
45 g distilled water 445 g The above protease solution was added dropwise to a propylene glycol-water mixed solution saturated with boric acid to prepare microcapsules, which were separated by filtration and stored in propylene glycol containing 25% water. .

Next, a gel detergent composition having the following composition containing propylene glycol in which the microcapsules were dispersed was prepared. Composition weight% of composition Polyoxyethylene alkyl ether sodium sulfate (C _13-15 , EO = 5) 8 Polyoxyethylene alkyl ether C _13-15 , EO = 10 25 Sodium stearate 3 Sodium citrate / 2 water Salt 10 Carboxymethylcellulose 1 Polyethylene glycol (MW1,000) 3 Propylene glycol dispersion of microcapsules (average protease activation, 1,600 nkat / ml) 10 Propylene glycol 14 Distilled water 16 Comparative Example 3 Alkaline protease (Sigma, P5380) 1,600nkat /
ml and calcium chloride (0.3%), magnesium chloride (0.8%), sodium ascorbyl monophosphate (0.
A propylene glycol solution containing 4) (25% water) was prepared, and a composition having exactly the same composition as the gel detergent of Example 3 was used except that this solution was used instead of the microcapsule dispersion of Example 3. Created.

The gel detergent compositions of Example 3 and Comparative Example 3 were treated at 38 ° C (10
The residual activity rate of the enzyme in the gel detergent composition after storage at 0 ° F) for 10 weeks was determined by Example 3 containing microcapsules.
In the case of Comparative Example 3 containing a propylene glycol solution of protease, it was 3%.
(Detection limit) or less.

Example 4 Thermostable amylase obtained by culturing Bacillus subtilis (Daiwa Kasei Co., Krystase TU20, titer 220,000 U /
g) and Bacillus subtilis cultured thermostable protease (Daiwa Kasei, Samoases PS, titer 500,000
PU / g) was used to prepare solutions D and E having the following compositions.

Next, the solutions D and E were dropped into a saturated aqueous solution of fluoric acid containing 10% ethanol and 20% ethylene glycol from a fine nozzle to separate the produced microcapsules, and 25% water was added.
It was dispersed in propylene glycol containing and stored.

Next, the above microcapsules were blended to prepare a dishwashing detergent composition having the following composition. Composition wt% Sodium dodecyl sulfate 20 Alcohol ethoxylate (C _13-15 , EO = 10 moles) 20 Carboxymethyl cellulose 1 Amylase-microcapsule dispersion (average amylase titer 3,000 U / ml) Protease-microcapsule dispersion (Average protease titer 1,500 nkat / ml) 47 Distilled water 47 Comparative Example 4 Heat-resistant amylase powder and heat-resistant protease powder were mixed with propylene glycol (25
% Propylene glycol solution with an average amylase titer of 3,000 U / ml and an average protease titer.
A 1,500 nkat / ml propylene glycol solution was prepared and used in place of the amylase and protease microcapsule dispersions of Example 4, respectively, except otherwise the dishwashing detergent composition was prepared.

After the detergent compositions of Example 4 and Comparative Example 5 were stored at 38 ° C. (100 ° F.) for 10 weeks, the residual activity ratio of the enzyme in the detergent composition was calculated in the case of Example 4 formulated as microcapsules, amylase. , 90 to 95% together with protease, but in Comparative Example 4 in which the enzyme was blended as a propylene glycol solution, it was 3% (detection limit) or less.

Example 5 Lysozyme isolated from chicken egg (manufactured by Sigma, product number)
L7001) was used to prepare a solution containing the following mixture.

Lysozyme 20 g Calcium chloride 3 g Propylene glycol 520 g Ascorbic acid monophosphate sodium salt 2 g Polyvinyl alcohol (average degree of polymerization 700, saponification rate 87%) 45
g Ethanol 20 g Distilled water 390 g This solution was used to prepare microcapsules using a spray dryer equipped with a rotating disk type disperser. The size of the microcapsules was about 20-100μ in diameter. Next, a shampoo composition having the following composition containing propylene glycol in which the microcapsules were dispersed was prepared. Composition wt% Polyoxyethylene lauryl ether Sodium sulfate 10 Sodium stearate 5 Sodium laurate 8 Propylene glycol 47 Ethyl alcohol 15 Lysozyme microcapsules Propylene glycol dispersion (average lysozyme titer 400U / ml) 5 Distilled water 10 Comparative example 5 Potency including lysozyme, calcium chloride (0.3%), sodium ascorbyl monophosphate (0.2%) 4
A shampoo composition having exactly the same composition as in Example 5 was prepared, except that a propylene glycol solution of 00U / ml of lysozyme was prepared and this solution was used instead of the lysozyme microcapsule dispersion liquid of Example 5.

The shampoo compositions of Example 5 and Comparative Example 5 were mixed at 30 ° C for 3
The residual activity ratio of the enzyme in the shampoo composition after monthly storage was 90 to 95% in the case of Example 5 formulated as microcapsules, but in Comparative Example 5 in which the enzyme was formulated as a propylene glycol solution. In case of 3% (detection limit)
It was below.

[Effects of the Invention] The present invention provides a detergent composition prepared by microencapsulating an enzyme-stabilized solution in a liquid or gel detergent, and according to the present invention, (1) Since the enzyme is coated with polyvinyl alcohol, which is insoluble and plastic in water, the enzyme remains stable during storage of the detergent. (2) It tends to inactivate the enzyme in the presence of water. Since the enzyme does not directly contact the surfactant and other detergent builders during storage of the detergent, the storage stability of the enzyme is significantly improved as compared with the conventional enzyme-containing liquid detergent. (3) Inactivate the enzyme Therefore, it can be applied to the case of using a cationic surfactant or anionic surfactant that could not take the detergency of the enzyme into consideration. Mixing element is separately excellent effects such as it has become possible by utilizing microencapsulated enzymes is obtained.

Claims (5)

[Claims] 1. An enzyme having a saponification rate of 80 to 99% and an average degree of polymerization of 200.
~ 4,000 polyvinyl alcohol or a cross-linked microcapsule-coated microcapsules are uniformly dispersed in a liquid or gel detergent having a water content of 5 to 70%. The microcapsules are insoluble in the detergent but do not dissolve in water. Is a liquid detergent composition having the property of dissolving. 2. The detergent composition according to claim 1, wherein the enzyme is microencapsulated in a state of being dissolved or dispersed in a water-containing polyhydroxy compound. 3. The detergent composition according to claim 2, wherein the alkaline earth metal salt is encapsulated in microcapsules together with the enzyme. 4. The average degree of polymerization of polyvinyl alcohol is 500.
The detergent composition according to any one of claims 1 to 3, wherein the detergent composition is 2,500. 5. A liquid or gel detergent mainly comprising a nonionic surfactant and / or an anionic surfactant as a surfactant.
Item 4. The detergent composition according to any one of items 4.