JPWO2011052501A1 - Liquid detergent composition and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide a liquid detergent composition capable of maintaining the storage stability of an enzyme well without reducing the enzyme activity even when the surfactant is contained in a high concentration, and a method for producing the same. . Liquid detergent composition characterized by containing the components shown in the following (A) to (D): (A) component: surfactant (however, nonionic surfactant is 60% by mass or more in component (A)) (B) component: homopolyamino acid and / or salt thereof; (C) component: enzyme; (D) component: water.

Description

The present invention relates to a liquid detergent composition and a method for producing the same.
This application claims priority on November 2, 2009 based on Japanese Patent Application No. 2009-252159 for which it applied to Japan, and uses the content here.

There are two types of cleaning agents for clothes used for washing at home: powder type and liquid type.
Since powder detergent contains less moisture, it is advantageous in stably blending functional materials that are unstable in water and functional materials that react in water. Products have been developed.

  Among functional materials used in detergents for clothing, enzymes are one of the important functional materials, especially in the harsh washing conditions in Japan (low temperature, low concentration, short time washing, etc.) It is used as an additive that demonstrates For this reason, enzymes are blended in many commercially available powder detergents for clothing, and many studies have been made to stably blend enzymes in detergents.

On the other hand, liquid detergents have been used not only in Japan but also in various countries in recent years because they are less likely to remain undissolved and can be applied directly to clothing.
However, the liquid detergent has a lower enzyme stability in the detergent than the powder detergent, and has not reached a satisfactory level. Therefore, improvement of the stability of the enzyme in the cleaning agent is an important issue for ensuring high detergency.

Examples of the enzyme stabilization technique in the liquid detergent include stabilization by adding a calcium salt that generates free calcium ions (see Patent Document 1), and short-chain carboxylates such as formate and lactate. Stabilization (see Patent Document 2), stabilization by blending a polyol and boric acid or a derivative thereof (see Patent Document 3), (meth) acrylic acid / (meth) acrylic ester copolymer And stabilization by blending polyethylene glycol with polyethylene glycol (see Patent Document 4), stabilization by bringing a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, guar gum or the like into contact with an enzyme (see Patent Document 5). .
As a method for stabilizing enzyme activity, for example, a method of adding polyglutamic acid to an enzyme (see Patent Document 6) is known.

Japanese Patent Laid-Open No. 5-179291 Japanese Patent Laid-Open No. 5-179292 Japanese Patent Laid-Open No. 7-501349 JP 11-193398 A JP-T-4-501653 JP 2007-97586 A

By the way, in recent years, considering the environment and convenience at the time of purchase, so-called "compact type" cleaning that can achieve the same number of times of use as before use is reduced even if the amount of use is reduced. Agents are mainstream.
Since this compact type liquid detergent contains a high concentration of surfactant, the proportion of water is small. For this reason, the enzyme mix | blended with the compact type liquid detergent became difficult to melt | dissolve, and it was easy to precipitate or modify | denature. In particular, when a protease is used as the enzyme, there is a problem that the enzyme activity tends to decrease due to autolysis.

For these problems, the methods described in Patent Documents 1 to 5 do not satisfy sufficient storage stability of the enzyme. In addition, when a storage test is performed assuming long-term storage, the enzyme activity may be reduced to a level at which the performance cannot be sufficiently exhibited. In particular, the liquid detergent containing a surfactant at a high concentration is prominent, and the enzyme activity tends to decrease.
The method described in Patent Document 6 is intended to impart resistance to temperature and pH to an enzyme, and is assumed to be applied in an environment where the enzyme is difficult to dissolve, such as a compact liquid detergent. Absent.

  The present invention has been made in view of the above circumstances, and even when a surfactant is contained in a high concentration, a liquid detergent that can maintain the storage stability of the enzyme satisfactorily without reducing the enzyme activity. It aims at providing a composition and its manufacturing method.

  As a result of intensive studies, the present inventors have found that a liquid detergent composition containing a surfactant contains a homopolyamino acid to suppress a decrease in enzyme activity even when an enzyme is added, and in particular, stable storage of the enzyme. The present inventors have found that the storage stability of the enzyme can be maintained well even when the surfactant, which has been difficult to make, is contained at a high concentration and stored for a long period of time, has led to the completion of the present invention.

That is, the liquid detergent composition of the present invention is characterized by containing the components shown in the following (A) to (D):
(A) component: Surfactant (however, a nonionic surfactant is included in the component (A) in an amount of 60% by mass or more);
(B) component: homopolyamino acid and / or salt thereof;
(C) component: enzyme;
(D) Component: Water.

Here, it is preferable that content of the said (A) component is 45-65 mass% in 100 mass% of liquid cleaning composition.
Moreover, it is preferable that content of the said (D) component is 20-40 mass% in 100 mass% of liquid cleaning composition.
Further, the homopolyamino acid is preferably polyglutamic acid and / or polyaspartic acid.
Moreover, even if the said (C) component is protease, the fall of enzyme activity can be suppressed.
Furthermore, the liquid detergent composition of the present invention is particularly suitable for clothing.
Moreover, the manufacturing method of the liquid cleaning composition of this invention mixes the remaining component, after mixing said (B) component, said (C) component, and a part or all of said (D) component. It is characterized by doing.

  According to the present invention, even when a surfactant is contained in a high concentration, there is provided a liquid detergent composition that can satisfactorily maintain the storage stability of an enzyme without reducing the enzyme activity and a method for producing the same. it can.

Hereinafter, the present invention will be described in detail.
The liquid detergent composition of the present invention contains the above components (A) to (D).
[(A) component]
(A) A component is surfactant and is used in order to provide detergency to a liquid detergent composition.
As for content of (A) component, 10-70 mass% is preferable in 100 mass% of liquid cleaning composition, More preferably, it is 30-70 mass%, Most preferably, it is 45-65 mass%.
If content of (A) component is 10 mass% or more, sufficient cleaning power can be provided to a liquid detergent composition. On the other hand, if content of (A) component is 70 mass% or less, high storage stability can be provided to a liquid detergent composition.
In particular, if the content of the component (A) is in the range of 45 to 65% by mass, the component (A) is contained at a high concentration, so the liquid detergent composition of the present invention is of a compact type. While being able to use suitably as a cleaning agent, generation | occurrence | production of the cloudiness of the external appearance derived from an enzyme can be suppressed.

In addition, since containing (A) component in high concentration leads to reduction of the content of water which is (D) component, when not containing (B) component mentioned later, enzyme which is (C) component Activity tends to decrease due to storage of the liquid detergent composition.
However, since the liquid detergent composition of the present invention contains the component (B), it is easy to form a complex with the component (B) and the component (C), and the component (C) is easily stabilized. Therefore, the liquid detergent composition of the present invention can maintain the storage stability of the enzyme well even when the component (A) is contained in a high concentration.

  As the component (A), a nonionic surfactant is used. Moreover, you may use together general surfactant used for cleaning agents, such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. In particular, it is preferable to use a nonionic surfactant and an anionic surfactant in combination in terms of superior cleaning performance.

<(A-1) component: nonionic surfactant>
(A-1) A component is a nonionic surfactant.
Although it does not restrict | limit especially as (A-1) component, For example, the polyoxyalkylene type nonionic surfactant represented with the following general formula (I) is used suitably.
_{^{R 1 -X- (EO) s /}} (PO) t -R 2 ··· (I)

In formula (I), R ¹ is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and may be linear or branched. Examples of the hydrophobic group include those derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides and the like.
-X- is a functional group such as -O-, -COO-, -CONH-.
EO represents an oxyethylene group [— (OCH ₂ CH ₂ ) —], which is a functional group obtained by addition reaction of ethylene oxide. PO represents an oxypropylene group [— (OCH ₂ CH (CH ₃ )) —], which is a functional group obtained by addition reaction of propylene oxide.
s represents the average added mole number of ethylene oxide, and is an integer of 3 to 20, preferably 5 to 18.
t represents the average added mole number of propylene oxide, and is an integer of 0 to 6, preferably 0 to 3.
R ² is a hydrogen atom, or an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom, or an alkyl group or alkenyl group having 1 to 3 carbon atoms.

In the formula (I), when EO and PO coexist in the same molecule, ethylene oxide and propylene oxide may be either random addition or block addition. Moreover, the addition order of ethylene oxide and propylene oxide is not particularly limited.
If the average added mole number s of ethylene oxide is less than 3, odor tends to be generated or the liquid detergent composition tends to deteriorate. On the other hand, if the average added mole number s of ethylene oxide exceeds 20, the HLB value becomes too high, and it is disadvantageous especially for sebum cleaning, so that the cleaning function tends to be lowered.
When the average added mole number t of propylene oxide exceeds 6, the storage stability of the liquid detergent composition at a high temperature tends to decrease.
Here, "HLB (Hydrophile-Lipophile Balance)" is the relative strength of hydrophilicity and lipophilicity of the surfactant molecule, and represents the hydrophilic-lipophilic balance quantitatively. Say.

The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited and is likely to vary depending on the reaction method in producing the nonionic surfactant. For example, the distribution of added moles of ethylene oxide or propylene oxide is compared when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. Tend to be widely distributed. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

In formula (I), when -X- is -O-, the nonionic surfactant is an alcohol ethoxylate. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ¹ is 10 to 22, preferably 10 to 20, and more preferably 10 to 18. R ¹ may have an unsaturated bond. In this case, R ² is preferably a hydrogen atom.

Further, when -X- is -COO- in formula (I), the nonionic surfactant is a fatty acid ester type nonionic surfactant. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ¹ is 9 to 21, preferably 11 to 21. R ² may have an unsaturated bond. In this case, R ² is preferably an alkyl group having 1 to 3 carbon atoms.

  Specific examples of the nonionic surfactant represented by the formula (I) include: Mitsubishi Chemical Co., Ltd .: trade name Diadol (C13, C represents the number of carbons; the same shall apply hereinafter); Shell Corporation: trade name Neodol (C12 / C13), manufactured by Sasol: a product obtained by adding 12 moles or 15 moles of ethylene oxide to an alcohol such as trade name Safol23 (C12 / C13), manufactured by P & G: trade names CO-1214 and CO Ethylene oxide equivalent to 12 moles or 15 moles of ethylene oxide added to natural alcohol such as -1270, or C13 alkene obtained by trimerizing butene to the oxo method (BASF: trade name Lutensol TO7) with pentanol as garvet 7 mol equivalent ethylene oxide added to the C10 alcohol obtained by the reaction (BASF: trade name Lutensol XL70), 6 mol equivalent ethylene oxide to the C10 alcohol obtained by subjecting the pentanol to the garbed reaction Addition (BASF, trade name: Lutensol XA60), or secondary alcohol having 12 to 14 carbon atoms added with 9 or 15 moles of ethylene oxide (Nippon Shokubai, trade name: Softanol 90 And softanol 150). Furthermore, with respect to palm fatty acid methyl (lauric acid / myristic acid = 8/2), using an alkoxylation catalyst, 15 mole equivalent of ethylene oxide (polyoxyethylene palm fatty acid methyl ester (hereinafter, “ MEE ”) and 15 moles of ethylene oxide).

Further, as the component (A-1), other nonionic surfactants other than the nonionic surfactant represented by the formula (I) may be used.
Other nonionic surfactants include, for example, alkylene oxide adducts such as alkylphenols, higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxides thereof. Examples include adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.

As the component (A-1), a single type of nonionic surfactant may be used alone, or a plurality of types of nonionic surfactants may be used in combination.
If the surfactant is contained in a high concentration, there are advantages that washing can be performed with a small amount of use and the detergent container can be made compact. In such a case, from the viewpoint of containing the surfactant at a high concentration, the component (A-1) is a compound obtained by adding ethylene oxide and propylene oxide to a primary or secondary alcohol, or a secondary alcohol. Gelation region even at high concentrations, such as compounds in which ethylene oxide is added to (secondary alcohol ethoxylates, Softanol series made by Nippon Shokubai Co., Ltd.) and compounds in which ethylene oxide is added to fatty acid methyl (MEE) Is preferably used. In particular, when a plurality of types of nonionic surfactants are used in combination, a compound in which ethylene oxide and propylene oxide are added to a primary or secondary alcohol from the viewpoint of gelation at the time of dilution and the usability of the composition, It is preferable to use a compound in which ethylene oxide is added to a secondary alcohol or a combination of MEE and a compound in which ethylene oxide is added to a primary alcohol. When two of these are used in combination, the ratio is preferably 3/7 to 10/0, more preferably 5/5 to 10/0, and particularly preferably 7/3 to 10/0. is there.

  (A-1) Content of a component is 60 mass% or more in 100 mass% of (A) component, and 90 mass% or more is preferable. If the content of the component (A-1) is 60% by mass or more, the formation of a complex of the component (B) and the component (C) described later is not hindered. Good storage stability can be maintained.

<(A-2) component: anionic surfactant>
(A-2) A component is an anionic surfactant.
(A-2) It does not restrict | limit especially as a component, A well-known anionic surfactant can be used and it can obtain easily in a market.
Examples of the component (A-2) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Alkane sulfonate having a group; α-sulfo fatty acid ester salt and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

As the component (A-2), the following are specifically preferable.
As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added (ie, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferred.
As the alkanesulfonate, a secondary alkanesulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms, is particularly preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
Among these, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are particularly preferable.

Further, as the component (A-2), other anionic surfactants other than those described above may be used.
Other anionic surfactants include, for example, higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, carboxylic acid types such as acylamino carboxylates, Examples thereof include phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts and glycerin fatty acid ester monophosphoric acid ester salts.

As the component (A-2), a single type of anionic surfactant may be used alone, or a plurality of types of anionic surfactants may be used in combination.
The content of the component (A-2) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and particularly preferably 0 to 10% by mass in 100% by mass of the component (A).

<(A-3) component: cationic surfactant>
(A-3) A component is a cationic surfactant.
Examples of the component (A-3) include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl benzyl dimethyl ammonium salts, and alkyl pyridinium salt cationic surfactants.

As the component (A-3), a single type of cationic surfactant may be used alone, or a plurality of types of cationic surfactants may be used in combination.
0-20 mass% is preferable in 100 mass% of (A) component, and, as for content of (A-3) component, 0-10 mass% is more preferable.

<(A-4) component: amphoteric surfactant>
The component (A-4) is an amphoteric surfactant.
As the component (A-4), for example, alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant Etc.

As the component (A-4), a single type of amphoteric surfactant may be used alone, or a plurality of types of amphoteric surfactants may be used in combination.
The content of the component (A-4) is preferably 0 to 20% by mass and more preferably 0 to 10% by mass in 100% by mass of the component (A).

[Component (B)]
The component (B) is a homopolyamino acid and / or a salt thereof, containing a surfactant at a high concentration, or without reducing the enzyme activity even if the liquid detergent composition is stored for a long period of time. Used as a stabilizer for maintaining good storage stability of the enzyme.
A homopolyamino acid is a polymer composed of a single amino acid. Examples of homopolyamino acid salts include sodium salts, potassium salts, calcium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts.

Typical examples of the homopolyamino acid include polylysine composed of lysine, polyglutamic acid composed of glutamic acid, polyaspartic acid composed of aspartic acid, and the like. Among these, polyglutamic acid and / or polyaspartic acid is preferable, and polyglutamic acid (γ-polyglutamic acid) formed by condensing a part or all of the carboxyl group at the γ-position and / or the carboxyl at the β-position More preferred is polyaspartic acid (β-polyaspartic acid) formed by condensation of a part or all of the groups, and γ-polyglutamic acid and / or β-polyaspartic acid represented by the following general formula (II) Is particularly preferable, and γ-polyglutamic acid represented by the following general formula (II) is most preferable.
^{H- (NH-CH (COOH)} -R 3 -CO-) n OH ··· (II)

In formula (II), R ³ is an alkylene group having 1 to 2 carbon atoms. When R ³ is an alkylene group having 2 carbon atoms, formula (II) represents γ-polyglutamic acid, and when R ³ is an alkylene group having 1 carbon atom, formula (II) represents β-polyaspartic acid. .
n is an integer of 4 to 200000. If n is 4 or more, the stability of the enzyme in the detergent composition tends to be improved. On the other hand, if n is 200,000 or less, component (B) or a premixed product containing component (B), which will be described later in detail, tends to suppress the occurrence of turbidity when blended with the remaining components.

As the component (B), γ-polyglutamic acid represented by the formula (II) and / or a salt thereof is most preferable among the above-mentioned components. The reason is estimated as shown below.
γ-polyglutamic acid and its salts are not limited to the fact that the amide bond at the γ-position can be present stably with almost no hydrolysis action on the enzyme (particularly protease) as component (C), and the type of component (A) And by adjusting the content, it is difficult for the (A) component to inhibit the formation of the complex of the (B) component and the (C) component. That is, by using a specific γ-polyglutamic acid and / or a salt thereof as the component (B), a complex of the component (B) and the component (C) is more easily formed, and the surfactant is added at a high concentration. Even when it is contained or the liquid detergent composition is stored for a long period of time, the storage stability of the enzyme can be maintained well without reducing the enzyme activity.

  In the present invention, “γ-polyglutamic acid and a salt thereof” may partially have an amide bond at the α-position as long as the amide bond at the γ-position is the main skeleton. Cross-linking may be performed between molecules, and a part or all of the side chain carboxylic acid may be a salt or an ester.

The glutamic acid constituting the polyglutamic acid may be D-type or L-type, but a higher ratio of L-type is preferred from the viewpoint of enhancing the storage stability of the enzyme.
However, since the water retention is improved when the proportion of the L-type is increased, free water in the liquid detergent composition is easily taken away, and as a result, the initial appearance and the appearance after storage of the liquid detergent composition are turbid, Each component may be separated. Therefore, from the viewpoint of maintaining transparency and maintaining the stability of the enzyme, the ratio of D type to L type (D / L ratio) is preferably 3/7 to 9/1, and 4/6 to 8 /. 2 is more preferable, and 5/5 to 8/2 is particularly preferable.

In addition, homopolyamino acids and salts thereof tend to improve the storage stability of the enzyme as the mass average molecular weight increases. In particular, a crosslinked homopolyamino acid obtained by irradiating γ rays and a salt thereof can provide a remarkable effect even in a small amount.
However, when a high molecular weight homopolyamino acid and / or a salt thereof is used as the component (B), precipitation of the enzyme is less likely to occur, but the liquid detergent composition becomes cloudy compared to the case of using a low molecular weight one, There is a tendency that components other than enzymes are easily separated.

As the homopolyamino acid and salts thereof, those having a mass average molecular weight of 5,000 to 20,000,000 are preferably used, more preferably 15,000 to 10,000,000, still more preferably 100,000 to 6,000,000. When the mass average molecular weight is within the above range, the turbidity of the liquid detergent composition and the separation of each component can be suppressed while improving the storage stability of the enzyme.
The mass average molecular weight of homopolyamino acids and salts thereof can be measured by gel permeation chromatography (GPC).

  As a specific example of the component (B), γ-polyglutamate sodium available from Nippon Polyglu: trade name γ-PGA series (D / L ratio is 8/2, low molecular weight; mass average molecular weight 200,000 to 400,000, high Molecular weight: mass average molecular weight 800,000 to 1,000,000, cross-linked type; mass average molecular weight 10 million or more), γ-polyglutamic acid available from Yakult Pharmaceutical Co., Ltd .: Trade name PGA series (D / L ratio is 1/1, A type; mass average molecular weight 1.5 million, B type; mass average molecular weight 500,000 to 800,000, C type; mass average molecular weight 200,000 to 400,000, D type; mass average molecular weight 10,000 to 100,000), Wako Pure Chemical Industries Poly-γ-glutamic acid and its sodium salt (D / L ratio is 7/3, mass average molecular weight 200,000 to 500,000, 1.5 million to 2.5 million, 4 million to 6 million) 3 types), α-poly-D-glutamic acid and its sodium salt available from Sigma (100% D, mass average molecular weights 20,000-15,000, 15,000-50,000), α- Poly-L-glutamic acid and sodium salt (L-form 100%, weight average molecular weight 750-5000, 35,000-15,000, 15,000-50,000, 50,000-100,000), obtained from LANXESS Sodium polyaspartate: trade name BaypureDS100 (mass average molecular weight: 20,000 to 30 thousand), sodium polyaspartate available from Ajinomoto Co., Inc .: trade name Aquadu SPA-30 (mass average molecular weight: 30,000 05,000).

  (B) Although content of a component is not specifically limited, 0.01 mass% or more is preferable in 100 mass% of liquid cleaning composition at the point which acquires the effect of the storage stability of an enzyme, 2.00 mass% or less is preferable at the point which suppresses turbidity and precipitation of each component (point of aesthetics). More preferably, it is 0.1-1.0 mass%, Most preferably, it is 0.2-1.0 mass%, Most preferably, it is 0.4-0.8 mass%.

[Component (C)]
Component (C) is an enzyme. Here, “enzyme” refers to an enzyme preparation.
The component (C) is not particularly limited as long as it is a general enzyme used in a cleaning agent. However, when the liquid cleaning composition of the present invention is used as a cleaning agent for clothing, protease, amylase, lipase, cellulase, Mannanase etc. are mentioned. Specific examples include the following.

As proteases, protease preparations available from Novozymes: Tradenames Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX 2.5, Ultra Ul 16L, Erase Ultra 16L, Esperase 8L , Liquidase Ultra 2.5L, Liquidase Ultra 2.5XL, Coronase 48L, Protease preparations available from Genencor Corporation: Tradenames Purefect L, Perfect Prime, Properase L and the like.
As the amylase, amylase preparations available from Novozymes: trade name Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, amylase preparation available from Genencor Corp. Examples include amylase preparations available from Enzyme: trade name pullulanase Amano, amylase preparations available from Seikagaku Corporation: trade name DB-250, and the like.
Examples of the lipase include lipase preparations available from Novozymes: trade names Lipex 100L, Lipolase 100L, and the like.
Examples of cellulases include cellulase preparations available from Novozymes: trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L, cellulase preparations available from Genencor, Inc .: trade name Puradux EG L, and the like.
Examples of mannanase include mannanase preparations available from Novozymes: trade name Mannaway 4L.

  Protease is an enzyme whose enzyme activity is likely to decrease due to self-digestion, but since the liquid detergent composition of the present invention contains the component (B) described above, it forms a complex with the component (B). By doing so, a decrease in enzyme activity can be suppressed, and the enzyme function of the protease can be fully exhibited.

In addition, when a protease is used in a powder cleaning agent, the surface thereof is easily covered with components other than the enzyme in the production process (particularly when powdered), so that stability in the cleaning agent can be ensured. On the other hand, when used in liquid detergents, selective protease surface coating is difficult compared to powder detergents. Therefore, it has not been easy to stably mix protease as an enzyme for liquid detergents without reducing enzyme activity over time.
However, in the case of the liquid detergent composition of the present invention, a decrease in enzyme activity over time can be suppressed by forming a complex with the component (B), and the enzyme function of the protease can be fully exhibited. Therefore, even if a protease is added, a sufficient effect can be obtained.

Among the proteases, those shown below are particularly easy to self-digest and have a remarkable decrease in enzyme activity. However, in the present invention, sufficient effects can be obtained even if these proteases are used.
Specific examples of proteases in which the effects of the present invention are particularly prominent include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Liquidase 2.5L, Liquidase UltraL 5XL and Coronase 48L are mentioned, and Everase 16L, Savinase 16L and Coronase 48L are particularly prominent.

  The content of the component (C) is not particularly limited from the viewpoint of storage stability, but is preferably 0.01% by mass or more in 100% by mass of the liquid detergent composition in terms of improving the cleaning performance. Considering enzyme precipitation and performance saturation in a small composition, 2.00% by mass or less is preferable. More preferably, it is 0.01-1.00 mass%, Most preferably, it is 0.03-0.80 mass%.

  Further, the mass ratio of the component (B) and the component (C) is not particularly limited, but considering the production cost and the storage stability of the enzyme, the component (B) / (C) component is 1 / 10.0 to 1/1 /. It is preferably 0.5, more preferably 1 / 4.0 to 1 / 0.5, and particularly preferably 1 / 1.0 to 1 / 0.5. If the mass ratio of (B) component and (C) component is in the said range, the effect of the storage stability of an enzyme is fully acquired.

[(D) component]
(D) A component is water. Examples of the component (D) include purified water, distilled water, ion exchange water, pure water, and ultrapure water.
(D) As for content of a component, 15-75 mass% is preferable in 100 mass% of liquid cleaning composition, More preferably, it is 25-65 mass%, Most preferably, it is 20-40 mass%.
If content of (D) component is 15 mass% or more, (C) component will become more difficult to precipitate. On the other hand, when the content of the component (D) is 75% by mass or less, the component (C) can be sufficiently stabilized by the component (B) while maintaining the cleaning performance.

In particular, if the content of the component (D) is in the range of 20 to 40% by mass, the component (A) will be contained at a high concentration, so the liquid detergent composition of the present invention is of a compact type. While being able to use suitably as a cleaning agent, the turbidity and isolation | separation of the liquid cleaning composition by (B) component and / or (C) component can be reduced.
In addition, content of (D) component means the total water content in a liquid detergent composition, the quantity mix | blended with water alone, and the said solution when a raw material (each component) is mix | blended as a solution. The total amount of water.

[Optional ingredients]
In the liquid detergent composition of the present invention, in addition to the components (A) to (D), if necessary, usual optional components used for the liquid detergent are blended within a range not impairing the effects of the present invention. Can do.
Examples of the optional component include those shown below.

<Water-miscible organic solvent>
Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, and tetraethylene glycol. Polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, polyglycols such as dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol monobutyl ether Is mentioned.
The content of the water-miscible organic solvent is preferably 0.1 to 15% by mass in 100% by mass of the liquid detergent composition.

<Thickener and solubilizer>
Examples of the thinning agent and the solubilizer include aromatic sulfonic acids or salts thereof. Specific examples include toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate, xylene sulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate. .
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
These thickeners and solubilizers can be used alone or in combination.
The content of the thinning agent and the solubilizer is preferably 0.01 to 15% by mass in 100% by mass of the liquid detergent composition. If it is in the said range, the effect which suppresses the production | generation of the membrane | film | coat formed when the said liquid detergent composition gelatinizes on the liquid surface of a liquid detergent composition will improve.

<Alkaline agent>
Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine and the like. These alkali agents can be used alone or in combination.
As for content of an alkaline agent, 0.5-5 mass% is preferable in 100 mass% of liquid cleaning composition.

<Metal ion scavenger>
The metal ion scavenger captures metals in tap water and can suppress a decrease in the activity of the anionic surfactant due to complex formation with these metals. In addition, it is generally used in liquid detergent compositions for the purpose of improving the stability of the dye contained in the liquid detergent composition and improving the pH buffering capacity. However, it is known that the activity tends to decrease with respect to the component (C) involving metal.
Examples of the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
The content of the metal ion scavenger is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% in 100% by mass of the liquid detergent composition. % By mass.

<Antioxidant>
The antioxidant is not particularly limited, but a phenolic antioxidant is preferred because of its good detergency and liquid stability, and monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole, Bisphenol antioxidants such as 2,2′-methylenebis (4-methyl-6-t-butylphenol) and polymer type phenolic antioxidants such as dl-α-tocopherol are more preferred, and monophenol antioxidants More preferred are polymer type antioxidants.
Of the monophenol antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymer type phenol antioxidants, dl-α-tocopherol is particularly preferable.
An antioxidant can be used 1 type or in mixture of 2 or more types.
As for content of antioxidant, 0.01-2 mass% is preferable in 100 mass% of liquid cleaning composition.

<Preservative>
Examples of the preservative include Rohm and Haas: trade name Kaison CG.
The content of the preservative is preferably 0.001 to 1% by mass in 100% by mass of the liquid detergent composition.

<Others>
Furthermore, the liquid detergent composition of the present invention comprises benzoic acid or a salt thereof (also effective as a preservative) for the purpose of improving the storage stability, boric acid, borax, formic acid or the like for the purpose of stabilizing the enzyme. 0-2% by mass of calcium salts such as salt, calcium chloride, calcium sulfate, etc., 0-5% by mass of silicone such as dimethyl silicone, polyether-modified silicone, amino-modified silicone for the purpose of improving the texture, improving whiteness of white clothing 0 to 1% by weight of a fluorescent whitening agent such as distyryl biphenyl type for the purpose of, polypyrrolic acid, acrylic acid-maleic acid copolymer for the purpose of improving re-contamination prevention, such as for the purpose of preventing dye transfer A recontamination inhibitor such as coalescence or carboxymethylcellulose may be contained in an amount of 0 to 2% by mass, a pearl agent, a soil release agent and the like.

Moreover, the liquid detergent composition of the present invention may contain a flavoring agent, a coloring agent, an emulsifying agent, an extract such as a natural product, and the like for the purpose of improving the added value of goods.
As a flavoring agent, the fragrance | flavor composition A, B, C, D etc. of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 can be used as a typical example.
The content of the flavoring agent is preferably 0.1 to 1% by mass in 100% by mass of the liquid detergent composition.

Colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR (all trade names) Is mentioned.
The content of the colorant is preferably about 0.00005 to 0.005% by mass in 100% by mass of the liquid detergent composition.

Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (manufactured by Syden Chemical Co., Ltd .: trade name Cybinol RPX-196 PE-3, solid content 40% by mass) and the like.
As for content of an emulsion, 0.01-0.5 mass% is preferable in 100 mass% of liquid cleaning composition.

Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, plant extracts, such as St. John's Wort.
The content of extracts such as natural products is preferably about 0 to 0.5% by mass in 100% by mass of the liquid detergent composition.

[Physical properties of liquid detergent composition: pH]
The liquid detergent composition of the present invention preferably has a pH of 4-9 at 25 ° C., more preferably 6-9. If pH is in the said range, the storage stability of a liquid detergent composition can be maintained favorable.
The pH of the liquid detergent composition can be adjusted with a pH adjuster. The pH adjuster is optional as long as the effects of the present invention are not impaired, but hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of stability.
The pH of the liquid detergent composition (temperature adjusted to 25 ° C.) indicates a value measured by a pH meter or the like.

[Production of liquid detergent composition]
The liquid detergent composition of the present invention is obtained by mixing the above-described components (A) to (D) and optional components as necessary, but the component (B), the component (C), and ( It is preferable to manufacture by the method of mixing the remaining component, after preparing a premix by mixing (premixing) a part or all of D) component.

The premixing procedure is preferably a procedure in which the component (B) is added to the component (D) and then the component (C) is added thereto. According to the above procedure, the component (B) can be mixed with the component (C) in a state where the component (B) is completely hydrated (dissolved in water). Even in such a difficult-to-handle form, it can be uniformly mixed with the component (C).
The amount of the component (D) in the premixing is preferably 8 to 18 times by mass ratio with respect to the component (B). If it is 8 times or more, the component (B) can be sufficiently dissolved. On the other hand, if it is 18 times or less, it is considered that the component (B) is surrounded around the component (C), and an almost irreversible shield is formed. Even if the liquid detergent composition is stored for a long period of time ( C) The activity of the component can be kept good.

  In addition, when adjusting the pH of the liquid detergent composition, after mixing the remaining components other than the components used for pre-mixing, adjusting to the desired pH with the pH adjuster, and mixing these with the pre-mix Good.

  The liquid detergent composition thus obtained can be suitably used as a detergent for clothing. As a method of use at that time, a normal method of use can be adopted. Specifically, the liquid detergent composition of the present invention (this composition) is poured into water together with the laundry at the time of washing, mud dirt And a method of directly applying the present composition to sebum stains, a method of previously dissolving the present composition in water and immersing clothes. Also preferred is a method in which the present composition is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. In that case, the usage-amount of this composition can be made smaller than the usage-amount of the conventional liquid cleaning composition.

Since the liquid detergent composition of the present invention described above contains the specific component (A), component (B), component (C), and component (D), the surfactant is contained in a high concentration. Even in this case, the storage stability of the enzyme can be maintained well without reducing the enzyme activity. Therefore, the liquid detergent composition of the present invention can be suitably used as a compact detergent.
Moreover, even if the liquid detergent composition of this invention preserve | saves for a long period of time, the fall of enzyme activity can be suppressed.

Moreover, if (B) component, (C) component, and (D) a part or all of (D) component are mixed beforehand, and a liquid cleaning composition is manufactured by the method of mixing the remaining components, (B Since the complex formation between the component (C) and the component (C) is performed in the absence of the component (A), a complex having stronger binding can be formed. The complex is considered to have a form in which the surface of the component (C) is covered with the component (B), and the protective effect of the component (B) suppresses a decrease in the activity of the enzyme and is stable in storage. The property can be maintained well. Moreover, the effect of suppressing the collapse | disintegration of the composite_body | complex by the (A) component which will coexist later is also acquired by mixing beforehand.
However, when the content of the component (D) is outside the range of 15 to 75% by mass, it is difficult to obtain the effect of the premixing.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. “%” Means “% by mass” unless otherwise specified.

[Raw materials]
As the component (A), the following compounds were used.
A-1-1: C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) ₁₅ OCH ₃ and C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) ₁₅ OCH ₃ in a mass ratio of 8/2, narrow ratio 33% synthetic.
A-1-1 was produced according to Production Example 1 in Examples described in JP-A No. 2000-144179.
That is, alumina hydroxide / magnesium hydroxide having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (trade name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina hydroxide / magnesium (unmodified) catalyst (2.2 g) obtained by calcining, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, Was charged into a 4 liter autoclave and the catalyst was reformed in the autoclave.
Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, 1052 g of ethylene oxide was introduced and reacted while stirring.
Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added respectively, and then the catalyst was filtered off to obtain A-1-1. The narrow ratio of A-1-1 was 33% by controlling the amount of alkali added to the catalyst.
The narrow rate of A-1-1 was determined as follows.

Using high performance liquid chromatography (HPLC), the distribution of ethylene oxide adducts with different numbers of added moles of ethylene oxide in A-1-1 was measured under the following measurement conditions. And the narrow rate (%) of A-1-1 was calculated based on the following numerical formula (S).
(Conditions for measuring the distribution of ethylene oxide adducts by HPLC)
Apparatus: LC-6A (manufactured by Shimadzu Corporation).
Detector: SPD-10A.
Measurement wavelength: 220 nm.
Column: Zorbax C8 (manufactured by DuPont).
Mobile phase: acetonitrile / water = 60/40 (volume ratio).
Flow rate: 1 mL / min.
Temperature: 20 ° C.

In the formula (S), n _max represents the number of moles of alkylene oxide added in the alkylene oxide adduct most present in the entire alkylene oxide adduct. i represents the number of added moles of alkylene oxide. Yi represents the proportion (%) of an alkylene oxide adduct in which the number of moles of alkylene oxide present in the entire alkylene oxide adduct is i.

A-1-2: A product obtained by adding 15 moles of ethylene oxide to natural alcohol CO-1270 manufactured by P & G.
A-1-2 was produced as follows.
That is, 224.4 g of natural alcohol CO-1270 manufactured by P & G and 2.0 g of 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, and A-1-2 was obtained. .

_{· A-1-3: (C n} H 2n + 1) CH (C m H 2m + 1) O (EO) 9 H ( polyoxyethylene alkyl ether having a branched alkyl group having 12 to 14 carbon atoms (manufactured by Nippon Shokubai Co. Manufactured: trade name Softanol 90); m + n = 11-13; average ethylene oxide 9 mol adduct of branched chain-containing secondary alcohol).

_{· (A-1-4): C} 11 H 23 CO (OCH 2 CH (CH 3)) n (OCH 2 CH 2) m OCH 3 and _{C 13 H 27 CO (OCH 2} CH (CH 3)) n ( OCH ₂ CH ₂ ) _m Mixture of 8/2 by mass ratio with OCH ₃ , m = average 15, n = average 1 (random), narrow ratio 37% by mass, synthetic product.
(A-1-4) uses 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, introduces 1052 g of ethylene oxide and 93 g of propylene oxide, and adjusts the amount of alkali added to the catalyst so that the narrow ratio is 37% by mass. (A-1-4) was produced in the same manner as in the synthesis method of (A-1-1) except for the adjustment.

-(A-1-5): A nonionic surfactant obtained by randomly adding 16 mol of ethylene oxide and 2 mol of propylene oxide to natural alcohol (C12 / C14 = 7/3).
As for (A-1-5), 224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 704 g of ethylene oxide (gaseous) and 116 g of propylene oxide were gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. I let you.
After the addition of ethylene oxide and propylene oxide, after aging for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, unreacted ethylene oxide and propylene oxide are distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. did.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product is about 7, and (A-1- 5) was obtained.

A-2-1: linear alkylbenzene sulfonic acid (LAS) (manufactured by Lion Corporation: trade name Rypon LH-200, carbon number 10-14, average molecular weight 322).

As the component (B), the following compounds were used.
B-1: sodium γ-polyglutamate (low molecular weight) (manufactured by Nippon Polyglu Co., Ltd .: trade name γ-PGA (Low molecular weight)).
-B-2: Sodium γ-polyglutamate (high molecular weight) (manufactured by Nippon Polyglu Co., Ltd .: trade name γ-PGA (High molecular weight)).
B-3: sodium γ-polyglutamate (cross-linked) (manufactured by Nippon Polyglu, trade name: γ-PGA (close link)).
B-4: γ-polyglutamic acid (manufactured by Yakult Pharmaceutical Co., Ltd .: trade name PGA C type).
-B-5: Sodium polyaspartate (Lanxess: trade name Baypure
DS100).
B-6: α-poly-D-glutamic acid (manufactured by Sigma: trade name Poly-D-glutamic acid (Mol wt 15000 to 50000)).
B-7: α-poly-L-glutamic acid (manufactured by Sigma: trade name Poly-L-glutamic acid, (Mol wt 15000 to 50000)).

Moreover, the compound shown below (protein which is not a homotype) was used as a substitute of (B) component.
-B'-1: Lactoferrin (made by Morinaga Milk Industry Co., Ltd.).

As the component (C), the following compounds were used.
C-1: Everase 16L (manufactured by Novozymes: trade name Everlase 16L Type EX).
C-2: Sabinase 16L (manufactured by Novozymes: trade name Savinase 16L).
C-3: Coronase 48L (manufactured by Novozymes: trade name Coronase 48L).

(D) Distilled water was used as a component.
In addition, the following reagents were used as optional components.
-Ethanol: Ethanol (99.5) (manufactured by Kanto Chemical Co., Inc.).
Citric acid: anhydrous citric acid (manufactured by Iwata Chemical).
MEA: monoethanolamine (manufactured by Kanto Chemical Co., Inc.)
NaOH: Sodium hydroxide (manufactured by Kanto Chemical Co., Inc.)
HCl: hydrochloric acid (manufactured by Kanto Chemical Co., Inc.)

[Evaluation]
<Evaluation of enzyme activity>
The enzyme activity after storing the liquid detergent composition in a constant temperature bath at 35 ° C. for 2 weeks and 4 weeks was evaluated as follows.
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem) is dissolved in 1N sodium hydroxide (1 mol / L, sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.), and the pH is adjusted to 10.5. After that, it was diluted with a 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Inc.) aqueous solution so that the concentration of milk casein was 0.6% to obtain a protease substrate.
1 g of the liquid detergent composition after storage for a predetermined period was diluted 25 times with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water to obtain a diluted solution. 5 g of the protease substrate was added to 1 g of the diluted solution, and after 10 seconds of vortexing, the mixture was allowed to stand at 37 ° C. for 30 minutes to proceed the enzyme reaction.
Thereafter, 5 g of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co.) 0.44M aqueous solution was added as an enzyme reaction terminator, vortexed for 10 seconds, allowed to stand at 20 ° C. for 30 minutes, and precipitated unreacted substrate Was removed with a 0.45 μm filter.
The concentration (absorbance A) of the enzyme-decomposed substrate present in the solution after removal with a filter was quantified at a measurement wavelength of 275 nm using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation: product name UV-160).

Separately, in order to remove the influence of absorption other than the target component, the absorbance B at 275 nm of the sample solution containing no protease substrate was measured.
In addition, except that a sample obtained by storing the liquid detergent composition at 5 ° C. for 4 weeks was used, the same operation as described above was performed to react with the protease substrate, the precipitate was removed, and the absorbance C at 275 nm of the filtrate was measured. This was measured and used as the initial value of the enzyme activity.
The enzyme activity (%) was determined from the absorbances A to C by the following formula. In addition, in order to exclude scattered light such as bubbles from the absorbance, the absorbance values A to C were used by subtracting the absorbance value at 600 nm measured at the same time.
Enzyme activity (%) = (absorbance A−absorbance B) / absorbance C × 100

<Evaluation of storage stability>
100 mL of a liquid detergent composition was added to a transparent glass bottle (Hiroguchi standard bottle, PS-NO.11), and the lid was closed and sealed. In this state, it was placed in a constant temperature bath at 35 ° C. and stored for 4 weeks, and then the appearance of the liquid was visually observed, and the storage stability was evaluated based on the following criteria.
○: No precipitated substance is observed at the bottom of the glass bottle.
Δ: Precipitate was observed at the bottom of the glass bottle, but the precipitate disappeared (dissolved) by gently shaking.
X: Precipitated substances were observed at the bottom of the glass bottle, and the precipitate did not disappear even when shaken lightly.

<Evaluation of cleaning power>
Artificial dirt cloth (manufactured by Laundry Science Association) produced by impregnating artificial dirt with oily co-fabricated cloth (unstained cloth) was cut into 5 × 5 cm to make a dirty cloth.
As a cleaning tester, Terg-O-meter (manufactured by UNITED STATES TESTING) was used.
As the washing liquid, one prepared by adding 300 μL of the liquid detergent composition to 900 mL of water and stirring for 30 seconds was used.
The washing liquid, the five artificial dirt cloths and the washing knitted cloth were put into a washing tester, and washed at 120 rpm and 20 ° C. for 10 minutes according to the bath ratio of 30 times. Then, it moved to the 2 tank type washing machine (Mitsubishi Electric Corp. make: product name CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (20 degreeC, 4 degree DH) for 3 minutes, and air-dried.
The reflectance was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd .: product name SE2000 type) for the unstained fabric and the artificial soiled fabric before and after cleaning, and the cleaning rate (%) was determined by the following formula. However, K / S is (1-R / 100) ² / (2R / 100) (R represents the reflectance (%) of the unsoiled cloth and the artificial soil cloth before and after washing).
Washing rate (%) = (K / S of artificial soil cloth before washing−K / S of artificial soil cloth after washing) / (K / S of artificial soil cloth before washing−K of unsoiled cloth) / S) × 100.

The washing rate was calculated for each of the five artificial soil cloths, and the average value was calculated as the washing rate of the liquid detergent composition. And detergency was evaluated based on the following reference | standard.
A: The cleaning rate is 80% or more.
○: The cleaning rate is 70% or more and less than 80%.
Δ: The cleaning rate is 65% or more and less than 70%.
X: The cleaning rate is less than 65%.

  Moreover, the cleaning rate was similarly calculated about the liquid detergent composition after storing for 2 weeks in a 35 degreeC thermostat, and the cleaning power was evaluated.

[Examples 1 and 3 to 27 and Comparative Examples 2 and 4 to 7]
<Preparation of liquid detergent composition>
Into a 50 mL beaker, the type and blending amount (mass%) of the component (B) shown in Tables 1 to 3 and the amount (D) of 8 times (%) of the component (B) are charged, and a magnetic stirrer. (MITUMURA RIKEN KOGYO INC.), The amount of liquid is about 1 cm from the bottom of the beaker, and stirred for 20 minutes with a stirrer chip having a length of 25 mm and a diameter of 8 mm, and then the types and combinations shown in Tables 1 to 3 An amount (mass%) of the component (C) was added and further premixed by stirring to obtain a premixed product.
Separately, in a 500 mL beaker, component (D) is 20.0%, ethanol is 7.0%, citric acid is 0.3%, and MEA is 1.0% as optional components. And (A) component in a blending amount (mass%) were added and stirred to dissolve these components.
Subsequently, it adjusted using sodium hydroxide and hydrochloric acid as a pH adjuster so that pH at 25 degreeC of a solution might be set to 7 using the pH meter (the product name HM-30G by Toa DKK Corporation). A pre-mixture was added to this, and the liquid detergent composition was obtained by adding (D) component which adjusted the compounding quantity so that the total amount of the liquid detergent composition which is a final product might be 100%. .

  The obtained liquid detergent composition was evaluated for enzyme activity, storage stability, and detergency. The results are shown in Tables 1-3.

[Example 2 and Comparative Examples 1 and 3]
<Preparation of liquid detergent composition>
In a 500 mL beaker, component (D) is 20.0%, ethanol is 7.0%, citric acid is 0.3%, and MEA is 1.0% as optional components. Components (A) and (B) in amounts (mass%) were added and stirred to dissolve these components.
Subsequently, it adjusted using sodium hydroxide and hydrochloric acid as a pH adjuster so that pH at 25 degreeC of a solution might be set to 7 using the pH meter (product name: HM-30G, the Toa DK Corporation make). After that, the components shown in Tables 1 and 3 and the amount (% by mass) of component (C) are added and further stirred, and the amount is adjusted so that the total amount of the liquid detergent composition as the final product is 100%. A liquid detergent composition was obtained by adding the adjusted component (D).

  The obtained liquid detergent composition was evaluated for enzyme activity, storage stability, and detergency. The results are shown in Tables 1-3.

  In Tables 1 to 3, “nonionic content” refers to the content (mass%) of the nonionic surfactant in 100 mass% of component (A).

As is clear from Tables 1 and 2, the liquid detergent composition obtained in each example was able to suppress a decrease in enzyme activity even when stored for a long period of time. In addition, the storage stability of the enzyme could be maintained well and excellent detergency could be demonstrated.
On the other hand, as is clear from Table 3, the liquid detergent composition obtained in Comparative Example 1 containing no component (B) was liable to have reduced enzyme activity.
Comparing Comparative Examples 2 and 3 in which the content of the nonionic surfactant in the component (A) is 24%, Comparative Example 2 in which the component (B), the component (C), and the component (D) are premixed and blended. Although there was a slight tendency that the decrease in enzyme activity was suppressed, the enzyme activity was significantly inferior to each example, and the enzyme activity was significantly decreased as compared with Comparative Example 1.
When comparing Comparative Examples 4 and 5 in which the content of the nonionic surfactant in the component (A) is 50%, the decrease in enzyme activity is suppressed in Comparative Example 4 with less component (D). Compared with each Example, the enzyme activity was remarkably inferior.
In the case of Comparative Example 6 in which (B′-1), which is not a homopolyamino acid, was used instead of the component (B), the enzyme activity was significantly reduced.
In Comparative Example 7 containing no surfactant, the enzyme activity was stabilized, but the detergency was remarkably low.

  According to the present invention, even when a surfactant is contained in a high concentration, there is provided a liquid detergent composition that can satisfactorily maintain the storage stability of an enzyme without reducing the enzyme activity and a method for producing the same. it can.

Claims (7)

A liquid detergent composition comprising the following components (A) to (D):
(A) component: Surfactant (however, a nonionic surfactant is included in the component (A) in an amount of 60% by mass or more);
(B) component: homopolyamino acid and / or salt thereof;
(C) component: enzyme;
(D) Component: Water.   Content of the said (A) component is 45-65 mass% in 100 mass% of liquid cleaning composition, The liquid cleaning composition of Claim 1 characterized by the above-mentioned.   The liquid detergent composition according to claim 1 or 2, wherein the content of the component (D) is 20 to 40 mass% in 100 mass% of the liquid detergent composition.   The liquid detergent composition according to any one of claims 1 to 3, wherein the homopolyamino acid is polyglutamic acid and / or polyaspartic acid.   The liquid cleaning composition according to any one of claims 1 to 4, wherein the component (C) is a protease.   It is an object for clothes, The liquid detergent composition as described in any one of Claims 1-5 characterized by the above-mentioned. It is a manufacturing method of the liquid detergent composition according to any one of claims 1 to 6,
A method for producing a liquid detergent composition, comprising mixing the component (B), the component (C), and a part or all of the component (D) and then mixing the remaining components.