JP6188239B2 - Liquid cleaning agent - Google Patents

Description

  The present invention relates to a liquid cleaning agent.

Liquid detergents are increasingly used as household detergents. It is necessary for the detergent for clothes to have a detergency against various stains adhering to clothes or the like (objects to be washed).
Conventionally, a surfactant is mainly used as a cleaning component in a liquid cleaning agent. In addition, an enzyme that exhibits various performances may be added to the liquid detergent as an additive, for example, a small amount improves the cleaning power. However, the enzyme is easily deactivated in the liquid detergent. For this reason, liquid detergents have problems that it is difficult to maintain enzyme activity as compared to granular detergents, and that the enzyme blending effect cannot be obtained sufficiently.
On the other hand, in order to maintain enzyme activity in a liquid cleaning agent, the technique which uses sodium lactate and calcium lactate together in addition to surfactant and an enzyme is disclosed (refer patent document 1).
Further, a nonionic surfactant, at least one component selected from the group consisting of an aminocarboxylic acid or a salt thereof, and a phosphonic acid or a salt thereof, an α-hydroxy-monocarboxylic acid or a salt thereof, and an enzyme, The liquid detergent to contain is disclosed (refer patent document 2).

International Publication No. 2011/110593 International Publication No. 2012/144601

However, in the technique described in Patent Document 1, in a composition having a high surfactant concentration and a low water content (so-called concentrated type), a precipitated substance is likely to be generated with storage over time, and a transparent and uniform appearance is stably maintained. It was difficult.
Moreover, in the liquid cleaning agent described in Patent Document 2, enzyme activity was not maintained due to differences in cleaning components and the like, and enzyme stabilization was insufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent having high enzyme activity stability and good appearance stability.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent of the present invention comprises (A) component: surfactant, (B) component: 45% by mass or less of water, and (C) component: methylglycine diacetic acid, ethylglycine diacetic acid, nitrilotrimethyl. At least one compound selected from the group consisting of acetic acid, iminodisuccinic acid and salts thereof; (D) component: sodium lactate; (E) component: calcium lactate; and (F) component: protease. The mass ratio represented by [(D) component + (E) component] / (C) component is 0.01-50.

  The liquid detergent of the present invention has high enzyme activity stability and good appearance stability.

The liquid detergent of the present invention comprises (A) component: surfactant, (B) component: 45% by mass or less of water, (C) component: methylglycine diacetic acid, ethylglycine diacetic acid, nitrilotriacetic acid, It contains at least one compound selected from the group consisting of iminodisuccinic acid and salts thereof, (D) component: sodium lactate, (E) component: calcium lactate, and (F) component: protease.
The liquid detergent of the present invention can be used for household and industrial applications, and can be suitably used for household use, and is particularly suitable for clothing.
Examples of the types of objects to be cleaned include those similar to those to be cleaned in laundry at home, and examples thereof include textiles such as clothing, cloths, towels, and sheets.

<(A) component: Surfactant>
The liquid cleaning agent of this invention has a cleaning effect by containing (A) component.
(A) As a component, the surfactant normally used for liquid detergents for clothes etc. can be used, Nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant etc. Can be mentioned.

≪Nonionic surfactant≫
As the nonionic surfactant in the component (A), nonionic surfactants commonly used in liquid detergents for clothing and the like can be used. For example, fatty acid alkyl esters, higher alcohols, alkylphenols, higher fatty acids or higher Alkylene oxide adducts such as amines; polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkylamine oxides, alkenylamine oxides , Alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glucosides and the like.
Of these, alkylene oxide adducts such as fatty acid alkyl esters, higher alcohols, alkylphenols, higher fatty acids or higher amines are preferred from the viewpoint of the viscosity and appearance stability of the liquid detergent.

  Preferable alkylene oxide adducts include, for example, polyoxyalkylene type nonionic surfactants represented by the following general formula (a1) (hereinafter also referred to as “component (a1)”).

^{R 1 -X - [(EO)} s / (PO) t] - (EO) u-R 2 ··· (a1)
[Wherein, R ¹ is a hydrocarbon group having 7 to 22 carbon atoms. -X- is a divalent linking group. R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. s represents the average number of repetitions of EO and is a number from 3 to 20. t represents the average number of repetitions of PO, and is a number from 0 to 6. u represents the average number of repetitions of EO, and is a number from 0 to 20. ]

In the formula (a1), the carbon number of ^{R 1} is 7 to 22, preferably 10 to 18. When the carbon number of R ¹ is not less than the above lower limit, the detergency is improved. On the other hand, liquid stability improves that it is below the said upper limit.
The hydrocarbon group for R ¹ is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group or an alkenyl group. The alkyl group or alkenyl group herein may be linear or branched.
Examples of the divalent linking group of —X— include —O (oxygen atom) —, —COO—, —CONH—, and the like.
The number of carbon atoms in the alkyl group in R ² is 1-6, 1-3 are preferred. The number of carbon atoms of the alkenyl group for R ² is 2-6, 2 or 3 are preferred.
The component (a1) in which —X— is —O—, —COO— or —CONH— is a primary or secondary higher alcohol (R ¹ —OH), higher fatty acid (R ¹ —COOH) or higher fatty acid amide (R ¹ -CONH) can be obtained as a raw material.

In said formula (a1), s is a number of 3-20, and the number of 5-18 is preferable. When s exceeds 20, the HLB value becomes too high, and the detergency against oil stains such as sebum stains tends to decrease. On the other hand, when s is less than 3, the effect of preventing odor degradation tends to be reduced.
In said formula (a1), t is a number of 0-6, and the number of 0-3 is preferable. When t exceeds 6, the storage stability of the liquid detergent at high temperature tends to be lowered.
In said formula (a1), u is a number of 0-20, and the number of 0-18 is preferable. If u exceeds 20, the hydrophilicity becomes too high and the detergency may be reduced.

When t is not 0, that is, when the component (a1) has both EO and PO, EO and PO may be added in a block shape or may be added in a random shape.
As a method of adding EO and PO in a block form, for example, a method of introducing propylene oxide after introducing ethylene oxide, a method of introducing ethylene oxide after introducing propylene oxide, or a method of introducing propylene oxide after introducing ethylene oxide. And a method of further introducing ethylene oxide.
The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited.

The added mole number distribution is likely to vary depending on the reaction method in producing the component (a1). For example, when ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of moles of ethylene oxide or propylene oxide is relatively wide. It tends to be. 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 of the number of moles of ethylene oxide or propylene oxide tends to be relatively narrow.

  In the formula (a1), the divalent linking group in -X- is preferably -O- or -COO-.

In the case of a compound in which —X— is —O—:
The number of carbon atoms of ^{R 1} in the formula (a1) is preferably from 10 to 22, more preferably from 10 to 20, more preferably 10 to 18. R ² is preferably a hydrogen atom. In this case, the compound represented by the general formula (a1) is an alcohol alkoxylate. Among these, a compound where t = 0 (that is, alcohol ethoxylate) is more preferable.

In the case of a compound in which —X— is —COO—:
The number of carbon atoms of ^{R 1} in the formula (a1) is preferably from 9 to 21, more preferably from 11 to 21, more preferably 11 to 17. R ² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. In this case, the compound represented by the general formula (a1) is a polyoxyalkylene fatty acid alkyl ester or a polyoxyalkylene fatty acid. Alkenyl ester. R ² is more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms.

  As a specific example of the compound in which —X— in the formula (a1) is —O— or —COO—, trade name Diadol (C13 alcohol, C represents the number of carbon atoms, manufactured by Mitsubishi Chemical Corporation. The same applies hereinafter. .), Equivalent to 12 moles with respect to an alcohol such as the trade name Neodol (C12 / C13: mixture of C12 alcohol and C13 alcohol) manufactured by Shell, or the product name Safol23 (C12 / C13) manufactured by Sasol 15 mol equivalent of ethylene oxide added; P & G's product name CO-1214 or CO-1270 or other natural alcohol added with 12 mol equivalent or 15 mol equivalent ethylene oxide; butene trimerized The C12 alkene obtained in this manner is subjected to 7 moles of ethylene Sid added (trade name Lutensol TO7 manufactured by BASF); 7 mole equivalent ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name Lutensol XL70 manufactured by BASF) ); A C10 alcohol obtained by subjecting pentanol to a garvet reaction to which 6 mole equivalent of ethylene oxide was added (trade name Lutensol XA60 manufactured by BASF); for a secondary alcohol having 12 to 14 carbon atoms 9 mol equivalent or 15 mol equivalent ethylene oxide (trade name Softanol 90 or Softanol 150 manufactured by Nippon Shokubai Co., Ltd.); alkoxylation catalyst, palm fatty acid methyl (lauric acid / myristic acid = 8/2) (Mass ratio)) 5 molar equivalent obtained by adding ethylene oxide (polyoxyethylene coconut fatty acid methyl ester EO15 mol), and the like.

A nonionic surfactant may be used individually by 1 type, and may use 2 or more types together.
As the nonionic surfactant, a compound represented by the general formula (a1) (component (a1)) is preferable. Among these, from the alcohol alkoxylate, the polyoxyalkylene fatty acid alkyl ester, and the polyoxyalkylene fatty acid alkenyl ester. More preferred is at least one selected from the group consisting of
Among these, a compound in which -X- in the formula (a1) is -COO- is preferable because more free water is present, precipitation of the component (E) is less likely to occur, and appearance stability is further improved. Among them, a compound in which R ² in formula (a1) is an alkyl group having 1 to 6 carbon atoms is more preferable, and a compound in which t in formula (a1) is 0 (that is, a polyoxyethylene fatty acid alkyl ester) is further included. Polyoxyethylene fatty acid methyl ester (hereinafter referred to as “MEE”) in which R ² in formula (a1) is a methyl group is particularly preferable.

  By containing the polyoxyethylene fatty acid alkyl ester, the liquid detergent of the present invention is excellent in solubility in water, and high detergency is easily obtained. Moreover, even if it contains a surfactant at a high concentration, it is difficult to cause a significant increase in viscosity (gelation), and a concentrated liquid cleaning agent having good fluidity can be obtained.

  Polyoxyethylene fatty acid alkyl ester (especially MEE) is a nonionic surfactant in which the orientation of molecules in an aqueous solution system is weak and the micelle is unstable, so that gelation or the like does not occur in a high concentration region. A large amount of the seed alone can be incorporated into the liquid detergent. Moreover, the solubility to water is favorable. Furthermore, it has good fluidity even at high concentrations. Therefore, after the polyoxyethylene fatty acid alkyl ester is poured into the water in the washing machine tub, the concentration in the washing liquid becomes uniform quickly. Thereby, when a polyoxyethylene fatty acid alkyl ester is used, since it can contact with a to-be-washed object by the predetermined density | concentration from the washing | cleaning initial stage, high detergency is acquired.

  As the polyoxyethylene fatty acid alkyl ester, the total content ratio of the fatty acid alkyl ester in which the number of added moles of ethylene oxide is 0 and the ethylene oxide adduct in which the number of added moles of ethylene oxide is 1 or 2, is a polyoxyethylene fatty acid What is 0.5 mass% or less is preferable with respect to the whole alkyl ester, and what is 0.2 mass% or less is more preferable. When the total content is 0.5% by mass or less, a liquid detergent having a lower raw material odor derived from the polyoxyethylene fatty acid alkyl ester is easily obtained.

  In the liquid detergent, by increasing the surfactant concentration, washing can be performed with a small amount of use, or the detergent container can be made compact. Examples of the surfactant suitable for use at such a high concentration include secondary alcohol ethoxylates obtained by adding ethylene oxide to secondary alcohols (for example, Softanol series manufactured by Nippon Shokubai Co., Ltd.) and the aforementioned MEE. It is done. Since these gel regions are small even at high concentrations, gelation is unlikely to occur when used at high concentrations.

As the nonionic surfactant, a secondary alcohol ethoxylate or MEE and a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol may be used in combination.
When the secondary alcohol ethoxylate or MEE and the primary alcohol ethoxylate are used in combination, the ratio of the secondary alcohol ethoxylate or MEE to the total amount (100% by mass) is 30 % By mass or more is preferable, 50% by mass or more is more preferable, and 70% by mass or more is more preferable.

In the liquid detergent, the content of the nonionic surfactant is preferably 0.1% by mass or more, more preferably 0.1 to 70% by mass, and further 5 to 65% by mass with respect to the total amount of the liquid detergent. 10 to 60% by mass is preferable.
When the content of the nonionic surfactant is not less than the preferable lower limit value, the detergency is increased. In particular, when the content is 10% by mass or more, the effects of the present invention are remarkably exhibited. On the other hand, by being below the above-mentioned preferable upper limit value, an increase in the viscosity of the liquid detergent is suppressed, particularly at a low temperature.

≪Anionic surfactant≫
As the anionic surfactant in the component (A), conventionally known anionic surfactants can be used. For example, linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonate, Examples thereof include a chain or branched alkyl sulfate ester salt, alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt, alkane sulfonate having an alkyl group, and α-sulfo fatty acid ester salt.
As a linear alkylbenzenesulfonic acid or its salt, a C8-C16 thing of a linear alkyl group is preferable, and a C10-C14 thing is more preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
The alkyl sulfate ester salt is preferably an alkyl group having 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms. And an average of 1 to 5 moles of alkylene oxide (ethylene oxide and / or propylene oxide) added (that is, polyoxyalkylene alkyl ether sulfate ester salt or polyoxyalkylene alkenyl ether sulfate ester salt) is preferable.
As the alkane sulfonate, an alkyl group having 10 to 20 carbon atoms is preferable, and an alkyl group having 14 to 17 carbon atoms is more preferable. Among these, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are more preferable.
The α-sulfo fatty acid ester salt is preferably a fatty acid residue having 10 to 20 carbon atoms.

  As the anionic surfactant, anionic surfactants other than those exemplified above may be used. Examples of anionic surfactants other than those exemplified above include alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl amide ether carboxylates, alkenyl amide ether carboxylates, and acylaminocarboxylates. Acid type anionic surfactants; phosphate type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, etc. Is mentioned.

  Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt.

An anionic surfactant may be used individually by 1 type, and may use 2 or more types together.
Among the above, the anionic surfactant is at least one selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate ester salt, and α-olefin sulfonate. Is preferred. Among these, when linear alkylbenzene sulfonic acid or its salt is used, the effect of this invention appears notably.
Enzymes are easily denatured by the action of linear alkylbenzene sulfonic acids or salts thereof among anionic surfactants. In the present invention, the enzyme activity is maintained over time even when linear alkylbenzene sulfonic acid or a salt thereof is contained.

In the liquid detergent, the content of the anionic surfactant is preferably 0.1% by mass or more, more preferably 0.1 to 35% by mass, and further preferably 1 to 25% by mass with respect to the total amount of the liquid detergent. 2 to 20% by mass is preferable.
When the content of the anionic surfactant is equal to or more than the preferable lower limit value, a cleaning effect and a recontamination preventing effect are easily obtained. On the other hand, by being below the preferable upper limit, denaturation of the enzyme protein is suppressed and the effects of the present invention can be easily obtained.

≪Cationic surfactant≫
Examples of the cationic surfactant in the component (A) include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts.
A cationic surfactant may be used individually by 1 type, and may use 2 or more types together.

≪Amphoteric surfactant≫
Examples of the amphoteric surfactant in the component (A) include 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, and phosphoric acid type. And amphoteric surfactants.
One amphoteric surfactant may be used alone, or two or more amphoteric surfactants may be used in combination.

In the liquid detergent, the component (A) may be used alone or in combination of two or more.
(A) As a component, at least 1 sort (s) chosen from the group which consists of a nonionic surfactant and an anionic surfactant is preferable, and it is more preferable to use a nonionic surfactant and an anionic surfactant together.
The ratio of the nonionic surfactant to the anionic surfactant is preferably less than 10 in terms of mass ratio represented by nonion / anion, more preferably 0.5 or more and less than 10, more preferably 1 to 8, and 2 to 6 Particularly preferred. If the nonion / anion is within the above-mentioned preferable range, the stability of the enzyme activity is increased, and the enzyme activity is easily maintained over time. On the other hand, if the non-ionic / anion is below the above-mentioned preferable lower limit value, the protein modification of the anionic surfactant Strength increases and enzyme is easily deactivated.
Moreover, as (A) component, since precipitation of (E) component does not arise easily and the effect of this invention becomes easy to be acquired, it is preferable that polyoxyethylene fatty acid methyl ester (MEE) is included.

In the liquid detergent, the content of the component (A) is preferably 30% by mass or more, more preferably 30 to 70% by mass, and further preferably 35 to 60% by mass with respect to the total amount of the liquid detergent.
When the content of the component (A) is equal to or more than the preferable lower limit, the effect of the present invention is more likely to appear. On the other hand, if it is below the preferable upper limit value, an increase in the viscosity of the liquid cleaning agent at a particularly low temperature is suppressed.

<(B) component: water>
The liquid detergent of the present invention contains water (component (B)) as a solvent.
As the component (B), for example, purified water, distilled water, ion exchange water, pure water, ultrapure water, or the like can be used.
In the liquid detergent, the content of the component (B) is 45% by mass or less with respect to the total amount of the liquid detergent, preferably 20 to 45% by mass, more preferably 25 to 40% by mass, and 30 to 40%. More preferred is mass%.
If content of (B) component is below the said upper limit, the effect of this invention will show notably, maintaining a cleaning performance. That is, the (F) component is sufficiently stabilized by the (D) component and / or the (E) component.
In particular, when the content of the component (B) is 30 to 40% by mass, the component (A) can be blended at a high concentration, and a concentrated liquid detergent can be easily prepared. In addition, turbidity and separation of the liquid detergent due to precipitation of the component (D) and / or the component (E) are further suppressed.
In addition, content of said (B) component means the total moisture content in a liquid detergent, and it is brought when the quantity mix | blended with water alone, for example, a raw material (each component) is mix | blended as aqueous solution. The total amount of water in the aqueous solution is shown.

<(C) component: specific compound>
The component (C) in the present invention is at least one compound selected from the group consisting of methylglycine diacetic acid, ethylglycine diacetic acid, nitrilotriacetic acid, iminodisuccinic acid, and salts thereof. By containing the component (C), mainly, precipitation of the component (E) is effectively suppressed without impairing the stability of the component (F).
(C) As a form of the salt of a component, an alkali metal salt is preferable and a sodium salt and potassium salt are more preferable.
As the component (C), one type may be used alone, or two or more types may be used in combination.
As the component (C), at least one compound selected from the group consisting of methylglycine diacetic acid, ethylglycine diacetic acid and salts thereof is preferable, and methylglycine diacetic acid or a salt thereof is particularly preferable.
In the liquid detergent, the content of the component (C) is preferably 0.1 to 5% by mass, more preferably 0.15 to 2% by mass with respect to the total amount of the liquid detergent, and 0.2 to 1. 5 mass% is more preferable. When the content of the component (C) is within the above preferable range, precipitation of the component (E) is more effectively suppressed. The reason why such an effect can be obtained is that the (E) component is effectively trapped by the (C) component, so that the dispersion and stabilization of the (E) component can be achieved in the liquid detergent.
Moreover, when content of (C) component is less than the said preferable lower limit, there exists a possibility of producing precipitation of (E) component, On the other hand, when exceeding the said preferable upper limit, dissolution of (C) component There is a possibility that precipitation of component (C) may occur when it is formulated.

<(D) component: Sodium lactate>
In the liquid detergent of the present invention, the aging stability of the component (F) is mainly enhanced by having both the component (D) and the component (E).
In the liquid detergent, the content of the component (D) is preferably 0.01 to 3% by mass, more preferably 0.1 to 2% by mass with respect to the total amount of the liquid detergent, and 0.2 to 1. 5 mass% is more preferable. When the content of the component (D) is within the above preferred range, the temporal stability of the component (F) is further enhanced. Moreover, when content of (D) component is less than the said preferable lower limit, there exists a possibility that the stabilization effect with respect to (F) component may become difficult to be obtained, On the other hand, when it exceeds the said preferable upper limit, formulation There is a possibility of causing precipitation of the component (D) when it is converted.

<(E) component: calcium lactate>
In the liquid detergent of the present invention, the aging stability of the component (F) is mainly enhanced by having both the component (E) and the component (D).
In the liquid detergent, the content of the component (E) is preferably 0.01 to 3% by mass, more preferably 0.1 to 2% by mass with respect to the total amount of the liquid detergent, and 0.2 to 1. 5 mass% is more preferable. When the content of the component (E) is within the above preferable range, the temporal stability of the component (F) is further improved. Moreover, when content of (E) component is less than the said preferable lower limit, there exists a possibility that the stabilization effect with respect to (F) component may become difficult to be obtained, On the other hand, when it exceeds the said preferable upper limit, formulation There is a possibility that precipitation of the component (E) occurs.

In the liquid cleaning agent, the total content of the component (D) and the component (E) is preferably 0.1 to 6% by mass and more preferably 0.15 to 4% by mass with respect to the total amount of the liquid cleaning agent. Preferably, 0.2-2 mass% is further more preferable. When the total content is less than the preferable lower limit value, it may be difficult to obtain a stabilizing effect on the component (F). On the other hand, when the total content exceeds the preferable upper limit value, a formulation is formed. May cause precipitation.
Although it is not clear why the (D) component and the (E) component are combined to improve the temporal stability of the (F) component, a complex of the (D) component and the (E) component is formed. This is considered to be because the action on the component (F) is stronger than in the case of each of them.

In the present invention, “mass ratio represented by (D) component / (E) component” means the content of (D) component relative to the content (% by mass) of (E) component contained in the liquid detergent ( % By mass).
The mass ratio represented by the component (D) / (E) (hereinafter referred to as “(D) / (E) mass ratio”) is preferably 0.06 to 18, and preferably 0.2 to 10. More preferably, 0.2 to 5 is more preferable, and 0.5 to 5 is particularly preferable. When the (D) / (E) mass ratio is less than the preferable lower limit, precipitation of the component (E) may occur when it is formulated. On the other hand, when the above preferable upper limit is exceeded, there is a possibility that the stabilizing effect on the component (F) is hardly obtained.

In the present invention, the “mass ratio represented by [(D) component + (E) component] / (A) component” refers to the content (mass%) of the (A) component contained in the liquid detergent ( The ratio of the total content (mass%) of D) component and (E) component is meant.
The mass ratio represented by [(D) component + (E) component] / (A) component (hereinafter referred to as “[(D) + (E)] / (A) mass ratio”) is 0. 0.001 to 10 is preferable, 0.005 to 5 is more preferable, and 0.01 to 3 is particularly preferable. If the [(D) + (E)] / (A) mass ratio is less than the above preferred lower limit value, the stabilizing effect on the component (F) may be difficult to obtain, while the above preferred upper limit value. Exceeding the value may cause precipitation when formulated.

  When the component (A) contains an anionic surfactant, the mass ratio represented by [(D) component + (E) component] / anionic surfactant is preferably 0.005-1, and 0.01-0. .5 is more preferable, 0.02 to 0.4 is more preferable, and 0.05 to 0.1 is particularly preferable. If this mass ratio is less than the above preferred lower limit value, the stabilizing effect on the component (F) may be difficult to obtain, whereas if it exceeds the above preferred upper limit value, precipitation will occur when formulated. May occur.

In the present invention, the “mass ratio represented by [(D) component + (E) component] / (C) component” refers to (C) component content (% by mass) contained in the liquid detergent ( The ratio of the total content (mass%) of D) component and (E) component is meant.
The mass ratio represented by [(D) component + (E) component] / (C) component (hereinafter referred to as “[(D) + (E)] / (C) mass ratio”) is 0. 0.01 to 50, preferably 0.1 to 25, more preferably 0.1 to 20, still more preferably 0.1 to 10, and particularly preferably 0.15 to 5. When the [(D) + (E)] / (C) mass ratio is within the above range, the enzyme stabilization effect is excellent, and the appearance stability is good. Further, when the [(D) + (E)] / (C) mass ratio is less than the lower limit value, it is difficult to obtain a stabilizing effect on the component (F), and it is difficult to ensure the stability of the enzyme activity. On the other hand, when the above upper limit is exceeded, there is a risk of precipitation when formulated, and the appearance stability tends to decrease.

<(F) component: protease>
In the liquid detergent of this invention, the washing | cleaning power with respect to protein soil increases by containing (F) component: protease.
In general, a preparation containing a protease (protease preparation) is commercially available. When preparing a liquid detergent, (F) component is normally mix | blended using this protease formulation.
Examples of protease preparations include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase 16L Type EX, Everse Ultra L, UltraseL L Examples include Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, and the like. In addition, trade names such as Purefect L, Purefect OX, Properase L and the like, which are available from Genencor, are listed.

(F) A component may be used individually by 1 type and may use 2 or more types together.
Protease preparations include, among others, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Liquidase 2.5L, Liquidase UltraL2.5, Liquidase UltraL 2.5L and Alcalase Ultra 2.5L are preferable, Everase 16L, Savinase 16L, Coronase 48L and Alcalase 2.5L are more preferable, Everase 16L, Coronase 48L and Alcalase 2.5L are more preferable, and Coronase 48L is particularly preferable.

The content of the component (F) in the liquid detergent is preferably about 0.001 to 0.2% by mass, and about 0.005 to 0.15% by mass as the amount of enzyme protein with respect to the total amount of the liquid detergent. More preferred is about 0.01 to 0.1% by mass.
When the amount of the protein in the component (F) is equal to or more than the preferable lower limit, the blending effect of the component (F) can be sufficiently obtained. On the other hand, by being below the preferable upper limit, precipitation of the component (F) during storage is suppressed, and the liquid stability is increased. Moreover, even if it exceeds the said preferable upper limit, performance reaches saturation and becomes economically disadvantageous.

  The amount of enzyme protein in the liquid detergent can be measured by the LOWRY method. For example, a method using a protein assay LOWRY kit manufactured by Nakarai Techs Co., Ltd. can be mentioned.

  When the component (F) is blended using a protease preparation, the amount of the protease preparation is preferably 0.01% by mass or more, and 0.03% by mass with respect to the total amount of the liquid detergent from the viewpoint of improving the cleaning performance. % Or more is more preferable, 0.1% by mass or more is more preferable, and 0.2% by mass or more is particularly preferable. On the other hand, from the viewpoint of enzyme precipitation and saturation of enzyme performance in a composition having a low water content, 2 mass% or less is preferable with respect to the total amount, 1.5 mass% or less is more preferable, and 1 mass% or less is more preferable.

In the present invention, the “mass ratio represented by the anionic surfactant / component (F)” means the blending amount (mass%) of the “formulation containing the component (F) (enzyme preparation)” contained in the liquid detergent. The ratio of the content (mass%) of an anionic surfactant with respect to is meant.
When the component (A) includes an anionic surfactant, the mass ratio represented by the anionic surfactant / (F) component is preferably 80 or less, more preferably 1 to 60, and particularly preferably 1 to 50. When this mass ratio is within the preferable range, the stability of the enzyme activity is further increased.
In addition, in the ratio of the anionic surfactant to the component (F), when the amount of the component (F) is expressed in terms of protein amount, the mass ratio represented by an anionic surfactant / (F) component (in terms of protein amount). Is preferably 800 or less, more preferably 10 to 600, and particularly preferably 10 to 500.

In the present invention, “mass ratio represented by [(D) component + (E) component] / (F) component” means “preparation containing (F) component (enzyme preparation)” contained in the liquid detergent. It means the ratio of the total content (% by mass) of the component (D) and the component (E) with respect to the blending amount (% by mass).
The mass ratio represented by [(D) component + (E) component] / (F) component (hereinafter referred to as “[(D) + (E)] / (F) mass ratio”)) is 0. 0.01 to 50 is preferable, 0.1 to 30 is more preferable, and 0.1 to 20 is more preferable. When the [(D) + (E)] / (F) mass ratio is less than the lower limit value, it becomes difficult to obtain a stabilizing effect on the component (F). There is a risk of precipitation when formulated.
Moreover, in the ratio of the component (D), the component (E), and the component (F), the amount of the component (F) is expressed in terms of protein amount: [(D) component + (E) component] / (F) 0.1-500 are preferable, as for mass ratio represented by a component (protein amount conversion), 1-300 is more preferable, and 1-200 is especially preferable.

<Optional component>
The liquid cleaning agent of the present invention may contain other components other than the above-described components as necessary as long as the effects of the present invention are not impaired.
The other components are not particularly limited, and include components that are usually blended in liquid detergents for clothing. For example, enzymes other than the component (F), water-miscible organic solvents, enzyme stabilizers, reducing agents Sticking agent and solubilizer, alkali agent, metal ion scavenger, antioxidant, preservative, texture improver, fluorescent brightener, recontamination inhibitor, pearl agent, soil release agent, flavoring agent, colorant, An emulsifying agent, an extract such as a natural product, a fragrance, a pH adjuster and the like can be used.

In the liquid cleaning agent of the present invention, an enzyme other than the component (F) may be used. By having both the component (F) and an enzyme other than the component (F), the detergency against various types of dirt increases. In addition, various performances can be provided as appropriate.
As the enzyme other than the component (F), known enzymes conventionally used in laundry detergents can be used, and examples thereof include amylase, lipase, cellulase, and mannanase.
In general, preparations (enzyme preparations) each containing these enzymes are commercially available. When preparing the liquid detergent, enzymes other than the component (F) are usually blended using the respective enzyme preparations.

Examples of the amylase-containing preparation (amylase preparation) include, for example, trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, and Steinzyme Plus 12L available from Geneboa Co., Ltd. Examples include trade name pullulanase Amano available from the company and trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase-containing preparation (lipase preparation) include trade names Lipex 100L and Lipolase 100L available from Novozymes.
Examples of cellulase-containing preparations (cellulase preparations) include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like available from Novozymes.
As a preparation containing mannanase (mannanase preparation), for example, trade name Mannaway 4L available from Novozymes is exemplified.

(F) Enzymes other than component may be used individually by 1 type, and may use 2 or more types together.
As the enzyme other than the component (F), among the above, cellulase is preferable from the viewpoint of the effect of the combined use with protease (improvement of detergency against oil stains such as sebum stain).

In the liquid detergent, the content of the enzyme other than the component (F) is preferably about 0.001 to 0.2% by mass as the amount of enzyme protein with respect to the total amount of the liquid detergent, 0.005 to 0.15 mass. % Is more preferable, and about 0.01 to 0.1% by mass is more preferable.
(F) When the protein amount in enzymes other than a component is more than the said preferable lower limit, each compounding effect of this enzyme is fully acquired. On the other hand, by being below the preferable upper limit value, precipitation of the enzyme during storage is suppressed, and liquid stability is enhanced. Moreover, even if it exceeds the said preferable upper limit, performance reaches saturation and becomes economically disadvantageous.

  When an enzyme other than the component (F) is blended using an enzyme preparation, the amount of the enzyme preparation is preferably 0.01% by mass or more, and 0.03% by mass or more as a lower limit with respect to the total amount of the liquid detergent. Is more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and on the other hand, the upper limit is preferably 2% by mass or less, more preferably 1.5% by mass or less, and 1% by mass or less. Is more preferable.

In the liquid cleaning agent of the present invention, a solvent other than water may be used from the viewpoint of improving the appearance stability. Examples of solvents other than water include water-miscible organic solvents.
In the present invention, the “water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
Examples of the water-miscible organic solvent 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, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, etc. And alkyl ethers.
The content of the water-miscible organic solvent is preferably 0.1 to 15% by mass with respect to the total amount of the liquid detergent.

Examples of the enzyme stabilizer include borax, boric acid, formic acid or salts thereof; calcium salts such as calcium chloride and calcium sulfate.
The content of the enzyme stabilizer is preferably 0 to 2% by mass with respect to the total amount of the liquid detergent.

Thickeners and solubilizers include aromatic sulfonic acids or salts thereof, such as toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid. , Cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, or salts thereof.
Examples of the salt form include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
The content of the thinning agent and the solubilizer is preferably 0.01 to 15% by mass with respect to the total amount of the liquid detergent. Within this preferred range, the formation of a film formed by gelation of the liquid detergent on the liquid surface of the liquid detergent is further suppressed.

  Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine and the like. As for content of an alkaline agent, 0.5-5 mass% is preferable with respect to the total amount of a liquid detergent.

  Examples of the metal ion scavenger (excluding the component (C)) 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 0.01 to 20% by mass with respect to the total amount of the liquid detergent.

The antioxidant is not particularly limited, but is preferably a phenolic antioxidant because of its good detergency and liquid stability; monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; 2 , 2′-methylenebis (bisphenol-based antioxidants such as 4-methyl-6-t-butylphenol, polymer-type phenolic antioxidants such as dl-α-tocopherol are more preferable, monophenolic antioxidants, high Molecular type phenolic antioxidants are more preferred.
Of the monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Among the high-molecular phenolic antioxidants, dl-α-tocopherol is particularly preferable. As for content of antioxidant, 0.01-2 mass% is preferable with respect to the total amount of a liquid detergent.

The liquid detergent of the present invention may contain, for example, Rohm & Haas Co., Ltd. product name: Caisson CG as a preservative in an amount of 0.001 to 1% by mass with respect to the total amount of the liquid detergent.
Moreover, you may contain a benzoic acid or its salt (it also has an effect as a preservative) for the purpose of an improvement in storage stability. Examples of the salt form include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like. The content of benzoic acid or a salt thereof is preferably from 0.1 to 5 mass%, more preferably from 0.15 to 2 mass%, based on the total amount of the liquid detergent.

The liquid detergent of the present invention may contain 0 to 5% by mass of silicone such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone for the purpose of improving the texture.
The liquid detergent of the present invention may contain 0 to 1% by mass of a fluorescent whitening agent such as a distyryl biphenyl type mainly for the purpose of improving the whiteness of white clothing. .

The liquid detergent of the present invention may contain 0 to 2% by mass of a recontamination inhibitor such as polyvinylpyrrolidone or carboxymethylcellulose for the purpose of preventing migration or recontamination, based on the total amount of the liquid detergent. .
As other components, a pearl agent, a soil release agent and the like may be contained.

The liquid detergent 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 the product.
As a flavoring agent, the fragrance | flavor composition A, B, C, D etc. of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399 are mentioned as a typical example. The content of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total amount of the liquid detergent.
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 with respect to the total amount of the liquid detergent.
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). The content of the emulsion is preferably 0.01 to 0.5% by mass with respect to the total amount of the liquid detergent.

Examples of extracts such as natural products include Inuenju, Ouurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, bay, honoki, burdock, confrey, potato, potato , Peonies, ginger, black-tailed peony, elderberry, sage, mistletoe, squirrels, thyme, velvet, clove, clove, mandarin orange, tea tree, barberry, dokudami, nanten, nyukou, yorigusa, shirogaya, boufu, dangwei, mountain hop Grape, Murasakitagayasan, Atlantic mint, Giant eel, Yamajiso, Eucalyptus, Lavender, Rose, Rosemary, Balun, Sugi, Gilead Munoki, 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 with respect to the total amount of the liquid detergent.

The pH of the liquid detergent can be adjusted by adding a pH adjuster as necessary.
Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid and citric acid; sodium hydroxide, potassium hydroxide and alkanolamine. Therefore, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable. A pH adjuster may be used individually by 1 type, and may use 2 or more types together.

The liquid detergent of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 6 to 9. When the pH is in the above preferred range, the storage stability of the liquid detergent is better maintained.
In the present invention, the pH of the liquid detergent indicates a value measured by adjusting the liquid detergent to 25 ° C. and using a pH meter or the like.

  The liquid cleaning agent of the present invention comprises water ((B) component), (A) component, (C) component, (D) component, (E) component, (F) component, It is produced by mixing other optional components as necessary.

The liquid detergent of the present invention described above contains (A) component: surfactant, (B) component: 45% by mass or less of water, and (F) component: protease, and (D ) Component: Sodium lactate and (E) component: Calcium lactate are used in combination, so that the component (F) can be stabilized and the enzyme activity is highly stable. In addition, component (C) (at least one compound selected from the group consisting of methylglycine diacetic acid, ethylglycine diacetic acid, nitrilotriacetic acid, iminodisuccinic acid, and salts thereof) is added to [(D) component + (E ) Component] / (C) By having the mass ratio of 0.01 to 50 represented by the component, a transparent and uniform appearance is maintained and appearance stability is improved.
Moreover, in the liquid detergent of this invention, even if it contains 2 or more types of enzymes, protease and other enzymes, any enzyme activity is maintained stably.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

The composition of the liquid cleaning agent in each example is shown in Tables 1-3.
The raw materials used in this example are as follows.

Component (A): Surfactant A-1: 8 parts by mass of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) ₁₅ OCH ₃ and ₂ parts by mass of C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) ₁₅ OCH ₃ Mixture with parts. A nonionic surfactant obtained by adding an average of 15 moles of ethylene oxide to a mixture of 8 parts by weight of methyl laurate and 2 parts by weight of methyl myristate. In the general formula (a1), R ¹ = alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, X = COO, R ² = methyl group, s = 15, t = 0, u = 0.

A-2: Obtained by block addition of 8 mol ethylene oxide, 2 mol propylene oxide, and 8 mol ethylene oxide in order to natural alcohol (mass ratio of 12 alcohols / 14 alcohols = 7/3) Nonionic surfactant. In the general formula (a1), R ¹ = C12 alkyl group and C14 alkyl group, X═O, R ² = hydrogen atom, s = 8, t = 2, u = 8.

A-3: A nonionic surfactant obtained by adding an average of 15 moles of ethylene oxide to natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble Co.). In the general formula (a1), R ¹ = C12 alkyl group and C14 alkyl group, X═O, R ² = hydrogen atom, s = 15, t = 0, u = 0.

  A-4: Linear alkylbenzene sulfonic acid, trade name “Lypon LH-200”, manufactured by Lion Corporation.

-(B) component: Water B-1: Distilled water.

Component (C): Specific compound C-1: Trisodium methylglycine diacetate (MGDA), trade name “Trilon M”, manufactured by BASF Corporation.
C-2: Ethylglycine diacetate, manufactured by Kanto Chemical Co., Inc.
C-3: Nitrilotriacetic acid, manufactured by Kanto Chemical Co., Inc.
C-4: Iminodisuccinic acid, manufactured by Kanto Chemical Co., Inc.

-Component (C '): Comparative component of component (C) C'-1: Ethylenediaminetetraacetic acid, manufactured by Kanto Chemical Co., Inc.

-(D) component: Sodium lactate D-1: Sodium lactate, the Kanto Chemical Co., Ltd. make.

-Component (D '): Comparative component of component (D) D'-1: Sodium acetate, manufactured by Kanto Chemical Co., Inc.

-(E) component: Sodium lactate E-1: Calcium lactate, the Kanto Chemical Co., Inc. make.

-(E ') component: Comparison component of (E) component E'-1: Calcium chloride, manufactured by Kanto Chemical Co., Inc.

-(F) component: Protease F-1: Coronase preparation, brand name "Coronase 48L", the product made by Novozymes.
F-2: Alcalase preparation, trade name “Alcalase 2.5 L”, manufactured by Novozymes.
F-3: Everase preparation, trade name “Everlase 16L”, manufactured by Novozymes.

-Optional component Cellulase: Cellulase preparation (enzyme), trade name “Carzyme Premium 4500L”, manufactured by Novozymes.
MEA: Monoethanolamine (alkaline agent, pH adjuster), manufactured by Nippon Shokubai Co., Ltd.
BHT: dibutylhydroxytoluene (antioxidant), trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd.
Ethanol: Water miscible organic solvent, trade name “specific alcohol 95 degree synthesis”, manufactured by Nippon Alcohol Sales Co., Ltd.
Fragrance | flavor: Fragrance | flavor agent, The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
PTS: p-toluenesulfonic acid (thickening agent and solubilizer, pH adjuster), manufactured by Kyowa Hakko Kogyo Co., Ltd.
Dye: Colorant, trade name “Green No. 3”, manufactured by Sakai Kasei Co., Ltd.

<Preparation of liquid detergent>
According to the composition shown in Tables 1 to 3 (compounding components, content (mass%)), liquid detergents of respective examples were prepared by the following production methods. The content shown in the table indicates the content of the compounding component (pure equivalent amount). In the table, a blank means that the blending component is not blended.
In the table, “(D) / (E) mass ratio” is synonymous with the mass ratio represented by (D) component / (E) component, and the content of (E) component contained in the liquid detergent. It means the ratio of the content (mass%) of the component (D) to (mass%).
“[(D) + (E)] / (C) mass ratio” is synonymous with the mass ratio represented by [(D) component + (E) component] / (C) component, and is a liquid detergent. It means the ratio of the total content (mass%) of the component (D) and the component (E) with respect to the content (mass%) of the component (C) contained in.
“[(D) + (E)] / (F) mass ratio” is synonymous with the mass ratio represented by [(D) component + (E) component] / (F) component, and is a liquid detergent. The ratio of the total content (mass%) of the component (D) and the ingredient (E) to the blending quantity (mass%) of the “formulation containing the component (F) (enzyme preparation)” contained in .
For each mass ratio, in Comparative Example 9, (C ′) component instead of (C) component, in Comparative Example 11, (D ′) component instead of (D) component, and in Comparative Example 3, instead of (E) component. The content (% by mass) of the component (E ′) was used.

The composition of the common component (X) contained in the liquid detergent of each example is shown below. Content (mass%) of each compounding component shows the ratio in a liquid detergent. The total content of the common component (X) is 10.5505% by mass with respect to the total mass of the liquid detergent.
In addition, 1 mass% of MEA and 1 mass% of PTS include an amount added to adjust the pH (25 ° C.) of the liquid detergent to 7.0.
Common component (X):
MEA 1% by mass, BHT 0.05% by mass, ethanol 8% by mass, perfume 0.5% by mass, PTS 1% by mass, dye 0.0005% by mass.

(Examples 1 to 26, Comparative Examples 1 to 11)
The liquid detergent for each example was prepared by the following procedure.
Into a 50 mL beaker, the component (D) or (D ′) and the component (E) or (E ′) are added, and a magnet stirrer (MITAMURA RIKEN KOGYO INC.) Is used to have a length of 25 mm and a diameter. The mixture was stirred for 20 minutes with an 8 mm stirrer chip to obtain a premix.
Separately, the component (A), the component (B), the component (C) or the component (C ′), and the optional component were put into a 500 mL beaker and stirred to dissolve these components. Next, the pre-mixture and the component (F) were added to the solution of the components (A) to (C) and the optional component and stirred. At that time, the mixture was dissolved by heating as necessary, and the temperature of the finally obtained mixed solution was adjusted to 20 ° C. ± 5 ° C.
Subsequently, using a pH meter (product name HM-30G, manufactured by Toa DKK Corporation), MEA and / or PTS as a pH adjuster so that the pH of the finally obtained mixed solution becomes 7.0 at 25 ° C. Was added to obtain a liquid detergent.

<Evaluation of liquid detergent>
With respect to the liquid detergents of the respective examples, evaluations of “stability of enzyme activity in the liquid detergent” and “appearance stability” were performed by the following evaluation methods. The results are also shown in Tables 1-3.

≪Evaluation of stability of enzyme activity in liquid detergents≫
The protease activity and cellulase activity of the liquid detergent were measured as follows.

[Measurement of protease activity]
After the preparation, protease activity was measured for the liquid detergent stored at 37 ° C. for 4 weeks (stored at 37 ° C.) and the liquid detergent stored at 4 ° C. for 4 weeks (stored at 4 ° C.) according to the following procedure.
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) is dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.), and the pH is 10 .5. This was diluted with 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) aqueous solution so that the concentration of milk casein was 0.6% by mass to obtain a protease substrate.
A solution obtained by diluting 1 g of the liquid detergent of each example 25 times (mass ratio) with 3 ° DH hard water (the hardness is adjusted with calcium chloride (special grade, manufactured by Kanto Chemical Co., Ltd.)) was used as a sample solution.
5 g of the protease substrate was added to 1 g of the sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37 ° C. for 30 minutes to proceed the enzyme reaction. Thereafter, 5 g of a 0.44 M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.), an enzyme reaction terminator, was added to the sample solution after the enzyme reaction, and the mixture was stirred for 10 seconds with a vortex mixer. Thereafter, this solution was allowed to stand at 20 ° C. for 30 minutes, the precipitate (unreacted substrate) was removed with a 0.45 μm filter, and the filtrate was recovered.
About the collect | recovered filtrate, the light absorbency (absorbance A) in wavelength 275nm was measured using Shimadzu Corporation ultraviolet visible spectrophotometer UV-160. The greater the absorbance A, the greater the amount of tyrosine (produced by the protease degrading the protease substrate) present in the filtrate.
In order to remove the influence of absorption other than the target component, 5 g of a 0.44 M aqueous solution of TCA was separately added to 1 g of each sample solution and stirred for 10 seconds with a vortex mixer. Thereafter, 5 g of protease substrate was added and stirred for 10 seconds with a vortex mixer. Next, the precipitate was removed with a 0.45 μm filter, and the filtrate was recovered. Thereafter, the absorbance of the collected filtrate (absorbance B) at a wavelength of 275 nm was measured using UV-160.

Based on the obtained absorbance A and absorbance B, the remaining rate of protease activity (%) was determined by the following formula (1).
Incidentally, the absorbance value at 275 nm of each sample substituted into the formula (1) is obtained by dividing the absorbance value at 600 nm measured at the same time in order to exclude scattered light such as bubbles from the absorbance.
Protease activity remaining rate (%)
= {(Absorbance A of a product stored at 37 ° C.) − (Absorbance B of a product stored at 37 ° C.)} / {(Absorbance A of a product stored at 4 ° C.) − (Absorbance B of a product stored at 4 ° C.)} × 100 1)
Then, the storage stability of the protease activity was evaluated according to the following evaluation criteria using the obtained protease activity remaining rate (%) as an index. The results are shown in Tables 1-3.
The better the storage stability of the protease activity, the higher the stability of the protease activity in the liquid detergent.
Evaluation criteria A: Protease activity remaining rate is 85% or more.
○: Protease activity remaining rate is 75% or more and less than 85%.
Δ: Protease activity remaining rate is 65% or more and less than 75%.
X: Protease activity remaining rate is less than 65%.

[Measurement of cellulase activity]
Cellulase activity was measured for the liquid detergent stored at 37 ° C. for 4 weeks (prepared at 37 ° C.) and the liquid detergent stored at 4 ° C. for 4 weeks (stored at 4 ° C.) by the following procedure. The titer of each liquid detergent was determined from a calibration curve using.
To 20 g of Avicel (manufactured by Fluka, No. 11365) which is a cellulose powder, 600 mL of an 85% by mass phosphoric acid solution was added and stirred slowly with a stirrer while cooling in an ice bath, and 400 mL of acetone was added thereto to swell. The obtained swelling liquid was filtered with a filter, washed with 400 mL of acetone three times, and washed with 1000 mL of MilliQ water seven times. To this was added 2000 mL of MilliQ water, which was used as a cellulase substrate.
A sample solution was prepared in advance in the same manner as in [Measurement of protease activity] described above.
In a centrifuge tube, 2 mL of the sample solution, 2 mL of 0.1 M phosphate buffer, and 2 mL of the cellulase substrate were placed, and the mixture was allowed to react for 60 minutes in a 50 ° C. water bath with stirring. Then, 1 mL of 2 mass% NaOH aqueous solution was added and reaction was stopped. This was centrifuged (4000 rpm, 10 minutes), and the supernatant was collected. To 4 mL of the supernatant, 2 mL of a coloring reagent PAHBAH solution was added and stirred. Thereafter, this solution was boiled at 100 ° C. for 8 minutes to react glucose reducing sugar with a coloring reagent. Thereafter, this solution was cooled in an ice bath, and the absorbance at a wavelength of 410 nm was measured.
The coloring reagent PAHBAH solution was added to 1.5 g of PAHBAH (4-Hydroxybenzhydrazide, Sigma, No. H-9882), 5.0 g of (+)-potassium sodium tartrate tetrahydrate and Bismuth (III) acetate. 193 g was added, and the volume was made up to 100 mL with a 2 mass% NaOH aqueous solution.
Separately, a standard enzyme solution was prepared by the following procedure, and a calibration curve was prepared.
0.175 g of standard enzyme (5700 ECU / g) was dissolved in 1 L of 0.1 M phosphate buffer to obtain a mother liquor. This mother liquor is diluted stepwise with 0.1M phosphate buffer, and 0.1M phosphate buffer alone, mother solution 250-fold diluted solution, 50-fold diluted solution, 25-fold diluted solution, 12.5-fold diluted solution 5 standard solutions were prepared respectively.
These standard solutions were processed in the same manner as the sample solution, the absorbance at a wavelength of 410 nm was measured, and a calibration curve was prepared.

The titer of the sample solution was determined from the obtained calibration curve, and the cellulase activity remaining rate (%) was determined by the following equation (2).
Cellulase activity remaining rate (%) = (titer of product stored at 37 ° C.) / (Titer of product stored at 4 ° C.) × 100 (2)
Then, the storage stability of protease activity was evaluated according to the following evaluation criteria using the obtained cellulase activity remaining ratio (%) as an index. The results are shown in Tables 1-3.
The better the storage stability of the cellulase activity, the higher the stability of the cellulase activity in the liquid detergent.
Evaluation criteria A: Cellulase activity remaining rate is 85% or more.
○: Cellulase activity remaining rate is 75% or more and less than 85%.
Δ: Cellulase activity remaining rate is 65% or more and less than 75%.
X: Cellulase activity remaining rate is less than 65%.

[Evaluation of appearance stability]
A transparent glass bottle (wide-mouth bottle, PS-NO.11) was filled with 100 mL of liquid detergent, and the lid was closed and sealed. In this state, it was stored in a constant temperature bath at 37 ° C. for 30 days.
After such storage, the appearance of the liquid was visually observed, and the appearance stability of the liquid detergent was evaluated according to the following evaluation criteria.
Evaluation criteria ○: No precipitated substance is observed at the bottom of the glass bottle.
Δ: Precipitated material is observed at the bottom of the glass bottle, but when the glass bottle is shaken lightly, the precipitated material disappears (dissolves).
X: A precipitated substance was observed at the bottom of the glass bottle, and the precipitated substance did not disappear even if the glass bottle was shaken lightly, or gelled or became cloudy immediately after the production of the liquid detergent.

  From the evaluation results shown in Tables 1 to 3, it was confirmed that the liquid detergents of Examples 1 to 26 to which the present invention was applied had high enzyme activity stability and good appearance stability.

Claims (1)

(A) component: surfactant,
(B) component: 45 mass% or less of water,
(C) component: at least one compound selected from the group consisting of methylglycine diacetic acid, ethylglycine diacetic acid, nitrilotriacetic acid, iminodisuccinic acid, and salts thereof;
(D) component: 0.01-3.2 mass% of sodium lactate,
(E) component: 0.01-3 mass% of calcium lactate,
(F) component: protease and
Containing
The liquid cleaning agent whose mass ratio represented by [(D) component + (E) component] / (C) component is 0.01-50.