JP2021098807A - Liquid detergent composition - Google Patents

Abstract

To provide a liquid detergent composition that contains an anionic surfactant in high concentration and yet ensures high stability of an enzyme and prevents enzymatic activity from deteriorating during storage.SOLUTION: A liquid detergent composition contains a non-soap anionic surfactant containing one or more selected from the group consisting of (A) component: (A1) component, (A2) component, and (A3) component, (B) component: a nonionic surfactant, (C) component: an organic solvent containing (C1) component and (C2) component, and (D) component: an enzyme. The (A1) component is linear alkylbenzene sulfonic acid or a salt thereof, (A2) component is polyoxyalkylene alkyl ether sulfate ester or a salt thereof, (A3) component is α-olefin sulfonic acid or a salt thereof, (C1) component is phenoxy ethanol, (C2) component is one or more selected from the group consisting of propyleneglycol and butylcarbitol.SELECTED DRAWING: None

Description

The present invention relates to a liquid detergent composition.

Conventionally, surfactants such as anionic surfactants have been used in liquid detergent compositions for textile products such as clothing. In addition, an enzyme is often added to supplement the detergency of the surfactant.
In recent years, a highly concentrated liquid detergent composition having a high surfactant concentration has been required so that a cleaning effect can be exhibited with a small amount of use (Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-129462

However, when an enzyme is added to a liquid detergent composition containing a high concentration of anionic surfactant, there is a risk that the enzyme activity may decrease during storage.
Therefore, an object of the present invention is to provide a liquid detergent composition which contains an anionic surfactant in a high concentration, has high stability of the blended enzyme, and the enzyme activity does not easily decrease during storage.

In order to achieve the above problems, the present invention has adopted the following configuration.
[1] Ingredient (A): A non-soap-based anionic surfactant containing one or more selected from the group consisting of the following (A1) component, the following (A2) component, and the following (A3) component.
(B) Ingredients: Nonion surfactant and
Component (C): An organic solvent containing the following component (C1) and the following component (C2),
A liquid detergent composition containing the component (D): an enzyme.
The component (A1) is a linear alkylbenzene sulfonic acid or a salt thereof.
The component (A2) is a polyoxyalkylene alkyl (alkenyl) ether sulfate ester or a salt thereof.
The component (A3) is α-olefin sulfonic acid or a salt thereof.
The component (C1) is phenoxyethanol.
The component (C2) is one or more selected from the group consisting of propylene glycol and butyl carbitol.
It contains 1 or more selected from the group consisting of the component (A1), the component (A2), and the component (A3), and the total content thereof is 15 with respect to the total mass of the liquid detergent composition. It is more than% by mass and
The total content of the component (C1) and the component (C2) is 10 to 20% by mass with respect to the total mass of the liquid detergent composition.
The total content of the component (A) and the component (B) is 50% by mass or more with respect to the total mass of the liquid detergent composition.
A liquid detergent composition in which the ratio [(A) / (B)] of the mass of the component (A) to the mass of the component (B) is 1.0 to 2.5.
[2] The liquid detergent composition according to [1], wherein the ratio of the mass of the component (C1) to the mass of the component (C2) [(C1) / (C2)] is 1 to 5.5. ..
[3] The liquid detergent composition according to [1] or [2], wherein the content of water is 30% by mass or less with respect to the total mass of the liquid detergent composition.

According to the liquid detergent composition of the present invention, the stability of the blended enzyme is high while the anionic surfactant is contained in a high concentration, and the enzyme activity is unlikely to decrease during storage.

The liquid detergent composition of the present invention is a liquid detergent composition containing the components (A), (B), (C), and (D) described later.
The description of the constituent elements described below may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value. Further, the content of the component that can take the form of an acid and the form of a salt is the content in the form of an acid unless otherwise specified.

<Ingredient (A)>
The component (A) is a non-soap-based anionic surfactant. The "non-soap-based anionic surfactant" is an anionic surfactant excluding higher fatty acids or salts thereof (so-called soap).
The component (A) includes one or more selected from the group consisting of the following components (A1), (A2), and (A3).
(A1) component: linear alkylbenzene sulfonic acid or a salt thereof,
(A2) Component: Polyoxyalkylene alkyl (alkenyl) ether sulfate ester or a salt thereof,
(A3) Component: α-olefin sulfonic acid or a salt thereof.

The number of carbon atoms of the alkyl group in the component (A1) is preferably 8 to 18, more preferably 8 to 16, and even more preferably 10 to 16.
Examples of the salt of the linear alkylbenzene sulfonic acid include an alkali metal salt with sodium, potassium and the like, an alkaline earth metal salt with magnesium and the like, an alkanolamine salt with monoethanolamine, diethanolamine and the like.

Examples of the component (A2) include a compound represented by the following general formula (a-1) (hereinafter, referred to as “compound (a-1)”).
R ^8- O-[(EO) _k / (PO) _n ] -SO ₃ ^- M ⁺ ... (a-1)
In formula (a-1), R ⁸ is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms, and EO is an oxy. It is an ethylene group, PO is an oxypropylene group, k is a number of 0.1 or more indicating the average number of repetitions of EO, n is a number of 0 to 6 indicating the average number of repetitions of PO, and [( EO) _k / (PO) _n ] indicates that there is no limitation on the sequence order of EO and PO, and M ⁺ is a counter cation.
The content of the component (a-0) in which k = 0 and n = 0 in the formula (a-1) is preferably 35 to 55% by mass with respect to the total mass of the component (A2).

R ⁸ is preferably a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, and more preferably a linear or branched alkyl group or alkenyl group having 12 to 14 carbon atoms.
In particular, a linear alkyl group having 10 to 20 carbon atoms is preferable, and a linear alkyl group having 12 to 14 carbon atoms is more preferable.
k is preferably 0.1 to 5, more preferably 0.1 to 3, more preferably 0.5 to 2, and particularly preferably 0.5 to 1.5.
n is preferably 0 to 3, more preferably 0.
k + n is preferably 0.1 or more, and more preferably 1 to 5.

Compound (a-1) is a polyoxyethylene alkyl ether sulfate ester in which k is 0.5 or more and n is 0 because of its good detergency and handling during the production of the liquid detergent composition. It is preferably the salt.
The k of the polyoxyethylene alkyl (alkenyl) ether sulfate ester or a salt thereof is preferably 0.1 to 5, more preferably 0.1 to 3, still more preferably 0.5 to 2, and 0.5 to 1.5. Is particularly preferable.

When neither k nor n is 0, that is, when compound (a-1) has both EO and PO, the distribution (sequence order) of EO and PO is not particularly limited, and even if they are arranged in a block shape. It may be arranged randomly.
As a method of arranging EO and PO in a block shape, for example, a method of introducing ethylene oxide and then introducing propylene oxide, a method of introducing ethylene oxide after introducing propylene oxide, and a method of introducing ethylene oxide and then introducing propylene oxide. Further, a method of introducing ethylene oxide and the like can be mentioned.
Examples of the salt of the polyoxyalkylene alkyl ether sulfate include an alkali metal salt with sodium, potassium and the like, an alkaline earth metal salt with magnesium and the like, an alkanolamine salt with monoethanolamine, diethanolamine and the like.

The carbon number of the component (A3) is preferably 8 to 24, and more preferably 10 to 20.
Examples of the salt of α-olefin sulfonic acid include alkali metal salts with sodium, potassium and the like, alkaline earth metal salts with magnesium and the like, alkanolamine salts with monoethanolamine, diethanolamine and the like.

Examples of the component (A) other than the component (A1), the component (A2) and the component (A3) include anionic surfactants conventionally used in liquid detergents for clothing and the like.
For example, a linear or branched alkyl sulfate ester or a salt thereof; an alkane sulfonic acid having an alkyl group or a salt thereof; an α-sulfo fatty acid ester or a salt thereof (MES); an internal olefin sulfonic acid or a salt thereof (IOS). , Hydroxyalcan sulfonic acid or salt thereof (HAS); alkyl ether carboxylic acid or salt thereof, polyoxyalkylene ether carboxylic acid or salt thereof, alkylamide ether carboxylic acid or salt thereof, alkenylamide ether carboxylic acid or salt thereof, acylamino Carboxylic acid type anionic surfactant such as carboxylic acid or salt thereof; alkyl phosphate ester or salt thereof, polyoxyalkylene alkyl phosphate ester or salt thereof, polyoxyalkylene alkylphenyl phosphate ester or salt thereof, glycerin fatty acid ester monoline Examples thereof include a phosphate ester type anionic surfactant such as an acid ester or a salt thereof.
Examples of the salt form of these anionic surfactants include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolammonium and diethanolammonium.

These components (A) are readily available on the market. Further, those synthesized by a known method may be used.
The component (A) may be used alone or in combination of two or more.

The total content of the component (A) is preferably 15 to 45% by mass, more preferably 20 to 40% by mass, and 25 to 40% by mass with respect to the total mass of the liquid detergent composition. It is more preferable to have.
When the total content of the component (A) is 15% by mass or more, the detergency against protein stains is enhanced.
When the total content of the component (A) is 45% by mass or less, the stability of the liquid detergent composition is enhanced.

The component (A) includes one or more selected from the group consisting of the component (A1), the component (A2), and the component (A3), and the total content thereof is based on the total mass of the liquid detergent composition. It is 15% by mass or more, preferably 15 to 45% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 40% by mass.
When it is 15% by mass or more, the detergency against protein stains is enhanced. When it is 45% by mass or less, the stability of the liquid detergent composition is enhanced.

The ratio of the total content of the component (A1), the component (A2) and the component (A3) to the total content of the component (A) in the liquid detergent composition is preferably 50 to 100% by mass, and is 70. It is more preferably to 100% by mass, and even more preferably 80 to 100% by mass.
When the ratio of the total content of the component (A1), the component (A2) and the component (A3) to the total content of the component (A) is 50% by mass or more, the protein detergency is enhanced.

The ratio of the mass of the component (A2) to the mass of the component (A1) in the liquid detergent composition [(A2) / (A1)] is preferably 0.1 to 5, more preferably 0.1 to 4. 0.2 to 3 is more preferable.
The ratio of the mass of the component (A3) to the mass of the component (A1) in the liquid cleaning agent composition [(A3) / (A1)] is preferably 0.1 to 5, more preferably 0.1 to 4. 0.2 to 3 is more preferable.
The ratio of the mass of the component (A3) to the mass of the component (A2) in the liquid cleaning agent composition [(A3) / (A2)] is preferably 0.1 to 5, more preferably 0.1 to 4. 0.2 to 3 is more preferable.

<Ingredient (B)>
The component (B) is a nonionic surfactant.
As the component (B), a polyoxyalkylene type nonionic surfactant is preferable from the viewpoint of detergency. Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (b-1) (hereinafter referred to as compound (b-1)).
R ^1- X-[(EO) _s / (AO) _t ]-(EO) _u- R ² ... (b-1)

In formula (b-1), R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, -X- is a divalent linking group, and R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkyl group. It is an alkenyl group having 2 to 6 carbon atoms.
EO is an oxyethylene group, and s is a number of 3 to 25 indicating the average number of EO repetitions.
AO represents at least one of PO (oxypropylene group) or BO (oxybutylene group). t is a number from 0 to 6 indicating the average number of repetitions of PO or BO. u represents the average number of repetitions of EO and is a number from 0 to 20.
When t is 1 or more, the order of arrangement of the oxyethylene group and the oxypropylene group or the oxyethylene group and the oxybutylene group is not limited _{in [(EO) s} / (AO) _{t], and even if it is a random polymerization.} It may be block polymerization or block polymerization.

In the formula (b-1), ^{the hydrocarbon group of R 1} has 8 to 22 carbon atoms, preferably 10 to 18, and more preferably 12 to 18. The hydrocarbon group may be a straight chain or a branched chain. Further, it may or may not have an unsaturated bond.
R ¹ is preferably a linear alkyl group.

Examples of the divalent linking group of −X− include −O−, −COO−, −CONH− and the like. ^{The carbon atom of R 1} to which X is bonded may be a primary carbon atom or a secondary carbon atom.
When R ² is an alkyl group, the number of carbon atoms is 1 to 6, preferably 1 to 3. When R ² is an alkenyl group, the number of carbon atoms is 2 to 6, preferably 2 to 3.

s is 3 to 25, preferably 5 to 18. When the average number of repetitions s of EO is 25 or less, the HLB value does not become too high and it is advantageous for sebum cleaning, so that the cleaning function is more easily exhibited. On the other hand, when the average number of repetitions s of EO is 3 or more, the cleaning effect on sebum stains is enhanced.
t is 0 to 6, preferably 0 to 3. When t is 6 or less, the storage stability of the liquid detergent composition under high temperature is further enhanced.
u is 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
The average number of moles of s + u, that is, the total EO addition of compound (b-1) is preferably 3 to 30, more preferably 10 to 25, and even more preferably 12 to 18. When s + u is 3 or more, it is easy to exert a cleaning effect on sebum stains. When s + u is 30 or less, the stability of the liquid detergent composition is enhanced. Especially when t is 0, the above range is more preferable.

When t is not 0, that is, when compound (b-1) has both EO and PO, or both EO and BO, the distribution (sequence order) of EO and PO, or EO and BO is not particularly limited and blocks. It may be arranged in a shape or may be arranged in a random shape.
As a method of arranging EO and PO in a block shape, for example, a method of introducing ethylene oxide and then introducing propylene oxide, a method of introducing ethylene oxide after introducing propylene oxide, and a method of introducing ethylene oxide and then introducing propylene oxide. Further, a method of introducing ethylene oxide and the like can be mentioned.
Examples of the method of arranging EO and BO in a block shape include a method of introducing butylene oxide after introducing ethylene oxide, a method of introducing ethylene oxide after introducing butylene oxide, and a method of introducing butylene oxide after introducing ethylene oxide. Further, a method of introducing ethylene oxide and the like can be mentioned.

-X- is -O- compound (b-1), it can be obtained by the primary alcohol or the secondary alcohol (R 1 ^-OH), adding ethylene oxide or ethylene oxide and propylene oxide.
The compound (b-1) in which −X− is −COO− ^{can be obtained from a fatty acid (R-1-} COOH) as a raw material. The compound -X- is -CONH- (b-1) can be obtained fatty acid amide ^(R 1 -CONH) as a raw material.

The component (B) preferably contains one or more selected from the group consisting of the following components (B1), (B2), and the following (B3).
(B1) Ingredients: Polyoxyethylene alkyl ether, which is an ethylene oxide adduct of primary alcohols,
(B2) Ingredients: Polyoxyethylene alkyl ether, which is an ethylene oxide adduct of a secondary alcohol,
(B3) Ingredient: Polyoxyethylene fatty acid alkyl ester.

In the component (B1), in compound (b-1), R ¹ is a linear alkyl group, -X- is -O-, t is 0, R ² is a hydrogen atom, and X is. carbon atoms bonded to R ¹ is a compound which is a primary carbon atom.
^{The carbon number of R 1} of the component (B1) is 8 to 22, preferably 10 to 18, and more preferably 12 to 18.
The s + u of the component (B1) is 3 to 25, preferably 5 to 18.

In the component (B2), in the formula (b-1), R ¹ is a linear alkyl group, -X- is -O-, t is 0, R ² is a hydrogen atom, and X is. carbon atoms bonded to R ¹ is a compound which is a secondary carbon atom.
^{The carbon number of R 1} of the component (B2) is 8 to 22, preferably 10 to 18, and more preferably 12 to 18.
The s + u of the component (B2) is 3 to 25, preferably 5 to 18.

In the component (B3), in compound (b-1), R ¹ is a linear alkyl group, -X- is -COO-, t is 0, R ² is an alkyl group, and X is. A compound in which the carbon atom of ^{R 1 to be} bonded is a secondary carbon atom.
^{The carbon number of R 1} of the component (B3) is 9 to 21, preferably 9 to 19, and more preferably 9 to 17.
^{The carbon number of R 2} of the component (B3) is 1 to 6, preferably 1 to 3, and most preferably 1. That is, the component (B3) is most preferably polyoxyethylene fatty acid methyl ester.
The s + u of the component (B3) is 3 to 25, preferably 10 to 20.

Examples of the component (B) other than the component (B1), the component (B2) and the component (B3) include nonionic surfactants conventionally used in liquid detergents for clothing and the like.
For example, alkylene oxide adducts such as polyoxyalkylene alkylamines, alkylphenols and higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyvalent Examples include alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hardened castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like.

These components (B) are readily available on the market. Further, those synthesized by a known method may be used.
The component (B) may be used alone or in combination of two or more.

The total content of the component (B) is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, and 20 to 30% by mass with respect to the total mass of the liquid detergent composition. It is more preferable to have.
When the total content of the component (B) is 10% by mass or more, the detergency against sebum stains is improved.
When the total content of the component (B) is 35% by mass or less, the stability of the liquid detergent composition is enhanced.

The component (B) includes one or more selected from the group consisting of the component (B1), the component (B2), and the component (B3), and the total content thereof is based on the total mass of the liquid detergent composition. It is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, and even more preferably 20 to 30% by mass.
When the total content of the component (B1), the component (B2) and the component (B3) is within the above range, the sebum detergency is enhanced and the stability of the liquid detergent composition is enhanced.

The ratio of the total content of the component (B1), the component (B2) and the component (B3) to the total content of the component (B) in the liquid detergent composition is preferably 70 to 100% by mass, preferably 80. It is more preferably to 100% by mass, and even more preferably 90 to 100% by mass.
When the ratio of the total content of the component (B1), the component (B2) and the component (B3) to the total content of the component (B) is 70% by mass or more, the detergency against sebum stains is improved.

The total content of the component (A) and the component (B) is 50% by mass or more, preferably 50 to 75% by mass, and 55 to 70% by mass with respect to the total mass of the liquid detergent composition. More preferably.
When the total content of the component (A) and the component (B) is 50% by mass or more, sufficient detergency can be exhibited with a small amount of use.
When the total content of the component (A) and the component (B) is 75% by mass or less, the stability of the liquid detergent composition at low temperature is improved.

The ratio of the mass of the component (A) to the mass of the component (B) [(A) / (B)] is 1.0 to 2.5, preferably 1.0 to 2.0, and 1 It is more preferably .2 to 2.0, further preferably 1.2 to 1.8, and particularly preferably 1.2 to 1.5.
Further, 1.0 or more is preferable, and 1.2 or more is more preferable. 2.5 or less is preferable, 2.0 or less is more preferable, 1.8 or less is further preferable, and 1.5 or less is particularly preferable.
When [(A) / (B)] is 1.0 or more, the detergency against protein stains and the anti-recontamination property are enhanced.
When [(A) / (B)] is 2.5 or less, the enzyme stability is enhanced.
The present invention can solve the problem of enzyme stability peculiar to a liquid detergent composition having a so-called anion-rich composition in which [(A) / (B)] is 1.0 or more.

<Ingredient (C)>
The component (C) is an organic solvent. The component (C) includes the following components (C1) and (C2).
(C1) Ingredient: Phenoxyethanol,
(C2) Ingredient: One or more selected from the group consisting of propylene glycol and butyl carbitol.

The component (C) may contain an organic solvent other than the component (C1) and the component (C2) as long as the effects of the present invention are not impaired.
Examples of the organic solvent other than the component (C1) and the component (C2) include organic solvents conventionally used for liquid detergents for clothing and the like.
For example, ethanol, 3-methoxy-3-methylbutanol, ethylene glycol and polyethylene glycol can be mentioned.
These components (C) are readily available on the market. Further, those synthesized by a known method may be used.

The total content of the component (C) is preferably 10 to 20% by mass, more preferably 10 to 18% by mass, and 10 to 16% by mass with respect to the total mass of the liquid detergent composition. It is more preferable to have.
When the total content of the component (C) is 10% by mass or more, the fluidity of the liquid detergent composition during low-temperature storage becomes good.
When the total content of the component (C) is 20% by mass or less, the appearance of the liquid detergent composition immediately after production is improved.

The total content of the component (C1) and the component (C2) is 10 to 20% by mass, preferably 10 to 18% by mass, and preferably 10 to 16% by mass with respect to the total mass of the liquid detergent composition. More preferably.
When the total content of the component (C1) and the component (C2) is 10% by mass or more, the fluidity of the liquid detergent composition at low temperature storage becomes good.
When the total content of the component (C1) and the component (C2) is 20% by mass or less, the appearance of the liquid detergent composition immediately after production is improved.
The total content of the component (C1) is preferably 7 to 17% by mass with respect to the total mass of the liquid detergent composition.
The total content of the component (C2) is preferably 3 to 13% by mass with respect to the total mass of the liquid detergent composition.

The ratio of the total content of the component (C1) and the component (C2) to the total content of the component (C) in the liquid detergent composition is preferably 50 to 100% by mass, preferably 70 to 100% by mass. Is more preferable, and 80 to 100% by mass is further preferable.
When the ratio of the total content of the component (C1) and the component (C2) to the total content of the component (C) is 50% by mass or more, the enzyme stability is likely to be improved.

The ratio of the mass of the component (C1) to the mass of the component (C2) [(C1) / (C2)] is preferably 1 to 5.5, more preferably 1 to 5, and 1.5. It is more preferably ~ 5, and particularly preferably 2-4.
[(C1) / (C2)] is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more. Further, 5.5 or less is preferable, 5 or less is more preferable, and 4 or less is further preferable.
When [(C1) / (C2)] is within the above range, the enzyme stability tends to be further enhanced.

The combinations of the (C1) component and the (C2) component are "phenoxyethanol (C1) and propylene glycol (C2)", "phenoxyethanol (C1) and butyl carbitol (C2)", and "phenoxyethanol (C1) and propylene glycol (C2)". ) And butyl carbitol (C2) ", and a combination of" phenoxyethanol (C1) and propylene glycol (C2) "and" phenoxyethanol (C1) and butyl carbitol (C2) "is more preferable.

The ratio of the total mass of the component (A) and the component (B) to the total mass of the component (C) [(A + B) / (C)] is preferably 3 to 7, and preferably 3 to 6. More preferably, it is more preferably 3 to 5.
When [(A + B) / (C)] is within the above range, solidification of the liquid detergent composition during low-temperature storage can be suppressed.
The ratio of the mass of the component (A) to the mass of the component (C) in the liquid detergent composition [(A) / (C)] is preferably 1 to 4, more preferably 1 to 3, and 1 to 2.5. Is even more preferable.
The ratio of the mass of the component (B) to the mass of the component (C) in the liquid detergent composition [(B) / (C)] is preferably 0.5 to 3, more preferably 0.5 to 2.5. , 1-2 are more preferable.

<Ingredient (D)>
The component (D) is an enzyme. Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase and the like.
It is preferable to contain both protease and amylase because it can enhance the detergency against protein stains and food stains.

As the protease, a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease, is preferable.
Enzyme preparations (protease preparations) containing proteases are commercially available. When preparing a liquid detergent, the protease is usually formulated using this protease preparation.
Examples of the protease preparation include the trade names Subinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase 2.5LaseAlseLaseAlseLaseAlseLase8, which can be obtained from Novozymes. , Liquane Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L Protease Uno 100L; trade names Purafect L, Pharmaceutical OX, Propase L and the like available from Genecore.

Examples of amylase include α-amylase, β-amylase, α-glucositase, and glucoamylase; glucoamylase, pullulanase, isoamylase, and amylo-1,6 glucositase / 4 that hydrolyze α-1,6 bonds such as starch and glycogen. -Α-Glucanotransferase, oligo-1,6-glucositase and the like are preferable.
Enzyme preparations containing amylase (amylase preparations) are commercially available. When preparing a liquid detergent, amylase is usually formulated using this amylase preparation.
Examples of the amylase preparation include Termamyl Ultra 300L, Duramyl 16L, Stainzyme 12L, Promozyme 200L, Amplify Prime (Amplify Prime) 100L, and Medley. (Mixed enzyme of protease and amylase. Above, trade name; manufactured by Novozymes); Maxamil (trade name, manufactured by Genencore), pullulanase amano (trade name, manufactured by Amano Pharmaceutical Co., Ltd.), DB-250 (trade name) , Aerobacter aerogenes ATCC9621-derived pullulanase, crude or crystallized product, manufactured by Biochemical Industry Co., Ltd.) and the like. Among them, as the component (B), Duramil 16L, Stainzyme 12L, Termamil Ultra 300L, and Amplify Prime 100L (above, trade name; manufactured by Novozymes) are preferable, and Amplify Prime 100L is more preferable.

Examples of the lipase preparation include trade names Lipex 100L and Lipase 100L available from Novozymes.
Examples of the cellulase preparation include Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (trade name, manufactured by Novozymes), Endolase 5000L (trade name, manufactured by Novozymes), and Cellclean 4500T (trade name, manufactured by Novozymes). (Manufactured by the company) and the like.
Examples of the mannanase preparation include the trade name Mannaway 4L available from Novozymes.

The total content of the component (D) is preferably 1 to 10% by mass, more preferably 1.5 to 5% by mass, based on the total mass of the liquid detergent composition as the enzyme preparation. It is more preferably 1.8 to 4% by mass, particularly preferably 2 to 4% by mass, and most preferably 2.5 to 4% by mass.
In the present invention, the total content of the protease is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the liquid detergent composition as the enzyme preparation. .2 to 4% by mass is more preferable, and 1.5 to 3% by mass is particularly preferable.
The total content of amylase is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total mass of the liquid detergent composition as the enzyme preparation. , 0.3 to 1% by mass, more preferably.
The ratio of the mass of amylase to the mass of protease [protease / amylase] is preferably 0.25 to 4, more preferably 1 to 4, and even more preferably 2 to 4.

When the total content of the component (D) is 1% by mass or more, the detergency is likely to be enhanced.
When the total content of the component (D) is 10% by mass or less, the enzyme-derived odor in the liquid detergent composition can be suppressed.
According to the present invention, high enzyme stability can be obtained even when the component (D) is blended in a high content.

The ratio of the mass of the component (C) to the mass of the component (D) in the liquid detergent composition [(C) / (D)] is preferably 1 to 10, more preferably 2 to 8, and 3 to 8. More preferred.
The ratio of the mass of the component (C) to the mass of the protease of the component (D) in the liquid detergent composition [(C) / (protease))] is preferably 1 to 10, more preferably 2 to 8. ~ 8 is more preferable.
The ratio of the mass of the component (C) to the mass of the amylase of the component (D) in the liquid detergent composition [(C) / (amylase))] is preferably 10 to 50, more preferably 15 to 40, and 20 ~ 35 is more preferable.

The ratio of the mass of the component (C1) to the mass of the component (D) in the liquid detergent composition [(C1) / (D)] is preferably 1 to 10, more preferably 2 to 8, and 2 to 5. More preferred.
The ratio of the mass of the component (C2) to the mass of the component (D) in the liquid detergent composition [(C2) / (D)] is preferably 0.5 to 5, more preferably 0.5 to 8. 1 to 5 are more preferable.
The ratio of the mass of the component (A) to the mass of the component (D) in the liquid detergent composition [(A) / (D)] is preferably 5 to 20, more preferably 5 to 15, and 8 to 15. More preferred.
The ratio of the mass of the component (B) to the mass of the component (D) in the liquid detergent composition [(B) / (D)] is preferably 5 to 20, more preferably 5 to 15, and 5 to 12. More preferred.

<Ingredient (E)>
The liquid detergent composition of the present invention may further contain the component (E).
The component (E) is a higher fatty acid or a salt thereof. "Higher fatty acid" means a fatty acid having 8 to 22 carbon atoms.
Although the higher fatty acid or a salt thereof is in the category of anionic surfactants, it has a different action from the non-soap-based anionic surfactant of the component (A), functions as a defoaming agent, and contributes to the improvement of rinsing property. When the rinsing property is improved, the number of rinsing treatments after the cleaning treatment can be reduced.

As the higher fatty acid, a chain monocarboxylic acid having 8 to 18 carbon atoms is preferable. Specific examples thereof include a compound represented by the formula (e-1).
R ^9- COOH ... (e-1)
In formula (e-1), R ⁹ is an aliphatic hydrocarbon group having 7 to 17 carbon atoms.

In the formula (e-1), ^{the aliphatic hydrocarbon group of R 9} may be linear or branched, an alkyl group of linear or branched chain, or a linear or branched alkyl group. Branched chain alkenyl groups are preferred. The aliphatic hydrocarbon group of R ⁹ has 7 to 17 carbon atoms, preferably 11 to 17 carbon atoms. When ^{the carbon number of R 9} is 7 or more, the defoaming effect can be easily obtained. On the other hand, when ^{the carbon number of R 9} is 17 or less, the solubility in water is further enhanced.

Examples of the salt form in the higher fatty acid include an alkali metal salt, an alkaline earth metal salt, an amine salt, an ammonium salt and the like. Examples of the alkali metal salt include sodium salt, potassium salt and the like. Examples of the alkaline earth metal salt include calcium salts and magnesium salts. Examples of the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

The content of the component (E) is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total mass of the liquid detergent composition.
When the total content of the component (E) is within the above range, the defoaming property is enhanced and the high temperature stability of the enzyme can be easily obtained.

<Water>
The liquid detergent composition of the present invention contains water. The water content is preferably 30% by mass or less, more preferably 5 to 25% by mass, and even more preferably 8 to 25% by mass with respect to the total mass of the liquid detergent composition. ..
When the total content of water is within the above range, the component (D) can be easily dissolved in the liquid detergent composition.
When the total content of water is 30% by mass or less, the components (A) and (B) can be contained in a required amount, and sufficient detergency can be easily obtained.

<Arbitrary ingredient>
In addition to the above-mentioned components (A) to (E) and water, the liquid detergent composition may contain components known in the field of liquid detergent as long as the effects of the present invention are not impaired.
Optional components include, for example, polymers (A), surfactants other than component (B), stabilizers, bleaching agents, fluorescent whitening agents, soil release agents, alkylene oxide adducts of polyalkylene amines, and the like. (P), dispersant, defoamer (excluding B component and E component), pH adjuster, chelating agent, alkaline agent, texture improver, antibacterial agent, preservative, antioxidant, fragrance, pigment, etc. Be done.
The total content of the components (A) to (E) and water does not exceed 100% by mass with respect to the total mass of the liquid detergent composition.

Examples of the surfactant other than the component (A) and the component (B) include a cationic surfactant, a semi-polar surfactant, an amphoteric surfactant and the like. Specific examples are shown below.

(Cationic surfactant)
Examples of the cationic surfactant include alkylamide amines. It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition.

(Amphoteric surfactant)
Examples of the amphoteric tenside include an alkyl betaine type, an alkylamide betaine type, an imidazoline type, an alkylaminosulfone type, an alkylaminocarboxylic acid type, an alkylamide carboxylic acid type, an amide amino acid type, and a phosphoric acid type. It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition.

(Semi-polar surfactant)
Examples of the semi-polar surfactant include lauryldimethylamine oxide and lauric acid amidopropyldimethylamine oxide. It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition.

Examples of the stabilizer include p-toluenesulfonic acid and cumenesulfonic acid. Examples of the form of the aromatic sulfonic acid salt include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), alkanolamine salts (monoethanolammonium salt, diethanolammonium salt, etc.), etc. Can be mentioned. These aromatic sulfonic acids or salts thereof may be used alone or in combination of two or more. As these stabilizers, 0.01 to 10% by mass is preferable with respect to the total mass of the liquid detergent composition.

Examples of the bleaching agent include hydrogen peroxide. The bleaching agent is preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent composition.

Examples of the fluorescent whitening agent include a biphenyl-type fluorescent whitening agent such as 4,4'-bis (2-sulfostilbene) biphenyl disodium salt, and 4,4'-bis ((4-amino-6-morpholino-1). , 3,5-Triazinyl-2) Amino) Stilbene-2, 2'-Disulfonate and other stilbene-type optical brighteners can be mentioned. These fluorescent whitening agents may be used alone or in combination of two or more. These fluorescent whitening agents are preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent composition.

Examples of the soil release agent include at least one repeating unit selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and a polymer having an oxyalkylene unit. Examples of such a polymer include those described in International Publication No. 2017/142012. Examples of commercially available SR agents include the trade name "TexCare SRN-170" manufactured by Clariant AG.

Further, a polymer such as an alkylene oxide adduct of polyalkylene amine can be mentioned. Examples of the alkylene oxide adduct of the polyalkylene amine include those described in International Publication No. 2017/142012 and JP-A-2017-5149667. Examples of commercially available products include the trade name "Sokalan HP20" manufactured by BASF.
In addition, cationized cellulose described in JP-A-2019-90057 can be mentioned.
These soil release agents are preferably 0.1 to 20% by mass based on the total mass of the liquid detergent composition.

Examples of the dispersant include polyacrylic acid and its salt, polymethacrylic acid and its salt, high molecular weight polycarboxylic acid or a salt thereof and the like. These dispersants are preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent composition.

Examples of the defoaming agent include propylene oxide adducts of alcohol (excluding component (B)), fatty acid esters and the like. Examples of the propylene oxide adduct (excluding the component (B)) of the alcohol include monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol with propylene oxide added; ethanediol. Examples thereof include diols such as diols, triols such as glycerin, tetraols such as erythritol, and polyhydric alcohols such as hexaols such as sorbitol, to which propylene oxide is added. The defoaming agent is preferably 0.1 to 10% by mass with respect to the total mass of the liquid detergent composition.

Examples of the fatty acid ester include 2-ethylhexyl 2-ethylhexanoate (also known as 2-ethylhexyl isooctylate, 2H08). 0.01 to 5% by mass is preferable with respect to the total mass of these defoaming agents and liquid detergent compositions.

Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. These pH adjusters may be used alone or in combination of two or more.

Examples of the chelating agent include lactic acid, ethylenediaminetetraacetic acid (EDTA), triethylenetetraacetic acid (TTHA), methylglycine diacetic acid (MGDA), hydroxyiminodisuccinic acid (HIDS), diethylenetriaminepentaacetic acid (DTPA), 1-. Examples thereof include organic phosphonic acids of acids such as hydroxyethylidene-1,1-diphosphonic acid (HEDP) or salts thereof. Examples of the salt form of the chelating agent include sodium, potassium, calcium, magnesium and the like. These chelating agents may be used alone or in combination of two or more. These chelating agents are preferably 0.001 to 10% by mass with respect to the total mass of the liquid detergent composition.

Examples of the alkaline agent include alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.) and the like. These alkaline agents may be used alone or in combination of two or more. These alkaline agents are preferably 0.1 to 5% by mass with respect to the total mass of the liquid detergent composition.

Examples of the texture improving agent include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone. Examples of these silicones include oil type, oil compound type, solution type, emulsion type, self-emulsifying type and the like. These texture improvers may be used alone or in combination of two or more. These texture improvers are preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent composition.

Examples of the antibacterial agent include diclosan, triclosan, and a cationic bactericidal agent of a quaternary ammonium salt (benzalkonium chloride, etc.). These antibacterial agents may be used alone or in combination of two or more. These antibacterial agents are preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, still more preferably 0.1 to 0.5% by mass, based on the total mass of the liquid detergent composition. ..

Examples of preservatives include "Caisson CG" (trade name) manufactured by Dow Chemical Co., Ltd., "Actiside MBS" (trade name) manufactured by So Japan, and "NIPACIDE BIT 20" (trade name) manufactured by Clariant. .. These preservatives may be used alone or in combination of two or more. These preservatives are preferably 0.001 to 1% by mass with respect to the total mass of the liquid detergent composition.

Examples of the antioxidant include BHT (dibutylhydroxytoluene) and BHA (butylhydroxyanisole). These antioxidants may be used alone or in combination of two or more. These antioxidants are preferably 0.01 to 3% by mass with respect to the total mass of the liquid detergent composition.

Examples of the fragrance include a fragrance raw material alone, or a fragrance composition containing a fragrance raw material, a fragrance solvent, a fragrance stabilizer, and the like, and a fragrance usually used in a liquid cleaning agent composition may be blended. it can. Further, a capsule fragrance may be blended. It is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent composition.

Examples of the dye include a quinone dye, a triphenylmethane dye, a xanthene dye, a quinoline dye, a pyrene dye and the like. In this specification, the following "CI" is an abbreviation for Color Index. The structure of each dye is described in the "Legal Dye Handbook" (edited by the Japan Cosmetic Industry Liaison Committee) and the Dye Handbook (edited by the Society of Synthetic Organic Chemistry).

Examples of the quinone dye include C.I. I. Product names such as Solvent Blue 63 (CI Solvent Blue 63, Blue No. 403), Liquitint Blue HP manufactured by Milliken, and Liquitint Blue BL can be mentioned.
Examples of the triphenylmethane dye include Green No. 3 (CI 42053) and the like.
Examples of the quinoline dye include Yellow No. 203 (CI Acid Yellow 3). The dye is preferably 0.1 to 100 mass ppm with respect to the total mass of the liquid detergent composition.

<Physical characteristics>
The pH of the liquid detergent composition at 25 ° C. is preferably 6 to 8, and more preferably 6.5 to 7.5.
The pH of the liquid detergent composition can be adjusted by adding a pH adjuster, if necessary.
The pH is a value measured by a pH meter (product name: HM-30G, manufactured by DKK-TOA CORPORATION) with a measurement target of 25 ° C.

<Manufacturing method>
The liquid detergent composition of the present invention can be produced according to a conventionally known method for producing a liquid detergent composition. For example, each component excluding a pH adjuster is added to a part of water and mixed, and then a pH adjuster is added as necessary to adjust the pH, and then the rest of the water is added to make the total amount 100% by mass. It can be manufactured by setting it to%. The obtained liquid detergent composition is preferably contained in a container such as a squeeze container to prepare a liquid detergent product in a container.

<Washing method>
The method of using the liquid detergent composition of the present invention is, for example, a method of putting the liquid detergent composition into water together with the object to be washed at the time of washing (normal washing), or dissolving the liquid detergent composition in water in advance. Examples thereof include a method of immersing the object to be washed in the liquid detergent aqueous solution prepared in the above. Further, the liquid detergent composition may be directly applied to the object to be washed and left for a certain period of time, and then normal washing may be performed (coating washing).
The liquid detergent composition of the present invention can be suitably used for cleaning textile products. Examples of textile products include clothing, cloths, bedding, curtains and the like.
The material of the textile product is not particularly limited, and may be any of natural fibers such as wool, cotton, silk and hemp, and chemical fibers such as polyester, acrylic, nylon, rayon and polyamide.

Since the liquid detergent composition of the present invention has a high surfactant concentration, it can exhibit a cleaning effect with a small amount of use.
Specifically, the amount of the liquid detergent composition of the present invention used is 3 g or more and less than 10 g with respect to 30 L of water.
The bath ratio (bath ratio = water amount L during washing / clothes amount kg), which is the amount of water per amount of clothes, is preferably 5 or more for a drum-type washing machine and 10 or more for a vertical-type washing machine.
The amount of the liquid detergent composition used in the cleaning treatment is preferably such that the ratio of the total mass (cloth amount) of the object to be washed / the total mass of the liquid detergent composition is 10 to 500, and 10 to 300. It is more preferable that it is, and it is further preferable that it is 10 to 100.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.
The raw materials used in this example are as shown in <Raw materials used> below.

<Raw materials used>
[(A) component]
(A1) Ingredients-LAS: A linear alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms, manufactured by Lion Co., Ltd., trade name "Lypon (registered trademark) LH-200".
(A2) Ingredients-AES: Polyoxyalkylene alkyl ether sulfate (mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average number of moles of EO added 1). ^{A compound in which R 8} in the formula (a-1) is a linear alkyl group having 12 and 14 carbon atoms, k is 1, n is 0, M is sodium, and k is 0 and n is 0 for the entire AES. The ratio of (component (a-0)) is 43% by mass. Synthesized by the method of Preparation Example 1 below.
(A3) Ingredients-AOS: Sodium α-olefin sulfonate, trade name "Liporan LB-840", manufactured by Lion.

[(B) component]
(B1) Ingredients-AE (15EO): 1 mol of primary alcohol (12 carbons by mass ratio / 14 alcohols = 7/3) with 15 mols of ethylene oxide added. In the formula (b-1), R ¹ is an alkyl group having 12 carbon atoms (C12) and an alkyl group having 14 carbon atoms (C14) (by mass ratio C12: C14 = 70:30), R ² is a hydrogen atom, and − ^{A compound in which X- is -O-, the carbon atom of R 1} to which X is bonded is a primary carbon atom, s is 15, t is 0, and u is 0.

AE (7EO): 1 mol of primary alcohol (12 carbons by mass ratio / 14 alcohols = 7/3) with ethylene oxide equivalent to 7 mols added. In the formula (b-1), R ¹ is an alkyl group having 12 carbon atoms (C12) and an alkyl group having 14 carbon atoms (C14) (by mass ratio C12: C14 = 70:30), R ² is a hydrogen atom, and − ^{A compound in which X- is -O-, the carbon atom of R 1} to which X is bonded is a primary carbon atom, s is 7, t is 0, and u is 0.

(B2) Ingredients-Softanol (7EO): 1 mol of secondary alcohol with ethylene oxide equivalent to 7 mol added. In formula (b-1), R ¹ is an alkyl group having 12 to 14 carbon atoms, R ² is a hydrogen atom, -X- is -O-, and the carbon atom of ^{R 1 to which X is bonded is a secondary carbon atom.} A compound in which s is 7, t is 0, and u is 0.

(B3) Ingredients-MEE: Polyoxyethylene fatty acid methyl ester. In formula (b-1), R ¹ is an alkyl group having 11 to 13 carbon atoms, R ² is a methyl group, -X- is -COO-, and the carbon atom of ^{R 1 to which X is bonded is a secondary carbon atom.} A compound in which s is 15, t is 0, and u is 0. Product name "CEAO-90", manufactured by Lion.

[(C) component]
(C1) Ingredients-Phenoxyethanol: Trade name "Phenylglycol", manufactured by Nippon Emulsifier.
(C2) Ingredients-Propylene glycol: Trade name "Propylene glycol", manufactured by Dow Chemical Co., Ltd.
-Butyl carbitol: Diethylene glycol monobutyl ether, manufactured by Nippon Embroidery Co., Ltd.

[(D) component]
-Protease: Trade name "ProgressUno", manufactured by Novozymes Japan.
-Amylase: Product name "Amplify Prime", manufactured by Novozymes Japan.

[(E) component]
・ Soap: Product name "Palm fatty acid", manufactured by NOF CORPORATION.

[Other ingredients]
-Lactic acid: Product name "Lactic acid soda 60E", manufactured by Musashino Chemical Laboratory Co., Ltd.
-PTS: Paratoluenesulfonic acid, trade name "PTS acid", manufactured by Kyowa Hakko Kogyo Co., Ltd.
-Monoethanolamine: Product name "Monoethanolamine", manufactured by Nippon Shokubai.
-Water: Product name "purified water", manufactured by Kanto Chemical Co., Inc.

[Preparation Example 1: Synthesis of AES]
In an autoclave with a capacity of 4 L, 400 g of CO1270 alcohol (a mixture of alcohol having 12 carbon atoms and alcohol having 14 carbon atoms in a mass ratio of 75/25) manufactured by Proctor & Gamble Co., Ltd. as a raw material alcohol and a catalyst for reaction As a result, 0.8 g of a potassium hydroxide catalyst was charged, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised while stirring.
Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, and the reaction was carried out to obtain alcohol ethoxylate.
Gas chromatograph: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25 m × φ0.2 mm × T0.11 μm), As a result of analysis using, the obtained alcohol ethoxylate had an average number of moles of ethylene oxide added of 1.0. In addition, the amount of the compound to which ethylene oxide was not added (the one that finally becomes the component (a-0)) was 43% by mass with respect to the total alcohol ethoxylate obtained.
Next, 237 g of the alcohol ethoxylate obtained above was taken in a 500 mL flask equipped with a stirrer, replaced with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfur) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, this was neutralized with an aqueous sodium hydroxide solution to obtain AES.

<Examples 1 to 18>
Ingredients (A) and (C) were added to a 500 mL beaker according to the blending amounts in Tables 1 to 3, and the mixture was sufficiently stirred with a magnet stirrer (manufactured by MITAMURA KOGYO INC.) To dissolve the component (A). .. Then, the component (E), pTS, and sodium lactate were added, and the mixture was further stirred.
Next, after adding an appropriate amount of monoethanolamine so that the pH at 25 ° C. becomes 7.0, the components (B) and (D) are added, and water is added so that the total amount becomes 100 parts by mass. In addition, a liquid detergent composition was obtained.
Examples 1 to 14 are examples, and examples 15 to 18 are comparative examples.

The cleaning power and enzyme stability of the obtained liquid detergent composition were evaluated by the following evaluation methods. The results are also shown in Tables 1 to 3. The unit of the blending amount in the table is "mass%", which indicates the net conversion amount. Further, the blank of the blending amount means that the component is not blended (blending amount 0% by mass).

However, the appropriate amount of monoethanolamine indicates that the amount is necessary and sufficient to set the pH of the liquid detergent composition to 7.0.
In addition, the blending amount of water is the blending amount calculated by assuming that the amount of monoethanolamine is zero, and the actual blending amount of water is the total blending amount of all the blended components including monoethanolamine ( Mass%) is an amount that is 100 mass%.

<Evaluation method>
[Sebum detergency]
An artificial dirt cloth (manufactured by the Laundry Science Association) prepared by impregnating an oligochemical cloth (unstained cloth) with artificial dirt was cut into a size of 5 x 5 cm and used as a contaminated cloth. A Terg-O-tometer (manufactured by UNITED TESTES TESTING) was used as a cleaning tester. As the cleaning liquid, the liquid detergent composition of each example was added to 900 mL of water (15 ° C., 5 ° C. DH) so as to be 200 ppm, and the mixture was prepared by stirring for 30 seconds.

The cleaning liquid, the above-mentioned 10 contaminated cloths, and the cleaning knitted cloth were put into a cleaning tester, and washed at 120 rpm and 15 ° C. for 10 minutes at a bath ratio of 20 times. Then, it was transferred to a two-tank washing machine (manufactured by Mitsubishi Electric Corporation: product name CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of water for 3 minutes, and air-dried.
The reflectance of the unstained cloth and the contaminated cloth before and after cleaning was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd .: product name SE7700), and the cleaning rate (%) was calculated by the following formula (i).
Cleaning rate (%) = (K / S of contaminated cloth before cleaning-K / S of contaminated cloth after cleaning) / (K / S of contaminated cloth before cleaning-K / S of unclean cloth) x 100・ ・ (I)
In formula (i), K / S is (1-R / 100) ² / (2R / 100) (where R is the reflectance (%) of the unstained cloth and the contaminated cloth before and after cleaning. Show.).

The cleaning rate was calculated for each of the 10 contaminated cloths, and the average value was calculated and used as the cleaning rate of the liquid detergent composition. Then, the detergency was evaluated based on the following criteria, and ◎ and ○ were evaluated as acceptable.
⊚: Cleaning rate is 65% or more.
◯: The cleaning rate is 60% or more and less than 65%.
Δ: The cleaning rate is 55% or more and less than 60%.
X: The cleaning rate is less than 55%.

[Protein detergency]
The cleaning rate (%) was determined in the same manner as the above-mentioned evaluation of sebum detergency, except that a commercially available protein-stained cloth (product name: EMPA117 manufactured by Swissate) was cut into 5 x 5 cm and used as a contaminated cloth. ..
The cleaning rate was calculated for each of the 10 contaminated cloths, and the average value was calculated and used as the cleaning rate of the liquid detergent composition. Then, the detergency was evaluated based on the following criteria, and ◎ and ○ were evaluated as acceptable.
⊚: Cleaning rate is 55% or more.
◯: The cleaning rate is 50% or more and less than 55%.
Δ: The cleaning rate is 40% or more and less than 50%.
X: The cleaning rate is less than 40%.

[Protease stability]
After producing the liquid detergent composition of each example, it was stored at 37 ° C. and 5 ° C. for 4 weeks, respectively. The following protease activities were measured for a liquid detergent composition stored at 37 ° C. for 4 weeks (37 ° C. storage product) and a liquid detergent composition stored at 5 ° C. for 4 weeks (5 ° C. storage product).

1. It was set to 5, and diluted with a 0.05 M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) so that the concentration of milk casein became 0.6%, and used as a protease substrate.
In addition, 0.1 g of each of the 37 ° C. and 5 ° C. preserved products of each example was diluted 25-fold with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water as a sample solution. ..

5 g of the above protease substrate was added to 1 g of the sample solution, and the mixture was stirred with a vortex mixer for 10 seconds and then allowed to stand at 37 ° C. for 30 minutes to proceed with the enzymatic reaction. Then, 5 g of a 0.44 M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.) as an enzyme reaction terminator was added to the solution, and the reaction was stopped by stirring with a vortex mixer for 10 seconds. Then, this solution was allowed to stand at 20 ° C. for 30 minutes, the precipitated unreacted substrate was removed with a 0.45 μm filter, and the filtrate was recovered.
The absorbance (absorbance A) of the recovered filtrate at a wavelength of 275 nm was measured using an ultraviolet visible spectrophotometer UV-160 manufactured by Shimadzu Corporation.

In order to eliminate the influence of absorption other than the target component, separately add 5 g of TCA, which is an enzyme reaction terminator, to 1 g of each sample solution, stir for 10 seconds with a vortex mixer, add 5 g of a protease substrate, and 10 with a vortex mixer. The mixture was stirred for seconds and allowed to stand at 20 ° C. for 30 minutes. Then, the insoluble component was removed with a 0.45 μm filter, and the filtrate was recovered. Then, the absorbance (absorbance B) of the filtrate at a wavelength of 275 nm was measured using UV-160.
The larger the difference between the absorbance A and the absorbance B, the larger the amount of tyrosine (produced by the protease decomposing the protease substrate) in the filtrate.

From the above measurement results of protease activity, the residual protease activity (%) was determined by the following formula (ii).
The absorbance value at 275 nm of each filtrate substituted in the following formula (ii) was used by subtracting 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 residual rate = (absorbance of 37 ° C. preserved product A-37 ° C. preserved product absorbance B) / (5 ° C. preserved product absorbance A-5 ° C. preserved product absorbance B) × 100 ... (ii)

Using the protease activity residual rate (%) as an index, the enzyme stability was evaluated based on the following criteria, and ◎◎, ◎, and ○ were accepted.
◎ ◎: 80% or more.
⊚: 70% or more and less than 80%.
◯: 60% or more and less than 70%.
X: Less than 60%.

[Amylase stability]
After producing the liquid detergent composition of each example, it was stored at 37 ° C. and 5 ° C. for 4 weeks, respectively. The amylase activity shown below was measured for a liquid detergent composition stored at 37 ° C. for 4 weeks (37 ° C. storage product) and a liquid detergent composition stored at 5 ° C. for 4 weeks (5 ° C. storage product).

As the amylase substrate, "Fadevas amylase test 50T" (manufactured by Magle Life Sciences) was used. This is a tablet in which a certain amount of bovine serum albumin is contained in a blue starch polymer which is a substrate. When α-amylase acts, it is hydrolyzed to a blue solution, and its absorbance (620 nm) is measured. Therefore, the amylase activity is required.

In addition, as a buffer solution, 20 g of sodium sulfite, 5 g of potassium dihydrogen phosphate, 10 g of disodium hydrogen phosphate / 12 hydrate, 0.05 g of calcium chloride / dihydrate, and 1 mL of Brij35 (30% aqueous solution) are ion-exchanged. A mixed solution made up to 1 L with water was used.
Further, 0.1 g of each of the 37 ° C.-preserved product and the 5 ° C.-preserved product of each example was diluted 300-fold with the above buffer solution, and this solution was used as a sample solution.

To 1 g of the sample solution, 5 g of the above buffer solution and 1 tablet of "Fadevas amylase test 50T" were added, stirred with a vortex mixer for 10 seconds, and then allowed to stand at 37 ° C. for 30 minutes to proceed with the enzymatic reaction. Then, 1 g of a 1N sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Inc.) as an enzyme reaction terminator was added to the solution, and the reaction was stopped by stirring with a vortex mixer for 10 seconds. Then, this solution was allowed to stand at 37 ° C. for 15 minutes, the insoluble component was filtered through a filter paper, and the filtrate was collected.
The absorbance (absorbance C) of the recovered filtrate at a wavelength of 620 nm was measured using an ultraviolet visible spectrophotometer UV-160 manufactured by Shimadzu Corporation.

In order to eliminate the influence of absorption other than the target component, 1 g of 1N sodium hydroxide aqueous solution, which is an enzyme reaction terminator, was separately added to 1 g of each sample solution, and after stirring with a vortex mixer for 10 seconds, the above buffer solution and "fade" were added. One tablet of "Bass amylase test 50T" was added, stirred with a vortex mixer for 10 seconds, and allowed to stand at 37 ° C. for 15 minutes. Then, the insoluble component was removed with a 0.45 μm filter, and the filtrate was recovered. Then, the absorbance (absorbance D) of the filtrate at a wavelength of 620 nm was measured using UV-160.
The larger the difference between the absorbance C and the absorbance D, the larger the amount of the blue starch polymer hydrolyzed in the sample solution.

From the above measurement results of amylase activity, the residual rate of amylase activity (%) was determined by the following formula (iii).
Residual amylase activity = (absorbance of 37 ° C. preserved product C-absorbance of 37 ° C. preserved product) / (absorbance of 5 ° C. preserved product C-5 ° C. preserved product absorbance D) × 100 ... (iii)

Using the residual rate of amylase activity (%) as an index, the enzyme stability was evaluated based on the following criteria, and ◎◎, ◎, and ○ were accepted.
◎ ◎: 60% or more.
⊚: 50% or more and less than 60%.
◯: 40% or more and less than 50%.
Δ: 30% or more and less than 40%.
X: Less than 30%.

As shown in Tables 1 and 2, Examples 1 to 14 were all excellent in detergency and enzyme stability.
On the other hand, as shown in Table 3, the enzyme stability was low in Examples 15 to 17 in which only one kind of organic solvent was used. Further, in Example 18 in which the total content of the component (A) and the component (B) was low, sufficient detergency could not be obtained.

Claims (3)

Ingredient (A): A non-soap-based anionic surfactant containing one or more selected from the group consisting of the following (A1) component, the following (A2) component, and the following (A3) component.
(B) Ingredients: Nonion surfactant and
Component (C): An organic solvent containing the following component (C1) and the following component (C2),
A liquid detergent composition containing the component (D): an enzyme.
The component (A1) is a linear alkylbenzene sulfonic acid or a salt thereof.
The component (A2) is a polyoxyalkylene alkyl (alkenyl) ether sulfate ester or a salt thereof.
The component (A3) is α-olefin sulfonic acid or a salt thereof.
The component (C1) is phenoxyethanol.
The component (C2) is one or more selected from the group consisting of propylene glycol and butyl carbitol.
It contains one or more selected from the group consisting of the component (A1), the component (A2), and the component (A3), and the total content thereof is 15 with respect to the total mass of the liquid detergent composition. It is more than% by mass and
The total content of the component (C1) and the component (C2) is 10 to 20% by mass with respect to the total mass of the liquid detergent composition.
The total content of the component (A) and the component (B) is 50% by mass or more with respect to the total mass of the liquid detergent composition.
A liquid detergent composition in which the ratio [(A) / (B)] of the mass of the component (A) to the mass of the component (B) is 1.0 to 2.5. The liquid detergent composition according to claim 1, wherein the ratio of the mass of the component (C1) to the mass of the component (C2) [(C1) / (C2)] is 1 to 5.5. The liquid detergent composition according to claim 1 or 2, wherein the content of water is 30% by mass or less with respect to the total mass of the liquid detergent composition.