JP2021105157A - Liquid detergent - Google Patents

Abstract

To provide a liquid detergent that has high detergency and is excellent in high temperature stability and low temperature stability.SOLUTION: A liquid detergent has (A) component: a non-soap-based surfactant, (B) component: at least one solvent selected from polyethylene glycol (b1) with a mass average molecular weight of 400-1500, diethylene glycol monobutyl ether (b2) and a compound represented by general formula (b3), (C) component: an enzyme, (D) component: water. The content of (A) component is 45 mass% or more relative to the total mass of the liquid detergent, the content of (B) component is 3-10 mass% relative to the total mass of the liquid detergent, the content of (C) component is 2 mass% or more relative to the total mass of the liquid detergent and the content of (D) component is 40 mass% or less relative to the total mass of the liquid detergent. (In the general formula (b3), R21, R22 and R23 independently represent a hydrogen atom or a C1-3 alkyl group, R24 is a hydrogen atom or an acetyl group).SELECTED DRAWING: None

Description

The present invention relates to a liquid detergent.

In the field of daily necessities such as liquid detergents for textile products, awareness of environmental load is increasing. For example, by downsizing the container that houses the liquid detergent, we are trying to reduce energy and waste in physical distribution.
With the miniaturization of containers, there is a demand for a liquid detergent having high detergency and a small amount used per washing. In response to these demands, concentrated liquid detergents having an increased concentration of surfactant have been proposed (for example, Patent Documents 1 to 3). In addition, an enzyme may be added to supplement the detergency of the surfactant.

Japanese Unexamined Patent Publication No. 2010-229387 Japanese Unexamined Patent Publication No. 2013-103951 Special Table 2016-520148 Gazette

However, liquid detergents containing a high concentration of surfactant have a lower water content than ordinary liquid detergents, so when concentrated liquid detergents are stored at high or low temperatures, enzymes precipitate. There was a risk of doing so. In particular, it was remarkable when the concentration of the enzyme was mixed at a high concentration.
An object of the present invention is to provide a liquid detergent having high detergency and excellent high temperature stability and low temperature stability.

The present invention has the following aspects.
[1]
Ingredient (A): Non-soap-based surfactant and
Component (B): One or more solvents selected from polyethylene glycol (b1) having a mass average molecular weight of 400 to 1500, diethylene glycol monobutyl ether (b2), and a compound represented by the following general formula (b3).
(C) Ingredient: Enzyme and
(D) Ingredients: water and
Including
The content of the component (A) is 45% by mass or more with respect to the total mass of the liquid detergent.
The content of the component (B) is 3 to 10% by mass with respect to the total mass of the liquid detergent.
The content of the component (C) is 2% by mass or more with respect to the total mass of the liquid detergent.
A liquid detergent having a content of the component (D) of 40% by mass or less based on the total mass of the liquid detergent.

In the general formula (b3), R ²¹ , R ²² and R ²³ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ²⁴ is a hydrogen atom or acetyl group.

[2]
The liquid detergent of [1], wherein the component (A) contains a nonionic surfactant and an anionic surfactant.
[3]
The nonionic surfactant
Compounds represented by the following general formula (a1) and
Compounds represented by the following general formula (a2) and
The liquid detergent of [2].
R ^11- O-[(EO) _s / (A ¹¹ O) _t ]-(EO) _u- R ¹² ... (a1)
(In the general formula (a1), R ¹¹ is a linear hydrocarbon group having 8 to 22 ^{carbon atoms. R 12} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. S is a number of 3 to 25 indicating the average number of EO repetitions. A ¹¹ O represents at least one of PO (oxypropylene group) and BO (oxybutylene group) t. Is a ^{number from 0 to 6 indicating the average number of repetitions of A 11} O. U is a number from 0 to 20 indicating the average number of repetitions of EO.)
R ^13- O-[(EO) _v / (A ¹² O) _w ]-(EO) _x- R ¹⁴ ... (a2)
(In the general formula (a2), R ¹³ is a branched chain hydrocarbon group having 8 to 22 ^{carbon atoms. R 14} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. V is a number of 3 to 25 indicating the average number of EO repetitions. A ¹² O represents at least one of PO (oxypropylene group) and BO (oxybutylene group) w. Is a ^{number from 0 to 6 indicating the average number of repetitions of A 12} O. X is a number from 0 to 20 indicating the average number of repetitions of EO.)
[4]
The liquid detergent according to [2] or [3], wherein the content of the compound represented by the following general formula (a3) is 10% by mass or less with respect to the total mass of the liquid detergent.
R ^15- X-[(EO) _p / (A ¹³ O) _q ]-(EO) _r- R ¹⁶ ... (a3)
(In the general formula (a3), R ¹⁵ is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R ¹⁶ is a hydrogen atom and has 1 to 6 carbon atoms. It is an alkyl group or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. P is a number of 3 to 25 indicating the average number of repetitions of EO. A ¹³ is PO (oxypropylene group) and BO (oxypropylene group). .q representing at least one of oxybutylene groups) .r is a number from 0 to 6 indicating an average repeating number of ^{a 13} O is the number of 0 to 20 which represents the average number of repeating EO.)

According to the present invention, it is possible to provide a liquid detergent having high detergency and excellent high temperature stability and low temperature stability.

[Liquid cleaner]
The liquid detergent of the present invention is a liquid composition containing the following components (A), (B), (C) and (D).

<Ingredient (A)>
The component (A) is a non-soap-based surfactant.
The non-soap-based surfactant is a surfactant that does not contain soap, which will be described later.
Examples of the component (A) include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants.
As the component (A), one kind of surfactant may be used, or two or more kinds of surfactants may be combined.
From the viewpoint of further enhancing the detergency, the component (A) preferably contains a nonionic surfactant and an anionic surfactant.
As the component (A), one or more of a nonionic surfactant and an anionic surfactant and one or more of a cationic surfactant, an amphoteric surfactant and a semi-polar surfactant may be used in combination.

Examples of the nonionic surfactant include a polyoxyalkylene type nonionic surfactant, an alkylphenol, an alkylene oxide adduct such as a fatty acid having 8 to 22 carbon atoms or an amine having 8 to 22 carbon atoms, and a polyoxyethylene polyoxypropylene block copolymer. Fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hardened castor oil, sugar fatty acid ester, N-alkyl Examples thereof include polyhydroxy fatty acid amides and alkyl glycosides.
Among them, a polyoxyalkylene type nonionic surfactant is preferable, and among them, a compound represented by the following general formula (a1) (hereinafter, also referred to as “compound (a1)”) and the following general formula (a2). A compound represented by (hereinafter, also referred to as “compound (a2)”) is more preferable. In particular, from the viewpoint of excellent high temperature stability, low temperature stability, and sebum detergency, the nonionic surfactant preferably contains the compound (a1) and the compound (a2).

The compound (a1) having a linear hydrocarbon group is a compound represented by the following general formula (a1).
R ^11- O-[(EO) _s / (A ¹¹ O) _t ]-(EO) _u- R ¹² ... (a1)
(In the general formula (a1), R ¹¹ is a linear hydrocarbon group having 8 to 22 ^{carbon atoms. R 12} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. S is a number of 3 to 25 indicating the average number of EO repetitions. A ¹¹ O represents at least one of PO (oxypropylene group) and BO (oxybutylene group) t. Is a ^{number from 0 to 6 indicating the average number of repetitions of A 11} O. U is a number from 0 to 20 indicating the average number of repetitions of EO.)

In the general formula (a1), ^{the hydrocarbon group of R 11} has 8 to 22 carbon atoms, preferably 10 to 18, and more preferably 12 to 18. The hydrocarbon group of R ^{11 is linear.} Further, ^{the hydrocarbon group of R 11} may or may not have an unsaturated bond.
^{The carbon atom of R 11} bonded to −O− may be a primary carbon atom or a secondary carbon atom.

When R ¹² is an alkyl group, the number of carbon atoms is 1 to 6, preferably 1 to 3.
When R ¹² is an alkenyl group, the number of carbon atoms is 2 to 6, preferably 2 to 3.
A hydrogen atom is particularly preferable for ^{R 12.}

s is 3 to 25, preferably 5 to 25, more preferably 7 to 20, even more preferably 7 to 18, particularly preferably 9 to 18, and most preferably 11 to 18.
t is 0 to 6, preferably 0 to 3.
u is 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
s + u is preferably 3 to 30, more preferably 5 to 25, even more preferably 5 to 20, particularly preferably 7 to 20, most preferably 9 to 18, and very preferably 11 to 18.

If t is non-zero, that is, if compound (a1) has EO and PO, EO and BO, or EO and PO and BO, then EO and PO, EO in [(EO) _s / (A ¹¹ O) _t ] And BO, or the distribution (arrangement order) of EO, PO, and BO is not particularly limited, and these may be arranged in a block shape or randomly. Further, EO ^{may be bound to "R 11-} O-", or PO or BO may be bound to "R ^11- O-".
If t is non-zero, compound (a1) preferably has EO and PO, or EO and BO.

The compound (a2) having a branched-chain hydrocarbon group is a compound represented by the following general formula (a2).
R ^13- O-[(EO) _v / (A ¹² O) _w ]-(EO) _x- R ¹⁴ ... (a2)
(In the general formula (a2), R ¹³ is a branched chain hydrocarbon group having 8 to 22 ^{carbon atoms. R 14} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. V is a number of 3 to 25 indicating the average number of EO repetitions. A ¹² O represents at least one of PO (oxypropylene group) and BO (oxybutylene group) w. Is a ^{number from 0 to 6 indicating the average number of repetitions of A 12} O. X is a number from 0 to 20 indicating the average number of repetitions of EO.)

In the general formula ^(a2), the carbon number of the hydrocarbon group ^{R 13} is from 8 to 22, preferably 10 to 18, 12 to 18 is more preferable. The hydrocarbon group of R ¹³ is a branched chain. Further, ^{the hydrocarbon group of R 13} may or may not have an unsaturated bond.
Carbon atoms of R ¹³ to bind to -O- may be a primary carbon atom at a secondary carbon atom.

When R ¹⁴ is an alkyl group, the number of carbon atoms is 1 to 6, preferably 1 to 3.
When R ¹⁴ is an alkenyl group, the number of carbon atoms is 2 to 6, preferably 2 to 3.
A hydrogen atom is particularly preferable for ^{R 14.}

v is 3 to 25, preferably 5 to 18, more preferably 5 to 15, further preferably 5 to 10, and particularly preferably 5 to 8.
w is 0 to 6, preferably 0 to 3.
x is 0 to 20, preferably 0 to 15, more preferably 0 to 10.
v + x is preferably 3 to 30, more preferably 5 to 25, further preferably 5 to 20, particularly preferably 5 to 15, most preferably 5 to 10, and very preferably 5 to 8.

If w is non-zero, that is, if compound (a2) has EO and PO, EO and BO, or EO and PO and BO, then EO and PO, EO in [(EO) _v / (A ¹² O) _w ] And BO, or the distribution (arrangement order) of EO, PO, and BO is not particularly limited, and these may be arranged in a block shape or randomly. Further, EO ^{may be bound to "R 13-} O-", or PO or BO may be bound to "R ^13- O-".
If w is non-zero, compound (a2) preferably has EO and PO, or EO and BO.

In general formula (a2), Examples of commercially available hydrocarbon group R ¹³ is a branched chain, for example, the next number of Mitsubishi Chemical Co. Diadol (R) (C13, C is carbon alcohol The numbers are shown below. The same applies hereinafter.), Neodol® (registered trademark) manufactured by Shell (mixture of C12 and C13), Safol® 23 (mixture of C12 and C13) manufactured by Sasol, EXXAL (registered trademark). ) 13 (C13) or the like with 3 to 10 mol of ethylene oxide added;
C13 alcohol obtained by subjecting an alkene having 12 carbon atoms obtained by quantifying butene to the oxo method, to which ethylene oxide equivalent to 3 or 5 mol or equivalent to 7 mol is added (Lutensol (registered trademark)). TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF);
C13 alcohol obtained by subjecting an alkene having 12 carbon atoms obtained by quantifying butene to an alcohol of C13, to which ethylene oxide equivalent to 12 mol or 15 mol is added (Lutensol® TO12, Lutensol). TO15, etc., manufactured by BASF);
C10 alcohol obtained by subjecting pentanol to a garbet reaction to which ethylene oxide equivalent to 9 mol is added (Lutensol XP90, manufactured by BASF);
7 mol of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to a garbet reaction (Lutensol XL70, manufactured by BASF);
Examples thereof include a C10 alcohol obtained by subjecting pentanol to a garbet reaction to which 6 mol of ethylene oxide is added (Lutensol XA60, manufactured by BASF).
Among these, Sasol's trade name Safol23 (branching rate: 50% by mass) (olefin obtained from gasification of coal obtained from alcohol by the oxo method and further hydrogenated) and Shell Chemicals' Co., Ltd. trade name NEODOL 23 (branch ratio: 20 mass%) (n-olefins produced by modified oxo process from those that have been rectified) as in the hydrocarbon group is branched R ¹³ in the general formula (a2) ^{In the case of a "mixture" of a compound of the above and a compound in which the hydrocarbon group of R 11} is linear in the general formula (a1), the compound having a branched chain is designated as compound (a2), while the compound has a linear chain. The thing is defined separately from the compound (a1). The "branching fraction" indicates the ratio (mass%) of the higher alcohol having a branched chain to the total higher alcohol.

The nonionic surfactant may contain a compound represented by the following general formula (a3) (hereinafter, also referred to as “compound (a3)”) as a polyoxyalkylene type nonionic surfactant. R ^15- X-[(EO) _p / (A ¹³ O) _q ]-(EO) _r- R ¹⁶ ... (a3)
(In the general formula (a3), R ¹⁵ is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R ¹⁶ is a hydrogen atom and has 1 to 6 carbon atoms. It is an alkyl group or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. P is a number of 3 to 25 indicating the average number of repetitions of EO. A ¹³ is PO (oxypropylene group) and BO (oxypropylene group). .q representing at least one of oxybutylene groups) .r is a number from 0 to 6 indicating an average repeating number of ^{a 13} O is the number of 0 to 20 which represents the average number of repeating EO.)

In the general formula ^(a3), the carbon number of the hydrocarbon group ^{R 15} is 7 to 21, preferably from 9 to 19, 11 to 19 is more preferable. Hydrocarbon group R ¹⁵ may be the straight-chain may be branched. Further, the hydrocarbon group for R ¹⁵ is may have an unsaturated bond or may not have.
Carbon atoms of ^{R 15} to bind to -X- is a secondary carbon atom.

When R ¹⁶ is an alkyl group, the number of carbon atoms is 1 to 6, preferably 1 to 3.
When R ¹⁶ is an alkenyl group, the number of carbon atoms is 2 to 6, preferably 2 to 3.
R ¹⁶ is particularly preferably an alkyl group.

p is 3 to 25, preferably 5 to 20, more preferably 10 to 18, and even more preferably 12 to 18.
q is 0 to 6, preferably 0 to 3.
r is 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
p + r is preferably 5 to 30, more preferably 5 to 25, even more preferably 5 to 20, and particularly preferably 10 to 20.

If q is non-zero, that is, if compound (a3) has EO and PO, EO and BO, or EO and PO and BO, then EO and PO, EO in [(EO) _p / (A ¹³ O) _q ] And BO, or the distribution (arrangement order) of EO, PO, and BO is not particularly limited, and these may be arranged in a block shape or randomly. Further, EO ^{may be bound to "R 15} -X-", or PO or BO may be bound to "R ¹⁵ -X-".
If q is non-zero, compound (a3) preferably has EO and PO, or EO and BO.

Examples of the anionic surfactant include linear alkylbenzene sulfonic acid or a salt thereof (LAS), α-olefin sulfonic acid or a salt thereof (AOS), linear or branched alkyl sulfate ester or a salt thereof (AS), and the like. Polyoxyalkylene alkyl (alkenyl) ether sulfate ester or its salt (AES), alcan sulfonic acid having an alkyl group or its salt, α-sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS), hydroxyalcan Sulfonic acid or its salt (HAS), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, acylaminocarboxylic acid or Carboxylic acid type anionic surfactant such as the salt; alkyl phosphate ester or salt thereof, polyoxyalkylene alkyl phosphate ester or salt thereof, polyoxyalkylene alkylphenyl phosphate ester or salt thereof, glycerin fatty acid ester monophosphate ester or Examples thereof include a phosphate ester type anionic surfactant such as the salt thereof.
Examples of the salt form of the anionic surfactant include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.), and the like. Can be mentioned.
These anionic surfactants may be used alone or in combination of two or more.
As the anionic surfactant, LAS, AOS, AS and AES are preferable, and among them, LAS and AES are more preferable from the viewpoint of further enhancing the detergency. The liquid detergent preferably contains at least AES, more preferably both LAS and AES.

The polyoxyalkylene alkyl (alkenyl) ether sulfate ester or a salt thereof (AES) is represented by the following general formula (a4).
R ^17- O-[(EO) _m / (PO) _n ] -SO ₃ ^- M ⁺ ... (a4)
(In the general formula (a4), R ¹⁷ 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. EO is It is an oxyethylene group. PO is an oxypropylene group. M is a number of 0.1 or more representing the average number of repetitions of EO. N is a number of 0 to 6 representing the average number of repetitions of PO. (EO) _m / (PO) _n ] indicates that there is no limitation on the sequence order of EO and PO, and M ⁺ is a countercation.)

The AES preferably has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and has an average of 1 to 5 mol of alkylene oxide added. The alkyl group or alkenyl group preferably has 10 to 20 carbon atoms, more preferably 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. Specific examples thereof include a dodecyl group, a tridecylic group, and a tetradecyl group.

m 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 0 to 6, preferably 0 to 3, and more preferably 0.
m + n is preferably more than 0, more preferably 1 to 5.

When n is not 0, that is, when AES has EO and PO, the distribution (arrangement order) of EO and PO in _{[(EO) m} / (PO) _{n] is not particularly limited, and these are arranged in a block shape.} It may be arranged randomly. Further, to EO may be attached to ^"R 17 -O-" may be coupled PO is the "-O- ^R 17".
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.
The compound of m = 0 and n = 0 in the above formula (a4) is preferably contained in an amount of 35 to 55% by mass with respect to the total mass of the compound represented by the formula (a4).

Examples of the cationic surfactant include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitate dimethylaminopropylamide, stearate dimethylaminopropylamide, and the like. Long-chain aliphatic amide alkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleate dimethylaminopropylamide or salts thereof; aliphatic ester alkyl tertiary amines such as palmitate ester propyl dimethylamine and stearate ester propyl dimethylamine. Or salts thereof; diethanolaminopropylamide palmitate, diethanol aminopropylamide stearate; alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridinium salt and other quaternary products. Examples of the salt form of the cationic surfactant include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.), and the like. Can be mentioned.
These cationic surfactants may be used alone or in combination of two or more.

Examples of amphoteric tenside agents include alkyl betaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric tenside. Can be mentioned.
These amphoteric surfactants may be used alone or in combination of two or more.

Examples of the semi-polar surfactant include alkylamine oxides and alkylamide propyldimethylamine oxides.
These semi-polar surfactants may be used alone or in combination of two or more.

The content of the component (A) is 45% by mass or more, preferably 50% by mass or more, based on the total mass of the liquid detergent. The content of the component (A) is preferably 75% by mass or less, more preferably 70% by mass or less, based on the total mass of the liquid detergent. That is, the content of the component (A) is preferably 45 to 75% by mass, more preferably 50 to 70% by mass, based on the total mass of the liquid detergent.
When the content of the component (A) is at least the above lower limit value, sufficient detergency can be obtained.

When the component (A) contains a nonionic surfactant, the content of the nonionic surfactant is preferably 20 to 65% by mass, more preferably 30 to 60% by mass, based on the total mass of the liquid detergent. When the content of the nonionic surfactant is at least the above lower limit value, the sebum detergency can be ensured. When the content of the nonionic surfactant is not more than the above upper limit value, compounding stability can be ensured.
When the nonionic surfactant contains the compound (a1), the content of the compound (a1) is preferably 15 to 50% by mass, more preferably 20 to 40% by mass, and 25 to 50% by mass with respect to the total mass of the liquid detergent. 40% by mass is more preferable. When the content of the compound (a1) is at least the above lower limit value, high temperature stability and low temperature stability can be ensured. When the content of the compound (a1) is not more than the above upper limit value, the sebum detergency can be ensured.
When the nonionic surfactant contains the compound (a2), the content of the compound (a2) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and 10 to 10% by mass with respect to the total mass of the liquid detergent. 20% by mass is more preferable. When the content of the compound (a2) is at least the above lower limit value, the sebum detergency can be ensured. When the content of the compound (a2) is not more than the above upper limit value, high temperature stability and low temperature stability can be ensured.
The content of the compound (a3) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the liquid detergent, and further, the liquid detergent does not substantially contain the compound (a3). preferable. Here, "substantially not contained" means that the compound (a3) is not positively blended except for those which are unintentionally contained. When the content of the compound (a3) is not more than the above upper limit value, the generation of precipitates can be further suppressed when the liquid detergent is stored at a high temperature (for example, 50 ° C. or higher), and the high temperature stability and the low temperature stability are improved. Improve more.
The mass ratio represented by the compound (a1) / compound (a2) (hereinafter, also referred to as “a1 / a2 ratio”) is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4.

When the component (A) contains an anionic surfactant, the content of the anionic surfactant is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and 5 to 5% by mass with respect to the total mass of the liquid detergent. 15% by mass is more preferable. When the content of the anionic surfactant is at least the above lower limit value, the protein detergency can be ensured. When the content of the anionic surfactant is not more than the above upper limit value, compounding stability can be ensured.
When the anionic surfactant contains LAS, the content of LAS is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and 1 to 5% by mass with respect to the total mass of the liquid detergent. % Is more preferable. When the LAS content is equal to or higher than the above lower limit, recontamination of clothing is prevented. When the content of LAS is not more than the above upper limit value, compounding stability can be ensured.
When the anionic surfactant contains AES, the content of AES is preferably 3 to 15% by mass, more preferably 5 to 13% by mass, still more preferably 5 to 10% by mass, based on the total mass of the liquid detergent. .. When the AES content is at least the above lower limit, the sebum detergency can be ensured. When the content of AES is not more than the above upper limit value, appearance stability can be ensured.
The mass ratio represented by AES / LAS (hereinafter, also referred to as “AES / LAS ratio”) is preferably 0.3 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

The mass ratio represented by the nonionic surfactant / anion surfactant (hereinafter, also referred to as “nonion / anion ratio”) is preferably more than 1, more preferably 1.2 or more, still more preferably 1.5 or more. 2 or more is particularly preferable. The nonionic / anion ratio is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less. That is, the nonionic / anion ratio is preferably more than 1, preferably 1.2 to 10, more preferably 1.5 to 7, and even more preferably 2 to 5. If the nonion / anion ratio exceeds the above lower limit, the sebum detergency can be ensured.

The mass ratio represented by the compound (a1) / anionic surfactant (hereinafter, also referred to as “a1 / anion ratio”) is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4. The mass ratio represented by the compound (a2) / anionic surfactant (hereinafter, also referred to as “a2 / anion ratio”) is preferably 0.1 to 5, more preferably 0.5 to 5, and 1-3. More preferred.
The mass ratio represented by (compound (a1) + compound (a2)) / anionic surfactant (hereinafter, also referred to as “(a1 + a2) / anion ratio”) is preferably 1 to 15, more preferably 1 to 10. , 1 to 6 are more preferable.

When the component (A) contains a cationic surfactant, the content of the cationic surfactant is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent. When the component (A) contains an amphoteric surfactant, the content of the amphoteric surfactant is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent.
When the component (A) contains a semi-polar surfactant, the content of the semi-polar surfactant is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent. preferable.

<Ingredient (B)>
The component (B) is polyethylene glycol having a mass average molecular weight of 400 to 1500 (hereinafter, also referred to as “(compound (b1)”)), diethylene glycol monobutyl ether (also known as butyl carbitol) (hereinafter, “(compound (b2))”. ”And a compound represented by the following general formula (b3) (hereinafter, also referred to as“ (compound (b3) ”)).

In the general formula (b3), R ²¹ , R ²² and R ²³ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ²⁴ is a hydrogen atom or acetyl group.

Examples of the compound (b3) include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, and 3-methoxy-2-methylbutano. -L, 3-Methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy-1-propylbutano -L, 3-Methoxybutyl acetate, 3-Methoxy-3-methylbutyl acetate, 3-Methoxy-3-ethylbutyl acetate, 3-Methoxy-3-propylbutyl acetate, 3-Methoxy-2-methylbutyl acetate, 3 -Methoxy-2-ethylbutyl acetate, 3-methoxy-2-propylbutyl acetate, 3-methoxy-1-methylbutyl acetate, 3-methoxy-1-ethylbutyl acetate, 3-methoxy-1-propylbutyl acetate, etc. Can be mentioned. Of these, 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2 methylbutanol, 3-methoxy-1-methylbutanol, and 3-methoxy-3-methylbutyl acetate are preferable, and 3-methoxy- 3-Methylbutanol is more preferred.

The mass average molecular weight of compound (b1) is 400 to 1500, preferably 400 to 1200, more preferably 600 to 1200, and even more preferably 800 to 1200. When the mass average molecular weight of polyethylene glycol is at least the above lower limit, the generation of precipitates can be suppressed and the low temperature stability is improved when the liquid detergent is stored at a low temperature (for example, 0 ° C. or lower). When the mass average molecular weight of polyethylene glycol is not more than the above upper limit value, the appearance stability when stored at a high temperature (for example, 50 ° C. or higher) or a low temperature is improved.
The mass average molecular weight of polyethylene glycol is a value calculated by gel permeation chromatography (GPC) using methanol as a solvent based on a calibration curve of polyethylene glycol.

As the component (B), at least one of compound (b1) and compound (b2) is particularly preferable from the viewpoint of further improving high temperature stability.
When two or more components (B) are used in combination, "Compound (b1) and Compound (b2)", "Compound (b1) and Compound (b3)", "Compound (b2) and Compound (b3)", "Compound (b2) and Compound (b3)", " The combination of "compound (b1), compound (b2) and compound (b3)" is preferable, and the combination of "compound (b1) and compound (b2)" is more preferable.

The content of the component (B) is 3 to 10% by mass, preferably 5 to 10% by mass, based on the total mass of the liquid detergent.
When the content of the component (B) is within the above range, the low temperature stability is improved. In particular, when the content of the component (B) is not more than the above upper limit value, the high temperature stability is improved.

The mass ratio represented by the component (A) / component (B) (hereinafter, also referred to as “A / B ratio”) is preferably 4.5 to 25, more preferably 5 to 20, and further 5 to 15. Preferably, 5 to 10 is particularly preferable. When the A / B ratio is equal to or higher than the above lower limit value, the appearance stability at high temperature is improved. When the A / B ratio is not more than the above upper limit value, the appearance stability at low temperature is improved.
The content of the total surfactant (total of the component (A) + soap) is preferably 45.5% by mass or more, more preferably 46% by mass or more, based on the total mass of the liquid detergent. Further, it is preferably 85% by mass or less, more preferably 83% by mass or less, based on the total mass of the liquid detergent. That is, the content of the total surfactant is preferably 45.5 to 85% by mass, more preferably 46 to 83% by mass, based on the total mass of the liquid detergent.

The mass ratio represented by the compound (a1) / (B) component (hereinafter, also referred to as “a1 / B ratio”) is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 6.
The mass ratio represented by the compound (a2) / (B) component (hereinafter, also referred to as “a2 / B ratio”) is preferably 0.5 to 10, more preferably 0.5 to 5, and 0.5. ~ 3 is more preferable. The mass ratio represented by the (compound (a1) + compound (a2)) / (B) component (hereinafter, also referred to as “(a1 + a2) / B ratio”) is preferably 1 to 15, preferably 1 to 10. Preferably, 2 to 8 are even more preferable.

<Ingredient (C)>
The component (C) is an enzyme.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase and the like.
Enzymes are generally marketed as preparations containing enzymes (enzyme preparations). When preparing a liquid detergent, the enzyme is usually formulated in the form of an enzyme preparation.

As the protease, a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease, is preferable.
Examples of the protease-containing preparation (protease preparation) include trade names Subinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase UltraLalaseAlseAlseAlseAlseAlseAlseAlseAlseAlseAl8L, Esla16L, which can be obtained from Novozymes. 5L, Subtilisin 2.5L, Subtilisin Ultra 2.5L, Subtilisin Ultra 2.5XL, Coronase 48L, Protease Evity 48L, Protease Uno101L;

Examples of the amylase-containing preparation (amylase preparation) include trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amano Core available from Novozymes, and Amano Corporation. Examples thereof include the trade name Pluranase Amano available from Enzyme; and the trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase-containing preparation (lipase preparation) include the trade names Lipex 100L and Lipase 100L available from Novozymes.
Examples of the cellulase-containing preparation (cellulase preparation) include the trade names Carezyme 4500L, Carezyme Premium 4500L, Endolase 5000L, and Cellclean 4500T available from Novozymes.
Examples of the mannanase-containing preparation (mannanase preparation) include the trade names Mannaway 4L and Mannaway 200L available from Novozymes.

These enzyme preparations may be used alone or in combination of two or more.
As the component (C), protease, amylase, and mannanase are preferable, and protease and amylase are more preferable, from the viewpoint of further improving detergency.
The combined use of protease and amylase, the combined use of protease and mannanase, the combined use of amylase and mannanase, the combined use of protease, amylase and mannanase are preferable, and the combined use of protease and amylase is more preferable.

The content of the component (C) is 2% by mass or more, preferably more than 2% by mass, more preferably 2.5% by mass or more, still more preferably 3% by mass or more, based on the total mass of the liquid detergent. The content of the component (C) is preferably 5% by mass or less, more preferably 4.5% by mass or less, based on the total mass of the liquid detergent. That is, the content of the component (C) is preferably 2 to 5% by mass, more preferably more than 2% by mass to 55% by mass or less, and more preferably 2.5 to 4.5% by mass with respect to the total mass of the liquid detergent. Is more preferable, and 3 to 4.5% by mass is further preferable.
When the content of the component (C) is at least the above lower limit value, sufficient detergency can be obtained.
The content of the component (C) is the mass as an enzyme preparation.

When the component (C) contains a protease, the content of the protease is preferably 1 to 5% by mass, more preferably 2 to 3% by mass, based on the total mass of the liquid detergent. When the protease content is at least the above lower limit, the protein detergency is improved. When the protease content is not more than the above upper limit value, the appearance stability at high temperature is improved.
When the component (C) contains amylase, the content of amylase is preferably 0.1 to 3% by mass, more preferably 0.1 to 2% by mass, based on the total mass of the liquid detergent. When the content of amylase is at least the above lower limit value, the detergency is further improved. When the content of amylase is not more than the above upper limit value, the appearance stability at high temperature is improved.
When the component (C) contains mannanase, the content of mannanase is preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass, based on the total mass of the liquid detergent. When the content of mannanase is at least the above lower limit value, the detergency is further improved. When the content of mannanase is not more than the above upper limit value, the appearance stability at high temperature is improved. It is preferable to add mannanase in terms of removing the biofilm.
It may contain protease, amylase and other enzymes with respect to the total mass of the liquid detergent, and may be blended so that the total content thereof is 2% by mass or more, and the total content of protease and amylase is 2% by mass. It is more preferable that the mixture is blended so as to be% or more.

The mass ratio represented by protease / amylase (hereinafter, also referred to as “protease / amylase ratio”) is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 6.
The mass ratio represented by the component (A) / component (C) (hereinafter, also referred to as “A / C ratio”) is preferably 10 to 30, more preferably 10 to 25, and even more preferably 10 to 20.
The mass ratio represented by the component (B) / component (C) (hereinafter, also referred to as “B / C ratio”) is preferably 0.6 to 5, more preferably 0.6 to 4, and 1 to 4 Is even more preferable.
The mass ratio represented by the compound (a1) / (C) component (hereinafter, also referred to as “a1 / C ratio”) is preferably 3 to 25, more preferably 5 to 25, and even more preferably 5 to 15.
The mass ratio represented by the compound (a2) / (C) component (hereinafter, also referred to as “a2 / C ratio”) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

<Ingredient (D)>
The component (D) is water.
The water is not particularly limited, and examples thereof include purified water, distilled water, ion-exchanged water, and tap water.
These waters may be used alone or in combination of two or more.

The content of the component (D) is 40% by mass or less, preferably 37% by mass or less, and more preferably 35% by mass or less, based on the total mass of the liquid detergent. The content of the component (D) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, based on the total mass of the liquid detergent. That is, the content of the component (D) is preferably 10 to 40% by mass, more preferably 15 to 37% by mass, and even more preferably 20 to 35% by mass with respect to the total mass of the liquid detergent.
When the content of the component (D) is not more than the above upper limit value, the liquid detergent can be made compact.

<Arbitrary ingredient>
The liquid detergent may contain components (arbitrary components) other than the components (A), (B), (C) and (D) as long as the effects of the present invention are not impaired. ..
Optional ingredients include, for example, soap, enzyme stabilizer, hydrotropic agent, pH adjuster, bleach, fluorescent whitening agent, soil release agent, dispersant, defoaming agent (however, component (A) and soap are excluded. ), Chelating agents, texture improvers, antibacterial agents, preservatives, antioxidants, fragrances, pigments and the like.
The total content of each component in the liquid detergent is 100% by mass.

Soap is a higher fatty acid or a salt thereof. "Higher fatty acid" means a fatty acid having 8 to 22 carbon atoms. If the liquid detergent contains soap, the rinsing property (defoaming property) is improved.
As the soap, any soap used in general liquid detergents can be used, and among them, fatty acids having 8 to 22 carbon atoms or salts thereof are preferable. The number of carbon atoms of the fatty acid is preferably 10 to 20, more preferably 12 to 18.
The fatty acid constituting the soap may be a saturated fatty acid, an unsaturated fatty acid, or a mixture of a saturated fatty acid and an unsaturated fatty acid. Examples of fatty acids include stearic acid, linoleic acid, oleic acid, and coconut fatty acids.
Examples of the salt form of the fatty acid include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.) and the like.
These soaps may be used alone or in combination of two or more.
The content of the soap is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, still more preferably 1.2 to 7% by mass, based on the total mass of the liquid detergent. When the soap content is at least the above lower limit value, the rinsing property is further improved, and when it is at least the above upper limit value, the liquid stability is excellent.

Examples of the enzyme stabilizer include boric acid, borax, formic acid or a salt thereof, benzoic acid, lactic acid or a salt thereof, calcium chloride, calcium sulfate and other calcium salts.
These enzyme stabilizers may be used alone or in combination of two or more.
The content of the enzyme stabilizer is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, based on the total mass of the liquid detergent.

Examples of the hydrotrope agent include paratoluenesulfonic acid or a salt thereof, cumenesulfonic acid or a salt thereof, benzoate, urea and the like.
These hydrotropes may be used alone or in combination of two or more.
The content of the hydrotrope agent is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent.

Examples of the pH adjuster include inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), sodium hydroxide, potassium hydroxide, alkanolamines (monoethanolamine, diethanolamine, etc.), ammonia, and the like.
These pH adjusters may be used alone or in combination of two or more.

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

Examples of the fluorescent whitening agent include biphenyl-type fluorescent whitening agents such as 4,4'-bis (2-sulfostilbene) biphenyl disodium salt; 4,4'-bis ((4-amino-6-morpholino-). Examples thereof include stilbene-type fluorescent whitening agents such as 1,3,5-triazinyl-2) amino) stilbene-2,2'-disulfonate.
These fluorescent whitening agents may be used alone or in combination of two or more.
The content of the fluorescent whitening agent is preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent.

Examples of the soil release agent (SR 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 soil release agents include the trade name "TexCare SRN-170" manufactured by Clariant AG.
Examples of the soil release agent include polymers such as an alkylene oxide adduct of polyalkyleneamine.
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.
Examples of the soil release agent include cationized cellulose described in JP-A-2019-90057.
These soil release agents may be used alone or in combination of two or more.
The content of the soil release agent is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent. It is preferable to add a soil release agent from the viewpoint of preventing recontamination.

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 may be used alone or in combination of two or more.
The content of the dispersant is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent.

Examples of the defoaming agent include propylene oxide adducts of alcohol (excluding component (A)), fatty acid esters, and the like.
Examples of alcohol propylene oxide adducts (excluding component (A)) include monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol with propylene oxide added; Examples thereof include diols such as ethanediol, triols such as glycerin, tetraols such as erythritol, and polyhydric alcohols such as hexaols such as sorbitol with propylene oxide added.
Specific examples of the fatty acid ester include 2-ethylhexyl 2-ethylhexanoate (also known as 2-ethylhexyl isooctylate, 2H08).
These antifoaming agents may be used alone or in combination of two or more.
The content of the defoaming agent is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent.

Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), triethylenetetraacetic acid (TTHA), methylglycine diacetic acid (MGDA), hydroxyiminodisuccinic acid (HIDS), diethylenetriaminepentaacetic acid (DTPA), and 1-hydroxyethylidene. Examples thereof include organic phosphonic acids of acids such as 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.
The content of the chelating agent is preferably 0.001 to 10% by mass with respect to the total mass of the liquid detergent.

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.
The content of the texture improver is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent.

Examples of antibacterial agents include diclosan, triclosan, quaternary ammonium salts (cationic fungicides such as benzalkonium chloride, bis- (2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8- Examples include oxyquinoline and polylysine.
These antibacterial agents may be used alone or in combination of two or more.
The content of the antibacterial agent is 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.

Examples of the preservative include a product name "Caisson CG" manufactured by Dow Chemical Co., Ltd., a product name "Actiside MBS" manufactured by Saw Japan Co., Ltd., and a product name "NIPACIDE BIT 20" manufactured by Clariant Co., Ltd.
These preservatives may be used alone or in combination of two or more.
The content of the preservative is preferably 0.001 to 1% by mass with respect to the total mass of the liquid detergent.

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

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 as a liquid detergent can be blended. Further, the capsule fragrance may be added to the liquid detergent.
The content of the fragrance is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent.

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 content of the dye is preferably 0.1 to 100 mass ppm with respect to the total mass of the liquid detergent.

<Physical characteristics>
(PH)
The pH of the liquid detergent at 25 ° C. is preferably 4 to 10, preferably 5 to 9, and more preferably 6 to 8.
The pH of the liquid detergent can be adjusted by adding a pH adjuster, if necessary. The pH in the present specification is a value measured by a pH meter (manufactured by DKK-TOA CORPORATION, product name "HM-30G") with a measurement target of 25 ° C.

(viscosity)
The viscosity of the liquid detergent at 25 ° C. is preferably 10 to 2000 mPa · s, more preferably 10 to 100 mPa · s, and even more preferably 10 to 500 mPa · s.
The viscosity of the liquid detergent is a value measured under the following conditions using a B-type viscometer.
<< Measurement conditions >>
-Rotor: No. 3 rotor (when less than 1000 mPa · s) or No. 4 rotor (when 1000 mPa · s or more).
-Rotation speed: 60 rpm.
-Measurement temperature: 25 ° C.
-Viscosity reading: 30 seconds after the start of rotation of the rotor.

<Manufacturing method>
The method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced according to a conventional method.
For example, the liquid detergent is a mixture of the above-mentioned component (A), component (B), component (C), a part of component (D), and if necessary, any component other than the pH adjuster. Then, if necessary, the pH is adjusted to a predetermined pH using a pH adjusting agent, and then the remaining component (D) is mixed to produce the product. When adjusting to a predetermined pH using a pH adjusting agent, it is preferable to add the component (C) after adjusting the pH.

<How to use>
Examples of the method of using the liquid detergent include a method of putting the liquid detergent into the inlet of the liquid detergent of the washing machine and then operating the washing machine, and a method of adding the liquid detergent to water together with the object to be washed at the time of washing. Method, method of immersing the object to be washed in a washing solution prepared by dissolving the liquid detergent in water in advance, applying the liquid detergent directly to the object to be washed, for example, leaving it for 3 minutes to 24 hours, and then usually Examples include a method of washing.

It is also preferable to use a washing machine having a detergent automatic injection function that has been put into practical use in recent years. The detergent automatic charging function is a function for automatically charging detergent from a tank containing detergent to a washing tub via a charging pipe. A measuring means such as a syringe pump is provided in the middle of the charging pipe so that a fixed amount set according to the amount of laundry can be transferred from the tank to the washing tub.

By using the automatic detergent injection function, not only the labor of weighing can be saved, but also it is possible to prevent the liquid cleaning agent from adhering to the hand or spilling and soiling the washing machine and the surroundings during weighing.
Further, since the liquid detergent of the present invention is a concentrated type, the amount used per washing may be very small, about 10 mL. It is difficult to accurately measure such a small amount of liquid detergent with a cap or the like, and the amount of liquid tends to be insufficient or excessive. If the automatic detergent addition function is used, even a small amount of liquid detergent can be accurately weighed, so that it is easy to exert sufficient cleaning power and waste due to overuse can be avoided, which is preferable.

It is also preferable to use an automatic dispenser that can automatically discharge a predetermined amount of liquid. Even when an automatic dispenser is used, it is preferable because even a small amount of liquid detergent can be accurately weighed, so that sufficient cleaning power can be easily exerted and waste due to overuse can be avoided.
Some automatic dispensers are commercially available that use an infrared sensor or the like to automatically discharge without touching a switch or the like. If such an automatic dispenser is used, the liquid detergent can be weighed simply by holding the container in one hand, and the effect of reducing the burden on the user is great.

Further, when using an automatic dispenser, it is also preferable to receive the liquid detergent discharged into the soft container and put the soft container into the washing machine as it is. As a result, the entire amount of the discharged liquid detergent can be reliably dissolved in the cleaning liquid.
Examples of the material of the soft container that can be directly put into the washing machine include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane and the like.

Examples of objects to be washed include textile products such as clothing (clothing), cloths, towels, sheets, and curtains. The material of the textile product is not particularly limited, and may be any of natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide.
When the liquid detergent is dissolved in water and used, it is preferably diluted 5 to 5000 times (volume basis), for example.
The bath ratio (mass of washing liquid at the time of washing / mass of clothes), 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.
Regarding the amount of the liquid detergent used in the cleaning treatment, the ratio of the total mass (cloth amount) of the object to be washed / the total mass of the liquid detergent is preferably 10 to 500, more preferably 10 to 300, and 10 to 100. Is even more preferable.
Liquid cleaning agents are suitable as cleaning agents for textile products.

<Effect>
The liquid detergent of the present invention is a concentrated type because it contains 45% by mass or more of the component (A), 2% by mass or more of the component (C), and the content of the component (D) is 40% by mass or less. Yes, it has excellent detergency. In addition, since the liquid detergent of the present invention contains 3 to 10% by mass of the component (B), although it is a concentrated type, it is difficult for a precipitate to form even when stored at a high temperature or a low temperature, and it is stable at a high temperature and a low temperature. Excellent in sex. In addition, the liquid detergent of the present invention is also excellent in solubility in cold water.
Since the liquid detergent of the present invention is a concentrated type, the amount used per washing is small. In addition, the container for accommodating the liquid detergent can be miniaturized, and energy reduction and waste reduction in physical distribution can be achieved.

A washing machine equipped with an automatic detergent charging function tends to raise the temperature inside the tank containing the detergent when the clothes are dried. Since the liquid cleaning agent of the present invention is excellent in high-temperature stability, it is unlikely that a precipitate will be formed even if it is stored in the tank of a washing machine equipped with an automatic detergent charging function. The liquid detergent of the present invention is less likely to form a precipitate when stored not only at a high temperature but also at a low temperature. Therefore, it is possible to prevent the inside of the injection pipe and the syringe pump of the washing machine having the automatic detergent addition function from being blocked by the sediment.

Further, since the liquid detergent of the present invention is unlikely to generate a precipitate even when stored at a high temperature or a low temperature, it is possible to prevent the nozzle and the discharge mechanism from being blocked by the precipitate even when an automatic dispenser is used. .. Therefore, it is also possible to install and use a washing machine and an automatic dispenser in a place where the temperature fluctuates drastically, such as a balcony.

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 and the evaluation methods in Examples and Comparative Examples are as follows.

[Raw materials used]
<Ingredient (A)>
A-1 (Linear AE (12EO)): Polyoxyethylene alkyl ether (manufactured by Lion, trade name "LMAL-90", in the general formula (a1), R ¹¹ is a linear alkyl having 12 carbon atoms. It is a group (C12) and a linear alkyl group (C14) having 14 carbon atoms (C12: C14 = 75: 25 by mass ratio), and ^{the carbon atom of R 11} bonded to the oxygen atom is a primary carbon atom. A ^{compound (a1) in which R 12} is a hydrogen atom, s is 12, t is 0, and u is 0).
A-2 (branched AE (7EO)): Polyoxyethylene alkyl ether (alcohol having 13 carbon atoms to which ethylene oxide equivalent to 7 mol is added. In the general formula (a2), R ¹³ is a branched chain having 13 carbon atoms. ^{The carbon atom of R 13} which is an alkyl group in the form of an oxygen atom is a primary carbon atom, R ¹⁴ is a hydrogen atom, v is 7, w is 0, and x is 0. A compound (a2), which is synthesized by the following synthetic method).
A-3 (Linear AE (15EO)): Polyoxyethylene alkyl ether (manufactured by Lion, trade name "LMAO-90", in the general formula (a1), R ¹¹ is a linear alkyl having 12 carbon atoms. It is a group (C12) and a linear alkyl group (C14) having 14 carbon atoms (C12: C14 = 75: 25 by mass ratio), and ^{the carbon atom of R 11} bonded to the oxygen atom is a primary carbon atom. A ^{compound (a1) in which R 12} is a hydrogen atom, s is 15, t is 0, and u is 0).
A-4 (MEE): Polyoxyethylene fatty acid methyl ester (manufactured by Lion, trade name "CEAO-90", in general formula (a3), R ¹⁵ is an alkyl group having 11 to 13 carbon atoms, and R ¹⁶ There is a methyl group, -X- is -COO-, carbon atoms ^{R 15} is bonded to X is a secondary carbon atom, p is 15, q is 0, at r is 0 A compound (a3).).
A-5 (LAS): A linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Rypon LH-200").
-A-6 (AES): Polyoxyethylene alkyl ether sulfate (natural alcohol (trade name "CO-1270" manufactured by P & G) to which ethylene oxide equivalent to 1 mol is added. In general formula (a4), R ¹⁷ is a linear alkyl group (C12) having 12 carbon atoms and a linear alkyl group (C14) having 14 carbon atoms (C12: C14 = 75: 25 by mass ratio), and m is 1. The ratio of the compound in which n is 0, M is sodium, m is 0 and n is 0 with respect to the whole A-6 is 43% by mass. Synthesized by the following synthesis method).

(Synthesis of A-2)
400 g of EXXAL (registered trademark) 13 manufactured by Sasol and 3.33 g of a 30 mass% NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Next, after dehydration at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, while stirring the reaction solution, 1145 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blow tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize the reaction product so that the pH of the 1% by mass aqueous solution of the reaction product became about 7, and A-2 was obtained. rice field.

(Synthesis of A-6)
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. The amount of the compound to which ethylene oxide was not added was 43% by mass based on 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 A-6.

<Ingredient (B)>
B-1: Polyethylene glycol (manufactured by Lion, trade name "PEG # 1000-L60", mass average molecular weight 1000, compound (b1)).
B-2: Butyl carbitol (manufactured by Nippon Emulsorium, trade name "diethylene glycol monobutyl ether", compound (b2)).
-B-3: 3-Methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd., trade name "Solfit", in general formula (b3), R ²¹ is a methyl group, and R ²² , R ²³ and R ²⁴ are hydrogen. A compound that is an atom (b3).).

<Component (B'): Comparison component of component (B)>
-B'-1: Propylene glycol (manufactured by Chuo Kasei Co., Ltd., trade name "Cosmetic Propylene Glycol").
-B'-2: Phenoxyethanol (manufactured by Nippon Emulsifier Co., Ltd., trade name "Phenylglycol").
-B'-3: Ethanol (manufactured by Japan Alcohol Trading Co., Ltd., trade name "specific alcohol 95 degree synthesis").
B'-4: 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol (manufactured by Solvey, trade name "Augeo Clean Multi").
-B'-5: Polyethylene glycol (manufactured by Junsei Chemical Co., Ltd., trade name "PEG # 200", mass average molecular weight 200).

<Ingredient (C)>
-C-1: Protease (manufactured by Novozymes, trade name "Progress Uno101L").
-C-2: Amylase (manufactured by Novozymes, trade name "Amplify Prime").
-C-3: Mannanase preparation, manufactured by Novozymes, trade name "Manaway 200L".

<Ingredient (D)>
-D-1: Water (ion-exchanged water).

<Arbitrary ingredient>
-Palm fatty acid: Soap (manufactured by NOF Corporation, trade name "palm fatty acid").
-Sodium lactate: Enzyme stabilizer (manufactured by Musashino Chemical Research Institute, trade name "sodium lactate 60E").
-Paratoluenesulfonic acid: Hydrotrope (manufactured by Kyowa Hakko Kirin Co., Ltd., trade name "PTS acid").
-Dichloromethane (4,4'-dichloro-2-hydroxydiphenyl ether) (manufactured by BASF, trade name "TINOSAN HP100").
-SR agent: Soil release polymer (manufactured by Clariant, trade name "TexCare SR N-170").
-Sodium hydroxide: pH adjuster (manufactured by Toagosei Co., Ltd., trade name "sodium hydroxide").
-Monoethanolamine: pH adjuster (manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine").

[Evaluation method]
<Evaluation of detergency>
An artificial dirt cloth (manufactured by the Laundry Science Association) made by impregnating an oil-based cloth (unstained cloth) with artificial dirt was cut into a size of 5 cm 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, a liquid detergent was added to 900 mL of water (25 ° C., 5 ° C. DH) so as to have a concentration of 200 ppm, and the mixture was stirred 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 25 ° 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 (25 ° C., 5 ° DH) 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 Kogyo Co., Ltd., product name "SE7700 type"), and the cleaning rate (%) was calculated from 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 = (1-R / 100) ² / (2R / 100). R is the reflectance (%).)
The cleaning rate (%) was calculated for 10 contaminated cloths, the average value was calculated, and the cleaning power was evaluated according to the following evaluation criteria. I and II are accepted.
<< Evaluation Criteria >>
I: The average cleaning rate is 60% or more.
II: The average cleaning rate is 55% or more and less than 60%.
III: The average cleaning rate is less than 55%.

<Evaluation of high temperature stability>
100 mL of liquid detergent was added to a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. After placing in a constant temperature bath at 50 ° C. and storing for 30 days in this state, the appearance of the liquid was visually observed, and the high temperature stability was evaluated according to the following evaluation criteria. I and II are accepted. << Evaluation Criteria >>
I: No deposit is found on the bottom of the glass bottle.
II: Precipitate is observed at the bottom of the glass bottle, but the precipitate disappears (dissolves) by gently shaking the glass bottle.
III: A precipitate is observed at the bottom of the glass bottle, and the precipitate does not disappear even if the glass bottle is shaken lightly.

<Evaluation of low temperature stability>
100 mL of liquid detergent was added to a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, the liquid was placed in a constant temperature bath at −5 ° C. and stored for 30 days, and then the appearance of the liquid was visually observed, and the low temperature stability was evaluated according to the following evaluation criteria. I and II are accepted. << Evaluation Criteria >>
I: No precipitate is found at the bottom of the glass bottle, and the liquid is fluid.
II: Precipitate is observed at the bottom of the glass bottle, but the precipitate disappears (dissolves) by gently shaking the glass bottle.
III: A precipitate is observed at the bottom of the glass bottle, and the precipitate does not disappear even if the glass bottle is shaken lightly, or gels or becomes cloudy immediately after the production of the liquid detergent.

[Examples 1 to 14, Comparative Examples 1 to 9]
A magnet stirrer (manufactured by MITAMURA KOGYO INC.) Is charged into a 500 mL beaker with the types and amounts (% by mass) of the component (A) and the component (B) or component (B') shown in Tables 1 to 4. The component (A) was dissolved in the component (B) or the component (B'). Then, the coconut fatty acid, paratoluenesulfonic acid, and sodium lactate in the blending amounts (% by mass) shown in Tables 1 to 4 are added, and the component (D) is adjusted to 94% by mass or 96 parts by mass in the total amount. Was added and stirred well. After adding a pH adjuster (sodium hydroxide and monoethanolamine) so that the pH at 25 ° C. becomes 7.0, the components (C) of the types and blending amounts (mass%) shown in Tables 1 to 4 are added. The mixture was added and the remaining component (D) was added so that the total amount was 100 parts by mass to obtain a liquid detergent. The pH and viscosity of the liquid detergent are shown in Tables 1 to 4.
The cleaning power, high temperature stability and low temperature stability of the obtained liquid detergent were evaluated. These results are shown in Tables 1-4.
The blending amount of the enzyme (component (C)) in the table is the blending amount as a pharmaceutical product. The blending amounts of other components in the table are net conversion values. In addition, the ingredients whose blending amount is not listed in the table are not blended. Further, "balance" in Tables 1 to 4 is an amount required to adjust the pH of the liquid detergent at 25 ° C. to 7.0.

As shown in Tables 1 and 2, the liquid detergents of each example had high detergency and were excellent in high temperature stability and low temperature stability.
On the other hand, as shown in Tables 3 and 4, the liquid detergents of Comparative Examples 1 to 5 containing the component (B') instead of the component (B) were inferior in high temperature stability or low temperature stability.
The liquid detergent of Comparative Example 6 containing no component (B) was inferior in low temperature stability.
The liquid detergent of Comparative Example 7 in which the content of the component (B) was 12% by mass was inferior in high temperature stability and low temperature stability.
The liquid detergent of Comparative Example 8 in which the content of the component (C) was 0.5% by mass was inferior in detergency.
The liquid detergent of Comparative Example 9 in which the content of the component (A) was 40% by mass and the content of the component (D) was 46% by mass was inferior in detergency.

Claims (4)

Ingredient (A): Non-soap-based surfactant and
Component (B): One or more solvents selected from polyethylene glycol (b1) having a mass average molecular weight of 400 to 1500, diethylene glycol monobutyl ether (b2), and a compound represented by the following general formula (b3).
(C) Ingredient: Enzyme and
(D) Ingredients: water and
Including
The content of the component (A) is 45% by mass or more with respect to the total mass of the liquid detergent.
The content of the component (B) is 3 to 10% by mass with respect to the total mass of the liquid detergent.
The content of the component (C) is 2% by mass or more with respect to the total mass of the liquid detergent.
A liquid detergent having a content of the component (D) of 40% by mass or less based on the total mass of the liquid detergent.

(In the general formula (b3), R ²¹ , R ²² and R ²³ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ²⁴ is a hydrogen atom or acetyl group.) The liquid detergent according to claim 1, wherein the component (A) contains a nonionic surfactant and an anionic surfactant. The nonionic surfactant
Compounds represented by the following general formula (a1) and
Compounds represented by the following general formula (a2) and
2. The liquid detergent according to claim 2.
R ^11- O-[(EO) _s / (A ¹¹ O) _t ]-(EO) _u- R ¹² ... (a1)
(In the general formula (a1), R ¹¹ is a linear hydrocarbon group having 8 to 22 ^{carbon atoms. R 12} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. S is a number of 3 to 25 indicating the average number of EO repetitions. A ¹¹ O represents at least one of PO (oxypropylene group) and BO (oxybutylene group) t. Is a ^{number from 0 to 6 indicating the average number of repetitions of A 11} O. U is a number from 0 to 20 indicating the average number of repetitions of EO.)
R ^13- O-[(EO) _v / (A ¹² O) _w ]-(EO) _x- R ¹⁴ ... (a2)
(In the general formula (a2), R ¹³ is a branched chain hydrocarbon group having 8 to 22 ^{carbon atoms. R 14} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. V is a number of 3 to 25 indicating the average number of EO repetitions. A ¹² O represents at least one of PO (oxypropylene group) and BO (oxybutylene group) w. Is a ^{number from 0 to 6 indicating the average number of repetitions of A 12} O. X is a number from 0 to 20 indicating the average number of repetitions of EO.) The liquid detergent according to claim 2 or 3, wherein the content of the compound represented by the following general formula (a3) is 10% by mass or less with respect to the total mass of the liquid detergent.
R ^15- X-[(EO) _p / (A ¹³ O) _q ]-(EO) _r- R ¹⁶ ... (a3)
(In the general formula (a3), R ¹⁵ is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R ¹⁶ is a hydrogen atom and has 1 to 6 carbon atoms. It is an alkyl group or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. P is a number of 3 to 25 indicating the average number of repetitions of EO. A ¹³ is PO (oxypropylene group) and BO (oxypropylene group). .q representing at least one of oxybutylene groups) .r is a number from 0 to 6 indicating an average repeating number of ^{a 13} O is the number of 0 to 20 which represents the average number of repeating EO.)