JP2024064153A - Liquid detergent composition for fiber products - Google Patents

Abstract

To provide a liquid detergent composition for fiber products that contains an enzyme, can exhibit high detergency with a small amount of use, and excels in enzymic stability, color tone stability at high temperatures, and low-temperature stability.SOLUTION: A liquid detergent composition for fiber products contains (A) a nonionic surfactant, (B) a non-soap-based anionic surfactant, (C) a compound represented by formula 1 (where R1, R2, R3 independently represent a hydrogen atom, a C1-6 alkyl group, or a methoxy group), (D) an enzyme, and (E) water. The content of component (E) is 40 mass% or less, and the mass ratio of the content of component (A) to the content of component (B), expressed as (A)/(B), is 1 or more.SELECTED DRAWING: None

Description

The present invention relates to a liquid detergent composition for textile products.

There is growing awareness of the environmental impact of liquid detergents for textile products. For example, containers for liquid detergents are being made smaller to reduce energy consumption and waste during distribution. As containers become smaller, there is a demand for liquid detergents that not only have high cleaning power but also require less use per wash. In response to this demand, concentrated liquid detergents have been proposed that reduce the water content and increase the concentration of surfactants (for example, Patent Document 1).

JP 2010-229387 A

Concentrated liquid cleaners often contain enzymes to achieve high cleaning power with less usage.
However, enzymes generally have the problem that they are easily inactivated when the water content in the liquid detergent decreases.

In recent years, transparent plastic containers are often used for liquid detergents from the viewpoints of environmental friendliness and design, so it is important that the color tone does not change easily. In particular, color tone changes may occur when liquid detergents are placed in high temperature conditions, and it is required to be able to suppress such color tone changes.
Furthermore, concentrated liquid detergents have the problem that they tend to gel or solidify in low temperature environments (e.g., 5° C.) in winter.

The present invention aims to provide a liquid detergent composition for textile products that contains an enzyme, can exert a high cleaning power with a small amount of use, and has good enzyme stability, color stability at high temperatures, and low temperature stability.

The present invention has the following aspects.
[1] A composition comprising: (A) a nonionic surfactant; (B) a non-soap anionic surfactant; (C) a compound represented by the following formula 1; (D) an enzyme; and (E) water;
The content of the (E) component is 40 mass% or less,
A liquid detergent composition for textile products, in which (A)/(B), which represents the mass ratio of the content of the (A) component to the content of the (B) component, is 1 or more.

(In the formula, R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methoxy group.)
[2] The liquid detergent composition for textile products described in [1], further comprising (F) monoethanolamine.

According to the present invention, a liquid detergent composition for textile products is obtained that contains an enzyme, exhibits high detergency even with a small amount used, has good enzyme stability, shows little color change at high temperatures, and has good low-temperature stability.

The liquid detergent composition for textile products of the present invention (hereinafter, also simply referred to as liquid detergent) is a composition containing the components (A), (B), (C), (D), and (E) described below. It is preferable that it further contains the component (F).
The following description of the components may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range including the numerical values before and after "to" as the lower and upper limits.

<Component (A)>
The component (A) is a nonionic surfactant.
The component (A) may be used alone or in combination of two or more types.

Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.

The nonionic surfactant preferably includes a polyoxyalkylene type nonionic surfactant.
Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (a1) (hereinafter also referred to as "compound (a1)"), a compound represented by the following general formula (a2) (hereinafter also referred to as "compound (a2)"), and a compound represented by the following general formula (a3) (hereinafter also referred to as "compound (a3)"):

[Compound (a1)]
The compound (a1) is a polyoxyalkylene-type nonionic surfactant having a linear hydrocarbon group.
R ¹¹ -O-[(EO) _s /(A ¹¹ O) _t ]-(EO) _u -R ¹² ... (a1)
(In 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 from 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 A ¹¹ O repetitions. u is a number from 0 to 20 indicating the average number of EO repetitions.)

In general formula (a1), the number of carbon atoms in the hydrocarbon group of R ¹¹ is 8 to 22, preferably 10 to 18, and more preferably 12 to 18. The hydrocarbon group of R ¹¹ is linear. In addition, the hydrocarbon group of R ¹¹ may or may not have an unsaturated bond.
The carbon atom of R ¹¹ that is bonded to --O-- may be a primary or secondary carbon atom.

When R ¹² is an alkyl group, it has 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms.
When R ¹² is an alkenyl group, it has 2 to 6 carbon atoms, and preferably 2 to 3 carbon atoms.
R ¹² is particularly preferably a hydrogen atom.

s is 3 to 25, and from the viewpoint of excellent effect of improving enzyme stability, 5 to 25 is preferable, 7 to 20 is more preferable, 7 to 18 is further more preferable, and 7 to 15 is particularly preferable.
t is an integer of 0 to 6, preferably 0 to 3.
u is an integer of 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
In view of the excellent effect of improving the enzyme stability, s+u is preferably 3-30, more preferably 5-25, even more preferably 5-20, particularly preferably 7-20, and most preferably 7-15.

When t is not 0, that is, when compound (a1) has EO and PO, EO and BO, or EO, PO and BO, there is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO and BO in [(EO)s/(A ¹¹ O)t], and they may be arranged in a block form or randomly. In addition, EO may be bonded to "R ¹¹ -O-", or PO or BO may be bonded to "R ¹¹ -O-".
When t is not 0, the compound (a1) preferably has EO and PO, or EO and BO.

[Compound (a2)]
The compound (a2) is a polyoxyalkylene-type nonionic surfactant having a branched hydrocarbon group.
R ¹³ —O—[(EO) _v /(A ¹² O) _w ]—(EO) _x —R ¹⁴ ... (a2)
(In 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 from 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 A ¹² O repetitions. x is a number from 0 to 20 indicating the average number of EO repetitions.)

In general formula (a2), the number of carbon atoms in the hydrocarbon group of R ¹³ is 8 to 22, preferably 10 to 18, and more preferably 12 to 18. The hydrocarbon group of R ¹³ is a branched chain. In addition, the hydrocarbon group of R ¹³ may or may not have an unsaturated bond.
The carbon atom of R ¹³ that is bonded to --O-- may be a primary or secondary carbon atom.

When R ¹⁴ is an alkyl group, it has 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms.
When R ¹⁴ is an alkenyl group, it has 2 to 6 carbon atoms, and preferably 2 to 3 carbon atoms.
R ¹⁴ is particularly preferably a hydrogen atom.

v is from 3 to 25, and from the viewpoint of excellent effect of improving enzyme stability, it is preferably from 5 to 18, more preferably from 7 to 15, and even more preferably from 7 to 12.
w is an integer of 0 to 6, preferably 0 to 3.
x is an integer of 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
In view of the excellent effect of improving the enzyme stability, v+x is preferably 3 to 30, more preferably 5 to 25, even more preferably 5 to 20, particularly preferably 7 to 15, and most preferably 7 to 12.

When w is not 0, that is, when compound (a2) has EO and PO, EO and BO, or EO, PO and BO, there is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO and BO in [(EO) _v /(A ¹² O) _w ], and they may be arranged in a block form or randomly. In addition, EO may be bonded to "R ¹³ -O-", or PO or BO may be bonded to "R ¹³ -O-".
When w is not 0, the compound (a2) preferably has EO and PO, or EO and BO.

Examples of commercially available products of compound (a2) include DIADOLL (registered trademark) manufactured by Mitsubishi Chemical Corporation (C13, the number after C indicates the carbon number of the alcohol, the same applies below), Neodol (registered trademark) manufactured by Shell (a mixture of C12 and C13), Safol (registered trademark) 23 (a mixture of C12 and C13), and EXXAL (registered trademark) 13 (C13) manufactured by Sasol, which are products in which 3 to 10 moles of ethylene oxide are added to alcohol;
an alkene having 12 carbon atoms, obtained by trimerizing butene, is subjected to an oxo process to obtain a C13 alcohol, to which 3, 5, or 7 moles of ethylene oxide are added (Lutensol (registered trademark) TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF);
A product in which 12 or 15 moles of ethylene oxide are added to a C13 alcohol obtained by subjecting an alkene having 12 carbon atoms, obtained by trimerizing butene, to an oxo process (Lutensol (registered trademark) TO12, Lutensol TO15, etc., manufactured by BASF);
A product in which 9 moles of ethylene oxide is added to a C10 alcohol obtained by subjecting pentanol to the Guerbet reaction (Lutensol XP90, manufactured by BASF);
A product in which 7 moles of ethylene oxide is added to a C10 alcohol obtained by subjecting pentanol to the Guerbet reaction (Lutensol XL70, manufactured by BASF);
Examples of such a copolymer include a C10 alcohol obtained by subjecting pentanol to a Guerbet reaction, to which 6 moles of ethylene oxide are added (Lutensol XA60, manufactured by BASF).
Among these, in the case of a "mixture" of a compound in which the hydrocarbon group of R 13 in general formula (a2) is a branched chain, such as Safol 23 (branching ratio: 50 mass%) manufactured by Sasol (an alcohol obtained by subjecting olefins obtained from coal gasification to the Oxo process, which is then hydrogenated) and Neodol ²³ (branching ratio: 20 mass%) manufactured by Shell Chemicals (an alcohol produced from ^n- olefins by an improved Oxo process and then rectified), the compound having a branched chain is defined as compound (a2), while the compound having a straight chain is defined as compound (a1). The "branching ratio" refers to the proportion (mass%) of higher alcohols having a branched chain relative to the total higher alcohols.

[Compound (a3)]
The compound (a3) is a polyoxyalkylene type nonionic surfactant having --COO-- or --CONH--.
R ¹⁵ -X-[(EO) _p /(A ¹³ O) _q ]-(EO) _r -R ¹⁶ ... (a3)
(In 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, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. p is a number from 3 to 25 indicating the average number of EO repetitions. A ¹³ represents at least one of PO (oxypropylene group) and BO (oxybutylene group). q is a number from 0 to 6 indicating the average number of A ¹³ O repetitions. r is a number from 0 to 20 indicating the average number of EO repetitions.)

In general formula (a3), the number of carbon atoms in the hydrocarbon group of R ¹⁵ is 7 to 21, preferably 9 to 19, and more preferably 11 to 19. The hydrocarbon group of R ¹⁵ may be linear or branched. In addition, the hydrocarbon group of R ¹⁵ may or may not have an unsaturated bond.
The carbon atom of R ¹⁵ that is bonded to --X-- may be a primary or secondary carbon atom.

When R ¹⁶ is an alkyl group, it has 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms.
When R ¹⁶ is an alkenyl group, it has 2 to 6 carbon atoms, and preferably 2 to 3 carbon atoms.
R ¹⁶ is particularly preferably an alkyl group.

p is 3 to 25, and is preferably 5 to 20, more preferably 10 to 18, and even more preferably 12 to 18, in that it is excellent in the effect of improving the enzyme stability.
q is an integer of 0 to 6, preferably 0 to 3.
r is an integer of 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
In view of the excellent effect of improving the enzyme stability, p+r is preferably 5-30, more preferably 5-25, even more preferably 5-20, and particularly preferably 10-20.

When q is not 0, that is, when compound (a3) has EO and PO, EO and BO, or EO, PO and BO, there is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO and BO in [(EO) _p /(A ¹³ O) _q ], and they may be arranged in a block form or randomly. In addition, EO may be bonded to "R ¹⁵ -X-", or PO or BO may be bonded to "R ¹⁵ -X-".
When q is not 0, the compound (a3) preferably has EO and PO, or EO and BO.

From the viewpoint of excellent low-temperature stability, the (A) component preferably contains one or both of the compounds (a1) and (a3) and the compound (a2), and more preferably contains the compound (a1) and the compound (a2).

<Component (B)>
Component (B) is a non-soap anionic surfactant. The term "non-soap anionic surfactant" refers to an anionic surfactant other than higher fatty acids or salts thereof (so-called soaps).
The component (B) may be used alone or in combination of two or more types.

Examples of the component (B) include carboxylic acid type anionic surfactants such as linear alkylbenzenesulfonic acid or a salt thereof (LAS), α-olefinsulfonic acid or a salt thereof (AOS), linear or branched alkyl sulfate or a salt thereof (AS), polyoxyalkylene alkyl(alkenyl)ether sulfate or a salt thereof (AES), alkanesulfonic acid having an alkyl group or a salt thereof, α-sulfofatty acid ester or a salt thereof, internal olefinsulfonic acid or a salt thereof (IOS), hydroxyalkanesulfonic acid or a salt thereof (HAS), alkyl ether carboxylic acid or a salt thereof, polyoxyalkylene ether carboxylic acid or a salt thereof, alkylamide ether carboxylic acid or a salt thereof, alkenylamide ether carboxylic acid or a salt thereof, and acylamino carboxylic acid or a salt thereof; and phosphate ester type anionic surfactants such as alkyl phosphate ester or a salt thereof, polyoxyalkylene alkyl phosphate ester or a salt thereof, polyoxyalkylene alkylphenyl phosphate ester or a salt thereof, and glycerin fatty acid ester monophosphate ester or a 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.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.).

As anionic surfactants, LAS, AOS, AS, and AES are preferred, and among them, LAS and AES are more preferred from the viewpoint of further enhancing cleaning power. It is preferable that the liquid detergent contains at least AES, and it is more preferable that it contains both LAS and AES.

The polyoxyalkylene alkyl(alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (b1).
R ¹⁷ —O—[(EO) _m /(PO) _n ]—SO ₃ ⁻ M ⁺ (b1)
(In general formula (b1), 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 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 order of arrangement of EO and PO, and M ⁺ is a counter cation.)

AES preferably has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, to which an average of 1 to 5 moles of alkylene oxide is added. The number of carbon atoms in the alkyl or alkenyl group is preferably 10 to 20, and more preferably 12 to 14. In particular, linear alkyl groups having 10 to 20 carbon atoms are preferred, and linear alkyl groups having 12 to 14 carbon atoms are more preferred. Specific examples include dodecyl groups, tridecyl groups, and tetradecyl groups.

m is preferably from 0.1 to 5, more preferably from 0.1 to 3, further preferably from 0.5 to 2, and particularly preferably from 0.5 to 1.5.
n is an integer of 0 to 6, preferably 0 to 3, and more preferably 0.
Preferably, m+n is greater than 0, and 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 they may be arranged in a block form or randomly. In addition, EO may be bonded to "R ¹⁷ -O-", and PO may be bonded to "R ¹⁷ -O-".
Examples of the method for arranging EO and PO in a block form include a method of introducing ethylene oxide and then propylene oxide, a method of introducing propylene oxide and then ethylene oxide, and a method of introducing ethylene oxide, then propylene oxide, and further introducing ethylene oxide.
The compound of formula (b1) where m=0 and n=0 is preferably contained in an amount of 35 to 55 mass % based on the total mass of the compound represented by formula (b1).

<Component (C)>
Component (C) is a compound represented by the following formula 1, which is phenylboronic acid or a derivative of phenylboronic acid. R ¹ , R ² , and R ³ in formula 1 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methoxy group.
The component (C) may be used alone or in combination of two or more types.

Examples of the (C) component include phenylboronic acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-ethylphenylboronic acid, 3-ethylphenylboronic acid, 4-ethylphenylboronic acid, 2-propylphenylboronic acid, 3-propylphenylboronic acid, 4-propylphenylboronic acid, 2-isopropylphenylboronic acid, 3-isopropylphenylboronic acid, 4-isopropylphenylboronic acid, 2-butylphenylboronic acid, 3-butylphenylboronic acid, 4-butylphenylboronic acid, 2-pentylphenylboronic acid, 3-pentylphenylboronic acid, 4-pentylphenylboronic acid, 2-hexylphenylboronic acid, 3-hexylphenylboronic acid, 4-hexylphenylboronic acid, 1,2-dimethylphenylboronic acid, 1,3-dimethylphenylboronic acid, 2,3-dimethylphenylboronic acid, 2-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, and 4-methoxyphenylboronic acid.
Of these, phenylboronic acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-ethylphenylboronic acid, 3-ethylphenylboronic acid, 4-ethylphenylboronic acid, 2-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, and 4-methoxyphenylboronic acid are preferred.
Furthermore, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, and 4-methoxyphenylboronic acid are more preferable, and 2-methylphenylboronic acid, 3-methylphenylboronic acid, and 4-methylphenylboronic acid are most preferable.

<Component (D)>
Component (D) is an enzyme.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, pectinase, etc. One type of enzyme may be used, or two or more types may be used in combination.
These enzymes are generally commercially available as preparations containing the enzymes (enzyme preparations), and when preparing liquid detergents, they are usually incorporated in the form of enzyme preparations.

The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as a serine protease.
Examples of preparations containing proteases (protease preparations) include products available from Novozymes under the trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Coronase Evity 48L, and Progress Uno101L; trade names Purafect L, Purafect OX, Properase L, etc. available from Genencor.

Examples of preparations containing amylase (amylase preparations) include those available from Novozymes under the trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, and Amplify Prime; those available from Genencor under the trade name Maxamyl; those available from Amano Enzyme under the trade name Pullulanase Amano; and those available from Seikagaku Corporation under the trade name DB-250.

Examples of preparations containing lipase (lipase preparations) include products available from Novozymes under the trade names Lipex 100L and Lipolase 100L.

Examples of preparations containing cellulase (cellulase preparations) include those available from Novozymes under the trade names Carezyme 4500L, Carezyme Premium 4500L, Endorase 5000L, and Cellclean 4500T.

Examples of preparations containing mannanase (mannanase preparations) include products available from Novozymes under the trade names Mannaway 4L and Mannaway 200L.

Examples of preparations containing pectinase (pectinase preparations) include Pectawash, Pectaway, XPect, and the like available from Novozymes.
These enzyme preparations may be used alone or in combination of two or more.

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

<Component (F)>
The component (F) is monoethanolamine (also known as 2-aminoethanol). Monoethanolamine contributes to improving low temperature stability.

<Other optional ingredients>
The liquid detergent may contain, as optional components other than the above components (A) to (F), components known in the field of liquid detergents for textile products, provided that the effects of the present invention are not impaired.
Examples of optional components include higher fatty acids or salts thereof (so-called soaps), other surfactants other than component (A) and component (B) (excluding higher fatty acids or salts thereof), enzyme stabilizers other than component (C) (for example, sodium lactate, etc.), hydrotropic agents (for example, aromatic sulfonic acids or salts thereof, etc.), chelating agents, detergent builders, stabilizers, alkali agents other than monoethanolamine (for example, alkanolamines such as diethanolamine and triethanolamine, etc.), metal ion scavengers, texture improvers such as silicone, preservatives, fluorescent agents, dye transfer inhibitors, pearlescent agents, antioxidants, antibacterial agents, general-purpose dyes or pigments as colorants, emulsifiers, fragrances, pH adjusters, and the like.

Examples of surfactants other than the components (A) and (B) include cationic surfactants, semi-polar surfactants, and amphoteric surfactants.
Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines other than monoethanolamine, and ammonia.

<Content>
The content of component (A) is preferably 20 to 60 mass %, more preferably 30 to 50 mass %, and most preferably 35 to 45 mass %, based on the total mass of the liquid detergent.
When it is equal to or higher than the lower limit of the above range, the enzyme stability is excellent, and when it is equal to or lower than the upper limit of the above range, the low-temperature stability is excellent.

The content of compound (a1) is preferably 1 to 55 mass %, more preferably 10 to 50 mass %, and most preferably 20 to 45 mass %, based on the total mass of the liquid detergent. When the content is equal to or more than the lower limit of the above range, the enzyme stability is excellent, and when the content is equal to or less than the upper limit of the above range, the low-temperature stability is excellent.
The content of compound (a2) is preferably 1 to 40 mass %, more preferably 10 to 35 mass %, and most preferably 15 to 30 mass %, based on the total mass of the liquid detergent. When the content is equal to or more than the lower limit of the above range, the enzyme stability is excellent, and when the content is equal to or less than the upper limit of the above range, the low-temperature stability is excellent.
The content of compound (a3) is preferably 1 to 55 mass %, more preferably 10 to 50 mass %, and most preferably 20 to 45 mass %, based on the total mass of the liquid detergent. When the content is equal to or more than the lower limit of the above range, the enzyme stability is excellent, and when the content is equal to or less than the upper limit of the above range, the low-temperature stability is excellent.

In the liquid detergent, (a1+a3)/(a2), which represents the mass ratio of the total content of compound (a1) and compound (a3) to the content of compound (a2), is preferably 0.1 or more, more preferably 0.1 to 10, even more preferably 1 to 10, and most preferably 1 to 5. When it is equal to or greater than the lower limit of the above range, the enzyme stability is excellent. When it is equal to or less than the upper limit, the sebum cleansing power is excellent, and a small amount of use can provide high cleansing power.

The content of component (B) is preferably from 2 to 31 mass %, more preferably from 4 to 26 mass %, and most preferably from 6 to 21 mass %, based on the total mass of the liquid detergent.
When it is equal to or more than the lower limit of the above range, the enzyme stability is excellent, and when it is equal to or less than the upper limit of the above range, the color stability at high temperatures is excellent.

The LAS content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and most preferably 10 to 20% by mass, based on the total mass of the liquid detergent. When the content is equal to or more than the lower limit of the above range, the enzyme stability is excellent, and when the content is equal to or less than the upper limit, the color stability at high temperatures is excellent.
The content of AES is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and most preferably 10 to 20% by mass, based on the total mass of the liquid detergent. When the content is equal to or more than the lower limit of the above range, the enzyme stability is excellent, and when the content is equal to or less than the upper limit of the above range, the low-temperature stability is excellent.

In liquid detergents, LAS/AES, which represents the mass ratio of LAS content to AES content, is preferably 0.1 or more, more preferably 0.1 to 20, even more preferably 0.5 to 20, and most preferably 0.5 to 10. When it is equal to or greater than the lower limit of the above range, low-temperature stability is excellent. When it is equal to or less than the upper limit, color stability at high temperatures is excellent.

In liquid detergents, (A)/(B), which represents the mass ratio of the content of component (A) to the content of component (B), is preferably 1 or more, more preferably 1 to 40, even more preferably 2.5 to 25, and most preferably 3.5 to 15. When it is equal to or greater than the lower limit of the above range, the enzyme stability is excellent. When it is equal to or less than the upper limit, the low-temperature stability is excellent.

The total content of components (A), (B) and other surfactants (hereinafter also referred to as "total surfactant amount") is preferably 40% by mass or more, more preferably 40 to 70% by mass, and most preferably 40 to 60% by mass, based on the total mass of the liquid detergent. If it is equal to or greater than the lower limit of the above range, it has excellent sebum cleansing power and can exert high cleansing power with a small amount used. If it is equal to or less than the upper limit, it has excellent color stability at high temperatures.

The content of component (C) is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.7% by mass, and most preferably 0.1 to 0.5% by mass, based on the total mass of the liquid detergent. If it is equal to or greater than the lower limit of the above range, the enzyme stability is excellent, and if it is equal to or less than the upper limit, low-temperature stability is less likely to decrease.

In liquid detergents, (A)/(C), which represents the mass ratio of the content of component (A) to the content of component (C), is preferably 70 or more, more preferably 70 to 120, and most preferably 80 to 100. When it is equal to or greater than the lower limit of the above range, the enzyme stability is excellent. When it is equal to or less than the upper limit, the color stability at high temperatures is excellent.

In liquid detergents, (B)/(C), which represents the mass ratio of the content of component (B) to the content of component (C), is preferably 10 or more, more preferably 10 to 100, even more preferably 15 to 50, and most preferably 15 to 40. When it is equal to or greater than the lower limit of the above range, the enzyme stability is excellent. When it is equal to or less than the upper limit, the color stability at high temperatures is excellent.

In the liquid detergent, (E)/(C), which represents the mass ratio of the content of component (E) to the content of component (C), is preferably 20 to 70, more preferably 25 to 60, and most preferably 40 to 60. If it is equal to or greater than the lower limit of the above range, the color tone of the liquid detergent is unlikely to change, and if it is equal to or less than the upper limit, the cleaning performance is unlikely to decrease.

In order to prevent color changes in the liquid detergent, it is preferable that the liquid detergent does not contain any phenylboronic acid derivatives other than component (C) (such as 4-formylphenylboronic acid), or if it does contain such a derivative, it should be in a small amount.
For example, the content of the phenylboronic acid derivative other than the component (C) relative to the total mass of the liquid detergent is preferably 0.5 mass% or less, more preferably 0.3 mass% or less, and even more preferably 0.1 mass% or less. It may be zero.

The content of component (D) is preferably 0.1 to 7 mass % of the total mass of the liquid detergent, more preferably 0.3 to 6 mass %, and most preferably 0.5 to 5 mass %. If it is equal to or greater than the lower limit of the above range, the cleaning power is excellent, and if it is equal to or less than the upper limit, the low-temperature stability is excellent.

The content of component (E) is 40% by mass or less, preferably 33% by mass or less, and more preferably 30% by mass or less, based on the total mass of the liquid detergent. The content of component (E) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total mass of the liquid detergent. That is, the content of component (E) is preferably 10 to 40% by mass, more preferably 15 to 33% by mass, and more preferably 20 to 30% by mass, based on the total mass of the liquid detergent.
When the content of component (E) is equal to or less than the above upper limit, the container for the liquid detergent can be easily made smaller.

When the liquid detergent contains the (F) component, the content of the (F) component is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total mass of the liquid detergent, in terms of the excellent effect of improving low-temperature stability. On the other hand, the content of the (F) component is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on the total mass of the liquid detergent, in terms of the suppression of color change in the liquid detergent. In other words, the content of the (F) component is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 30% by mass, based on the total mass of the liquid detergent.

<Physical Properties>
The pH of the liquid detergent at 25° C. is preferably 6 to 9, more preferably 6.5 to 8.5, and even more preferably 7 to 8.
The pH of the liquid cleaner can be adjusted, if necessary, by adding a pH adjuster.
The pH is a value measured at 25° C. using a pH meter (product name: HM-30G, manufactured by DKK-TOA Corporation).

<Production Method>
The liquid detergent of the present invention can be produced according to a conventional method for producing a liquid detergent. For example, the liquid detergent can be produced by adding each component except the pH adjuster to a part of water and mixing them, then adding the pH adjuster as necessary to adjust the pH, and then adding the remainder of the water to make the total amount 100% by mass. The obtained liquid detergent is preferably contained in a container such as a bottle container, a squeeze container, or a pouch container to make a container-packed liquid detergent product.

As one embodiment of the container for the packaged liquid detergent product, a plastic container having a plastic container body and a plastic cap can be used. The container body has a mouth, and the cap is configured to be removably attached to the mouth.
The material of the container body is preferably a transparent or semi-transparent synthetic resin such as a polyethylene resin, a polypropylene resin, polyethylene terephthalate (PET), etc. The container body can be formed, for example, by biaxial stretch blow molding.
The cap is preferably a cap having a shape with a measuring tube portion capable of measuring the liquid detergent (hereinafter, also referred to as a measuring cap). The material of the cap is preferably a transparent or semi-transparent synthetic resin such as polyethylene resin, polypropylene resin, or polyethylene terephthalate (PET). The cap can be formed by injection molding.
The shape of the measuring cap may be a known shape, for example, as described in JP 2020-200095 A, which has a measuring tube portion extending in the axial direction and a tongue-shaped portion provided at the tip of the measuring tube portion in the axial direction in a part of the circumferential direction centered on the axis and protruding in the axial direction.

<How to use>
Methods for using liquid detergents include, for example, putting the liquid detergent into the liquid detergent inlet of a washing machine and then running the washing machine, putting the liquid detergent into water together with the items to be washed when washing, immersing the items to be washed in a cleaning liquid prepared by dissolving the liquid detergent in water in advance, applying the liquid detergent directly to the items to be washed and leaving it for, for example, 3 minutes to 24 hours, and then washing as usual.

It is also preferable to use a washing machine equipped with an automatic detergent dispenser function, which has been put to practical use in recent years.
The automatic detergent dispenser function automatically dispenses detergent from a tank containing the detergent into the washing tub via a dispenser pipe. A measuring device such as a syringe pump is provided in the dispenser pipe, and a fixed amount of detergent, set according to the amount of laundry, can be transferred from the tank to the washing tub.

Using the automatic detergent dispensing function not only saves you the trouble of measuring out the detergent, but also prevents liquid detergent from getting on your hands when measuring out the detergent, or from spilling and soiling the washing machine or surrounding area.
In addition, since the liquid detergent of the present invention is a concentrated type, the amount used per wash may be very small, about 10 mL. It is difficult to accurately measure such a small amount of liquid detergent using a cap, etc., and the amount of liquid is likely to be insufficient or excessive. By using the automatic detergent dispensing function, it is possible to accurately measure even a small amount of liquid detergent, making it easier to demonstrate sufficient cleaning power and avoiding waste due to overuse, which is preferable.

It is also preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. When an automatic dispenser is used, it is also preferable because it is possible to accurately measure even a small amount of liquid detergent, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse.
Some automatic dispensers on the market use infrared sensors to automatically dispense liquid detergent without the need to touch a switch, etc. By using such an automatic dispenser, the user can measure out the liquid detergent simply by holding the container in one hand, greatly reducing the burden on the user.

In addition, when using an automatic dispenser, it is also preferable to receive the liquid detergent dispensed into a soft container and then put the soft container directly into the washing machine, so that the entire amount of the dispensed liquid detergent can be reliably dissolved in the cleaning liquid.
Examples of materials for 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 items to be washed include textile products such as clothing, dishcloths, towels, sheets, curtains, etc. The material of the textile products is not particularly limited, and may be any of natural fibers such as cotton, silk, wool, etc., and chemical fibers such as polyester, polyamide, etc.
When the liquid detergent is used by dissolving it in water, it is preferable to dilute it, for example, 5 to 5,000 times (by volume).
The liquor ratio, which is the amount of water per amount of clothes (mass of washing liquid during washing/mass of clothes), is preferably 5 or more for a drum type washing machine and 10 or more for a vertical washing machine.
The amount of liquid detergent used in the cleaning process is preferably 10 to 500, more preferably 10 to 300, and even more preferably 10 to 100, in terms of the ratio of the total mass of the items to be washed (mass of fabric) to the total mass of the liquid detergent.
The liquid detergent is suitable as a detergent for textile products.

The liquid detergent of the present invention is a concentrated type liquid detergent containing an enzyme, and can exert a high detergency even with a small amount used. In addition, despite being highly concentrated with a high surfactant concentration, it has excellent enzyme stability, low temperature stability, and high temperature color stability.
In particular, since amylase is easily inactivated, the present invention is highly effective when applied to concentrated liquid detergents that contain amylase.
Furthermore, as shown in the examples below, when 4-formylphenylboronic acid is added to a concentrated liquid detergent containing an enzyme, the enzyme stability is obtained, but the liquid detergent is prone to yellowing when placed under high temperature conditions. In contrast, the liquid detergent of the present invention can simultaneously achieve enzyme stability, color stability at high temperatures, and low temperature stability by adding component (C) having a specific molecular structure and by achieving a specific balance between (A) and (B).

In a washing machine with an automatic detergent dispenser function, the temperature in the tank that contains the detergent is likely to rise when drying clothes. In addition, the tank is not completely sealed because the detergent in the tank is sucked and transferred using a syringe pump or the like. As shown in the examples below, when liquid detergent is stored in the tank of a washing machine with an automatic detergent dispenser function, the enzyme residual rate tends to decrease.
The liquid detergent of the present invention has excellent color stability and enzyme stability at high temperatures, and is therefore suitable as a liquid detergent for automatic detergent dispensing, which is stored in the tank of a washing machine equipped with an automatic detergent dispensing function. In addition, since it is a concentrated liquid detergent that can exert high detergency with a small amount of use, it is also suitable as a liquid detergent for automatic detergent dispensing, since it can be used many times with the capacity of the washing machine tank.

A preferred embodiment of the liquid detergent of the present invention is, for example, embodiment I below.
(Aspect I)
The liquid detergent comprises components (A), (B), (C), (D), (E), and (F),
the component (A) contains one or more EO-containing polyoxyalkylene-type nonionic surfactants (A1), and the average number of moles of EO added per mole of the component (A1) is 7 to 15 moles,
The component (B) contains one or both of LAS and AES,
The component (C) includes (C1) which is one or more selected from 2-methylphenylboronic acid, 3-methylphenylboronic acid, and 4-methylphenylboronic acid,
(D1) in which the component (D) is one or both of a protease and an amylase,
The content of the (E) component is 30% by mass or less based on the total mass of the liquid detergent,
The content of the (F) component is 1% by mass or more based on the total mass of the liquid detergent,
An embodiment in which (A)/(B) is 1 or more.
In the present invention, the total content of each component of the liquid detergent does not exceed 100% by mass.

In embodiment I, the proportion of the total amount of the component (A1) relative to the total amount of the component (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. It may be 100% by mass.
In embodiment I, the proportion of the total of LAS and AES relative to the total mass of the component (B) is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more. It may be 100 mass%.
In embodiment I, the proportion of the total amount of the component (C1) relative to the total amount of the component (C) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. It may be 100% by mass.
In embodiment I, the proportion of the total amount of the (D1) component relative to the total amount of the (D) component is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. It may be 100% by mass.
In embodiment I, the liquid detergent is preferably a liquid detergent for automatic detergent dispensing, which is used by being contained in the tank of a washing machine equipped with an automatic detergent dispensing function.

The present invention will be described in detail below 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.

<Ingredients used>
[Component (A)]
Linear AE (20EO): A compound in which 20 moles of ethylene oxide are added to 1 mole of a primary alcohol (mass ratio of alcohol having 12 carbon atoms to alcohol having 14 carbon atoms = 7/3). In the formula (a1), R ¹¹ is an alkyl group having 12 carbon atoms (C12) and an alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14 = 70:30), R ¹² is a hydrogen atom, the carbon atom of R ¹¹ bonded to -O- is a primary carbon atom, s is 20, t is 0, and u is 0.
Linear AE (15EO): the linear AE (20EO) obtained by changing the amount of ethylene oxide added to 1 mole of the primary alcohol to 15 moles, and changing s in the formula (a1) to 15.
Linear AE (12EO): the linear AE (20EO) obtained by changing the amount of ethylene oxide added to 1 mole of the primary alcohol to 12 moles, and changing s in the formula (a1) to 12.
Linear AE (9EO): the linear AE (20EO) obtained by changing the amount of ethylene oxide added to 1 mole of the primary alcohol to 9 moles, and changing s in the formula (a1) to 9.
Linear AE (7EO): the linear AE (20EO) obtained by changing the amount of ethylene oxide added to 1 mole of the primary alcohol to 7 moles, and changing s in the formula (a1) to 7.
Linear AE (5EO): the linear AE (20EO) obtained by changing the amount of ethylene oxide added to 1 mole of the primary alcohol to 5 moles, and changing s in the formula (a1) to 5.

MEE (15EO): Polyoxyethylene fatty acid methyl ester. In the formula (a3), R ¹⁵ is an alkyl group having 11 to 13 carbon atoms, R ¹⁶ is a methyl group, -X- is -COO-, the carbon atom of R ¹⁵ to which X is bonded is a secondary carbon atom, p is 15, q is 0, and r is 0.
Primary branched AE (7EO): polyoxyethylene alkyl ether (a compound in which 7 moles of ethylene oxide are added to an alcohol having 13 carbon atoms. In the general formula (a2), R ¹³ is a branched alkyl group having 13 carbon atoms, the carbon atom of R ¹³ bonded to the oxygen atom is a primary carbon atom, R ¹⁴ is a hydrogen atom, v is 7, w is 0, and x is 0. This compound (a2) was synthesized by the following synthesis method.
Primary branched AE (10EO): A C10 alcohol obtained by subjecting pentanol to the Guerbet reaction, to which 10 moles of ethylene oxide have been added.
Secondary branched (7EO): 7 moles of ethylene oxide are added to 1 mole of secondary alcohol. In formula (a2), R ¹³ is an alkyl group having 12 to 14 carbon atoms, R ¹⁴ is a hydrogen atom, the carbon atom of R ¹³ bonded to -O- is a secondary carbon atom, v is 7, w is 0, and x is 0.
Secondary branched (12EO): 12 moles of ethylene oxide are added to 1 mole of secondary alcohol. In formula (a2), R ¹³ is an alkyl group having 12 to 14 carbon atoms, R ¹⁴ is a hydrogen atom, the carbon atom of R ¹³ bonded to -O- is a secondary carbon atom, v is 7, w is 0, and x is 0.

[Component (B)]
LAS: Linear alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms, manufactured by Lion Corporation, trade name "Lipon (registered trademark) LH-200".
AES: polyoxyalkylene alkyl ether sulfate (a mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average mole number of EO added: 1). In formula (b1), R ¹⁷ is a linear alkyl group having 12 and 14 carbon atoms, m is 1, n is 0, M is sodium, and the proportion of compounds in which m is 0 and n is 0 relative to the total amount of AES is 43% by mass. Synthesized by the method of Preparation Example 1 below.
[Component (C)]
C-1: 4-Methylphenylboronic acid:
C-2: 4-Methoxyphenylboronic acid:
Comparative component 1: 4-formylphenylboronic acid [component (D)]
- Protease 1: Product name "Progress Uno", manufactured by Novozymes Japan.
Amylase 1: Product name "Amplify Prime 100L", manufactured by Novozymes Japan.
Mannanase 1: Product name "Mannaway 200L", manufactured by Novozymes Japan.
Cellulase 1: Product name "Carezyme Premium 4500L", manufactured by Novozymes Japan.
Pectinase 1: Trade name "Xpect1000L", manufactured by Novozymes Japan.
[Component (E)]:
- Water: Product name "Purified Water", manufactured by Kanto Chemical Co., Ltd.
[Component (F)]
- Monoethanolamine: Trade name "Monoethanolamine", manufactured by Nippon Shokubai Co., Ltd.

[Optional ingredients]
Polyethylene glycol: Junsei Chemical Co., Ltd., product name "PEG #1000", weight average molecular weight 1000.
Solfit: 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd., trade name "Solfit").
・Coconut fatty acid: Soap (manufactured by NOF Corporation, product name "Coconut Fatty Acid").
Sodium lactate: enzyme stabilizer (manufactured by Musashino Chemical Laboratory, product name "Sodium Lactate 60E").
- Paratoluenesulfonic acid: a hydrotropic agent (manufactured by Kyowa Hakko Kirin Co., Ltd., trade name "PTS acid").
Citric acid: (manufactured by Ipposha Yushi Kogyo Co., Ltd., product name "Liquid Citric Acid").
Diclosan: 4,4'-dichloro-2-hydroxydiphenyl ether (manufactured by BASF, trade name "TINOSAN HP100").
BIT: 1,2-benzisothiazolin-3-one (manufactured by Clariant Japan, trade name "NIPACIDE BIT20").
BHT: Antioxidant, dibutylhydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER BHT-R").
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.
- Colorant: manufactured by Kishi Chemical Co., Ltd., product name "Green No. 3".
NaOH: Sodium hydroxide, pH adjuster (manufactured by Toagosei Co., Ltd., product name "Sodium Hydroxide").

[Preparation Example 1: Synthesis of AES]
Into a 4 L autoclave, 400 g of Procter &Gamble's trade name CO1270 alcohol (a mixture of an alcohol having 12 carbon atoms and an alcohol having 14 carbon atoms in a mass ratio of 75/25) was charged as a raw material alcohol, and 0.8 g of potassium hydroxide catalyst was charged as a reaction catalyst. The atmosphere inside the autoclave was replaced with nitrogen, and the temperature was raised with 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 reacted to obtain an alcohol ethoxylate.
Analysis using a gas chromatograph: GC-5890 manufactured by Hewlett-Packard, a detector: a flame ionization detector (FID), and a column: Ultra-1 (manufactured by HP, L25m×φ0.2mm×T0.11μm) showed that the average number of moles of ethylene oxide added in the obtained alcohol ethoxylate was 1.0. In addition, the amount of compounds to which ethylene oxide was not added (those that ultimately became component (a-0)) was 43% by mass based on the total amount of the obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after replacing with nitrogen, 96 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40° C. After the dropwise addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. This was then neutralized with an aqueous sodium hydroxide solution to obtain AES.

<Storage container>
The container used to store the liquid detergent was either container A or container B described below.
Container A: A container for a containerized liquid detergent product, comprising a transparent plastic container body (volume 500 mL, wall thickness 0.05 to 1.2 mm, maximum wall thickness 1.2 mm) made by biaxially stretching and blow molding polyethylene terephthalate (PET) resin, and a transparent plastic measuring cap injection molded from a resin composition whose main component is polypropylene (PP).
Container B: Tank of a washing machine equipped with an automatic detergent dispenser function. An automatic detergent dispenser tank (part number BD-SX110CL-002, capacity: approximately 1000 mL, non-sealed container) attached to a Hitachi drum-type washing machine (BD-SX110E) was used.

<Examples 1 to 24 and Comparative Examples 1 to 7>
Liquid detergents were produced according to the blending amounts shown in Tables 1 to 6. The blending amounts of optional components are shown in Table 7. The contents shown in Table 7 are percentages (mass%) relative to the total mass of the liquid detergent.
Specifically, components (A), (B), and (E) were placed in a 500 mL beaker and thoroughly stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.), and then component (C) was added and dissolved, followed by addition of components (F) and (D) and further thorough stirring.
Next, an appropriate amount of NaOH was added so that the pH at 25° C. was 7.7, and then water was added so that the total amount became 100% by mass, thereby obtaining a liquid detergent.

The resulting liquid detergents were evaluated for detergency (sebum detergency), color stability at high temperatures, enzyme stability, and low temperature stability by the following evaluation methods. The evaluation results are shown in Tables 1 to 6.
In each stability evaluation, storage container A or B shown in the table was used. Storage container A contained 400 mL of liquid detergent and was sealed, and storage container B contained 400 mL of liquid detergent and was closed with a lid.
In the table, the unit of blending amount is "mass %" and indicates the amount converted to a pure content. Also, a blank column for blending amount means that the component is not blended (blending amount 0 mass %).
The appropriate amount of NaOH refers to a necessary and sufficient amount to adjust the pH of the liquid detergent to 7.7.
In addition, the amount of water is calculated by regarding the amount of NaOH as zero, and the actual amount of water is an amount such that the total amount (mass %) of all ingredients, including NaOH, is 100 mass %.

<Evaluation method>
[Method for evaluating enzyme (amylase) stability]
Since amylase is particularly susceptible to inactivation, the stability of amylase was evaluated as the enzyme stability of liquid detergents containing amylase.
That is, after production, each liquid detergent was placed in a storage container and stored for two weeks at 40° C. and 5° C. The amylase activity of the liquid detergent stored at 40° C. for two weeks (40° C. storage product) and the liquid detergent stored at 5° C. for two weeks (5° C. storage product) was measured as shown below.

The amylase substrate used was "Phadebas Amylase Test 50T" (Magle Life Sciences). This is a tablet containing a certain amount of bovine serum albumin in a blue starch polymer substrate. When α-amylase acts on it, it undergoes hydrolysis to produce a blue solution, and amylase activity can be determined by measuring the absorbance (620 nm).

(Preparation of Buffer Solution)
20.0 g of sodium sulfite (manufactured by Junsei Chemical Co., Ltd., special reagent grade, etc.), 6.15 g of potassium dihydrogen phosphate (manufactured by Hayashi Pure Chemical Industries, Ltd., special grade, etc.), 10.86 g of disodium hydrogen phosphate 12-hydrate (manufactured by Kanto Chemical Co., Ltd., special grade, etc.), 0.015 g of calcium chloride dihydrate (manufactured by Kanto Chemical Co., Ltd., deer grade 1, etc.) and 0.75 mL of Brij35 (30% aqueous solution, manufactured by MERCK) were precisely weighed out, dissolved in ion-exchanged water, and the volume was adjusted to 1 L to prepare a buffer solution.
0.1 g of each of the samples stored at 40° C. and 5° C. in each example was diluted with the above buffer solution to prepare a sample solution.

5 mL of the above buffer solution and 1 tablet of the above "Phadebas Amylase Test 50T" were added to 1 g of the sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then allowed to stand at 40°C for 5 minutes to allow the enzyme reaction to proceed. Then, 1 mL of 1 mol/L (1N) sodium hydroxide solution (manufactured by Kanto Chemical Co., Ltd.), which is an enzyme reaction stopper, was added to the solution, and the reaction was stopped by stirring for 10 seconds with a vortex mixer. Then, the unreacted substrate remaining in the solution was removed with filter paper, and the filtrate was collected.
The absorbance (absorbance A) of the recovered filtrate at a wavelength of 620 nm was measured using a Shimadzu UV-160 ultraviolet-visible spectrophotometer.

In order to eliminate the influence of absorption other than that of the target component, 1 mL of 1 mol/L (1N) sodium hydroxide solution, which is an enzyme reaction stopper, was added to 1 g of each sample solution, and the mixture was stirred for 10 seconds with a vortex mixer. One tablet of the above-mentioned "Phadebas Amylase Test 50T" was then added, the mixture was stirred for 10 seconds with a vortex mixer, and the mixture was allowed to stand at 40°C for 15 minutes. Then, the insoluble components were removed with a 0.45 μm filter, and the filtrate was collected. Then, the absorbance (absorbance B) of the filtrate at a wavelength of 620 nm was measured using UV-160.
A larger difference between absorbance A and absorbance B means that a larger amount of decomposition products of the substrate was present in the filtrate.

From the results of the amylase activity measurement, the residual amylase activity (%) was calculated according to the following formula (i).
Residual amylase activity=(absorbance A of sample stored at 40° C.−absorbance B of sample stored at 40° C.)/(absorbance A of sample stored at 5° C.−absorbance B of sample stored at 5° C.)×100 (i)

Using the residual amylase activity (%) as an index, enzyme stability was evaluated based on the following criteria, with "◎" and "◯" being deemed acceptable.
<Evaluation criteria>
⊚: Enzyme residual rate is 80% or more and 100% or less.
Good: Enzyme remaining rate is 60% or more but less than 80%.
△: Enzyme remaining rate is 40% or more and less than 60%.
×: Enzyme remaining rate is 0% or more and less than 40%.

[Method for evaluating color stability at high temperatures]
The liquid detergent was placed in storage container A or B and stored in a thermostatic chamber at 50° C. for 7 days.
To evaluate the color change before and after storage, the absorbance of the liquid detergent was measured at a wavelength of 420 nm using a UV-160 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. The color change was evaluated according to the following evaluation criteria based on the absolute value of the difference in absorbance before and after storage, with "◎" and "○" being considered as passing.
<Evaluation criteria>
⊚: The absolute value of the difference in absorbance is 0.10 or less.
◯: The absolute value of the difference in absorbance is greater than 0.10 and is 0.30 or less.
Δ: The absolute value of the difference in absorbance is greater than 0.30 and is 0.50 or less.
×: The absolute value of the difference in absorbance exceeds 0.50.

[Method for evaluating low temperature stability]
The liquid detergent was placed in storage container A or B and stored in a thermostatic chamber at 5° C. for 7 days.
After storage, the appearance of the liquid in the storage container was visually observed and the low-temperature stability was evaluated according to the following evaluation criteria, with "A" and "B" being considered as acceptable.
<Evaluation criteria>
◎: The liquid is transparent with no visible precipitates and has high fluidity.
○: The liquid is transparent with no visible precipitates and low fluidity.
Δ: The liquid is turbid, but has fluidity.
×: The liquid was turbid and had no fluidity.

[Method for evaluating cleaning power]
An artificially soiled cloth (manufactured by the Laundry Science Association, a general incorporated foundation) was prepared by impregnating an unsoiled cloth with artificial soil, and the resulting cloth was cut into a size of 5 cm x 5 cm to prepare a soiled cloth.
The cleaning tester used was a Terg-O-tometer (manufactured by United States Testing Co.).
The cleaning liquid used was prepared by adding a liquid cleaning agent to 900 mL of water (25° C., 5° DH) so that the concentration was 200 ppm, and stirring for 30 seconds.
The cleaning solution, 10 of the above soiled fabrics, and the cleaned knitted fabric were placed in a cleaning tester, and washed for 10 minutes at 120 rpm and 25° C. with a bath ratio of 20. The fabrics were then transferred to a twin-tub washing machine (manufactured by Mitsubishi Electric Corporation, product name "CW-C30A1-H1") and dehydrated for 1 minute, then rinsed in 30 L of water (25° C., 5° DH) for 3 minutes and air-dried.
The reflectance of the unsoiled cloth and the soiled cloth before and after cleaning was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700 type"), and the cleaning rate (%) was calculated according to the following formula (i).
Cleaning rate (%)=(K/S of soiled cloth before cleaning−K/S of soiled cloth after cleaning)/(K/S of soiled cloth before cleaning−K/S of unsoiled cloth)×100 (i)
(In formula (i), K/S=(1−R/100) ² /(2R/100). R is the reflectance (%).)
The cleaning rate (%) was calculated for 10 pieces of soiled cloth and the average value was calculated. Using the average cleaning rate (%) as an index, the sebum cleansing power was evaluated according to the following criteria, with "◎" and "◯" being deemed acceptable.
<Evaluation criteria>
⊚: The average cleaning rate is 80% or more and 100% or less.
Good: The average cleaning rate was 60% or more and less than 80%.
Δ: The average cleaning rate was 40% or more and less than 60%.
×: The average cleaning rate was 0% or more and less than 40%.

As shown in the results in Tables 1 to 6, the liquid detergents of Examples 1 to 24 were able to exert high cleaning power even with small amounts used, and also had good enzyme stability, color stability at high temperatures, and low temperature stability.

Example 1 and Example 20 are examples in which the liquid detergent has the same composition but different storage containers. Example 20, in which the liquid detergent was stored in the tank (storage container B) of a washing machine equipped with an automatic detergent dispenser function, had a lower enzyme residual rate than Example 1, in which the liquid detergent was stored in storage container A, which is an airtight container.

Comparing Example 1 and Comparative Example 1, Comparative Example 1 not containing component (C) had the same high temperature color stability and low temperature stability as Example 1, but had significantly inferior enzyme stability.
Comparative Example 2 is an example in which the type and total amount of the surfactant are the same as those in Example 1, but the mass ratio of (A)/(B) is small. Compared to Example 1, the color stability at high temperatures and the low temperature stability were inferior.
In Comparative Example 3, the types of ingredients were the same as in Example 1, but the proportion of water was high and the proportion of nonionic surfactant was low, resulting in poor detergency. In other words, Comparative Example 3 was not a concentrated type, and therefore could not exert sufficient detergency with a small amount used.
Comparative Example 4 is an example in which 4-formylphenylboronic acid (Comparative Component 1) was blended in place of Component (C) of Comparative Example 3. However, since it was not a concentrated type, no yellowing occurred even when placed under high temperature conditions.

Comparing Example 1 and Comparative Example 5, Comparative Example 5, which used Comparative Component 1 (4-formylphenylboronic acid) instead of Component (C), had the same level of enzyme stability as Example 1, but the liquid detergent turned yellow when placed under high temperature conditions.
Comparing Example 20 with Comparative Examples 6 and 7, Comparative Example 6, which does not contain component (C), had similar color stability at high temperatures and low temperature stability as Example 20, but was significantly inferior in enzyme stability. Comparative Example 7, which contained comparative component 1, 4-formylphenylboronic acid, instead of component (C), had the same level of enzyme stability as Example 20, but yellowing occurred when the liquid detergent was placed under high temperature conditions.

Claims (2)

The composition contains (A) a nonionic surfactant, (B) a non-soap anionic surfactant, (C) a compound represented by the following formula 1, (D) an enzyme, and (E) water,
The content of the (E) component is 40 mass% or less,
A liquid detergent composition for textile products, in which (A)/(B), which represents the mass ratio of the content of the (A) component to the content of the (B) component, is 1 or more.

(In the formula, R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methoxy group.) The liquid detergent composition for textile products according to claim 1, further comprising (F) monoethanolamine.