Liquid detergent composition for textile products

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

[Technical Field]

[0001] This invention relates to a liquid detergent composition for textile products. [Background technology]

[0002] In the field of liquid detergents for textile products, there is a growing awareness of environmental impact. For example, efforts are being made to reduce energy consumption in logistics and decrease waste by miniaturizing the containers that hold the liquid detergents. With the miniaturization of containers, there is a demand for liquid detergents that not only have high cleaning power but also require less product per wash. In response to these demands, concentrated liquid detergents with reduced water content and increased surfactant concentration have been proposed (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2010-229387 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Concentrated liquid detergents sometimes use enzymes to achieve high cleaning power with a small amount of product. However, enzymes generally have the problem of being easily deactivated when the water content in the liquid detergent decreases.

[0005] Furthermore, in recent years, transparent plastic containers are sometimes used for liquid detergents due to environmental considerations and aesthetic appeal, so it is important that the containers do not easily change color. In particular, color changes can occur when liquid detergents are exposed to high temperatures, so it is necessary to be able to suppress such color changes. Furthermore, concentrated liquid detergents have the problem of being prone to gelation or solidification in low-temperature environments during winter (for example, 5°C).

[0006] The present invention aims to provide a liquid detergent composition for textile products that contains enzymes, exhibits high cleaning power with a small amount of use, and has good enzyme stability, color stability at high temperatures, and low-temperature stability. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] (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 component (E) is 40% by mass or less, A liquid detergent composition for textile products, wherein the mass ratio (A) / (B), which represents the mass ratio of the content of component (A) to the content of component (B), is 1 or more.

[0008] [ka]

[0009] (In the formula, R 1 , R 2 , R 3 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a methoxy group. [2] The liquid detergent composition for textile products according to [1], further comprising (F) monoethanolamine. [Effects of the Invention]

[0010] According to the present invention, a liquid detergent composition for textile products is obtained that contains an enzyme, exhibits high cleaning power with a small amount of use, has good enzyme stability, shows little change in color at high temperatures, and has good low-temperature stability. [Modes for carrying out the invention]

[0011] The liquid detergent composition for textile products of the present invention (hereinafter also simply referred to as "liquid detergent") is a composition containing components (A), (B), (C), (D), and (E) described later. It is preferable that it further contains component (F). The following descriptions of constituent elements may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, numerical ranges represented by "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits.

[0012] <(A) component> (A) Component is a nonionic surfactant. (A) One component may be used, or two or more components may be combined.

[0013] Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids 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.

[0014] It is preferable that the nonionic surfactant includes a polyoxyalkylene-type nonionic surfactant. Examples of polyoxyalkylene-type nonionic surfactants include the compound represented by the following general formula (a1) (hereinafter also referred to as "compound (a1)"), the compound represented by the following general formula (a2) (hereinafter also referred to as "compound (a2)"), and the compound represented by the following general formula (a3) ​​(hereinafter also referred to as "compound (a3)").

[0015] [Compound (a1)] Compound (a1) is a polyoxyalkylene-type nonionic surfactant having a straight-chain 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 repeating units of EO. 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 repeating units of A 11 O. u is a number from 0 to 20 representing the average number of repeating units of EO.)

[0016] In general formula (a1), the hydrocarbon group of R 11 has 8 to 22 carbon atoms, preferably 10 to 18, more preferably 12 to 18. The hydrocarbon group of R 11 is linear. Also, the hydrocarbon group of R 11 may or may not have an unsaturated bond.) The carbon atom of R bonded to -O 11 may be a primary carbon atom or a secondary carbon atom.)

[0017] When R 12 is an alkyl group, it has 1 to 6 carbon atoms, preferably 1 to 3.) When R 12 is an alkenyl group, it has 2 to 6 carbon atoms, preferably 2 to 3.) R 12 is particularly preferably a hydrogen atom.)

[0018] s is from 3 to 25, and in terms of excellent effect of improving enzyme stability, 5 to 25 is preferable, 7 to 20 is more preferable, 7 to 18 is even more preferable, and 7 to 15 is particularly preferable.) t is from 0 to 6, preferably 0 to 3.) u is from 0 to 20, preferably 0 to 15, more preferably 0 to 10.) In terms of its excellent effect in improving enzyme stability, s+u is preferably 3 to 30, more preferably 5 to 25, even more preferably 5 to 20, particularly preferably 7 to 20, and most preferably 7 to 15.

[0019] If t is not 0, that is, if compound (a1) has EO and PO, EO and BO, or EO, ​​PO and BO, then [(EO)s / (A 11 In O)t], there are no particular limitations on the distribution (arrangement order) of EO and PO, EO and BO, or EO, ​​PO and BO; they may be arranged in blocks or randomly. Also, if EO is "R 11 -O-" may be added, or PO or BO may be added to "R 11 It may be combined with "-O-". If t is not 0, compound (a1) preferably has EO and PO, or EO and BO.

[0020] [Compound (a2)] Compound (a2) is a polyoxyalkylene-type nonionic surfactant having branched hydrocarbon groups. R 13 -O-[(EO) v / ( A 12 O) w ]-(EO) x -R 14 ...(a2) (In general formula (a2), R 13 R is a branched hydrocarbon group with 8 to 22 carbon atoms. 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 between 3 and 25 indicating the average repeating number of EO. A 12 O represents at least one of PO (oxypropylene group) and BO (oxybutylene group). w is A 12 x is a number between 0 and 6 representing the average number of repetitions of O. x is a number between 0 and 20 representing the average number of repetitions of EO.

[0021] In general formula (a2), R 13 The number of carbon atoms in the hydrocarbon group is 8 to 22, preferably 10 to 18, and more preferably 12 to 18.13 The hydrocarbon group is a branched chain. Also, R 13 The hydrocarbon group may or may not have an unsaturated bond. -O- binding R 13 The carbon atoms can be either primary or secondary carbon atoms.

[0022] R 14 If it is an alkyl group, the number of carbon atoms is 1 to 6, and preferably 1 to 3. R 14 If the group is an alkenyl group, the number of carbon atoms is 2 to 6, and preferably 2 to 3. R 14 Hydrogen atoms are particularly preferred.

[0023] v is between 3 and 25, with 5 to 18 being preferred, 7 to 15 being more preferred, and 7 to 12 being even more preferred, due to its excellent effect in improving enzyme stability. w is between 0 and 6, and preferably between 0 and 3. x is between 0 and 20, preferably between 0 and 15, and more preferably between 0 and 10. In terms of its excellent effect in improving 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.

[0024] If w is not 0, that is, if compound (a2) has EO and PO, EO and BO, or EO, ​​PO and BO, then [(EO) v / ( A 12 O) w In [ ], there are no particular restrictions on the distribution (arrangement order) of EO and PO, EO and BO, or EO, ​​PO and BO; they may be arranged in blocks or randomly. Also, if EO is "R 13 -O-" may be added, or PO or BO may be added to "R 13 It may be combined with "-O-". If w is not 0, compound (a2) preferably has EO and PO, or EO and BO.

[0025] Examples of commercially available compounds (a2) include, for example, alcohols such as Diadol (registered trademark) (C13, the number after C indicates the number of carbon atoms in the alcohol; the same applies hereinafter) manufactured by Mitsubishi Chemical Corporation, Neodol (registered trademark) (a mixture of C12 and C13) manufactured by Shell Corporation, Safol (registered trademark) 23 (a mixture of C12 and C13) manufactured by Sasol Corporation, and EXXAL (registered trademark) 13 (C13), to which 3 to 10 moles of ethylene oxide have been added; A C13 alcohol obtained by trimerizing butene to a C12 alkene and subjecting it to the oxo process is to be added with 3 or 5 moles, or 7 moles, of ethylene oxide (Lutensol® TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF). A C13 alcohol obtained by trimerizing butene to a C12 alkene and subjecting it to the oxo process is then modified by adding 12 moles or 15 moles of ethylene oxide (e.g., Lutensol® TO12, Lutensol TO15, manufactured by BASF). A C10 alcohol obtained by subjecting pentanol to the Garbet reaction is then modified by adding 9 moles of ethylene oxide (Lutensol XP90, manufactured by BASF). A C10 alcohol obtained by subjecting pentanol to the Garbet reaction is then modified by adding 7 moles of ethylene oxide (Lutensol XL70, manufactured by BASF). Examples include Lutensol XA60 (manufactured by BASF), which is obtained by adding 6 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to the Garbet reaction. Among these, products such as Sasol's trade name Safol23 (branching rate: 50% by mass) (an alcohol obtained from olefins obtained from coal gasification by the oxo process and then hydrogenated) and Shell Chemicals' trade name Neodol23 (branching rate: 20% by mass) (produced from n-olefins by the improved oxo process and then rectified) have R in the general formula (a2). 13 Compounds in which the hydrocarbon group is a branched chain, and in general formula (a1) R 11In the case of a "mixture" of compounds in which the hydrocarbon group is straight-chain, the compound with a branched chain is defined as compound (a2), while the compound with a straight chain is defined as compound (a1). The "branching rate" refers to the proportion (by mass) of branched higher alcohols to the total higher alcohols.

[0026] [Compound (a3)] 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 either -COO- or -CONH-. 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 between 3 and 25 indicating the average repeating number of EO. A 13 represents at least one of PO (oxypropylene group) and BO (oxybutylene group). q is A 13 r is a number between 0 and 6 representing the average number of repetitions of O. r is a number between 0 and 20 representing the average number of repetitions of EO.

[0027] In general formula (a3), R 15 The number of carbon atoms in the hydrocarbon group is 7 to 21, preferably 9 to 19, and more preferably 11 to 19. 15 The hydrocarbon group may be a straight chain or a branched chain. Also, R 15 The hydrocarbon group may or may not have an unsaturated bond. -X-bond R 15 The carbon atoms can be either primary or secondary carbon atoms.

[0028] R 16 If it is an alkyl group, the number of carbon atoms is 1 to 6, and preferably 1 to 3. R16 If the group is an alkenyl group, the number of carbon atoms is 2 to 6, and preferably 2 to 3. R 16 Alkyl alkyl groups are particularly preferred.

[0029] p is between 3 and 25, with 5 to 20 being preferred, 10 to 18 more preferred, and 12 to 18 even more preferred, due to its excellent effect in improving enzyme stability. q is between 0 and 6, and preferably between 0 and 3. r is between 0 and 20, preferably between 0 and 15, and more preferably between 0 and 10. In terms of its excellent effect in improving enzyme stability, p+r is preferably 5 to 30, more preferably 5 to 25, even more preferably 5 to 20, and particularly preferably 10 to 20.

[0030] If q is not 0, that is, if compound (a3) ​​has EO and PO, EO and BO, or EO, ​​PO and BO, then [(EO) p / ( A 13 O) q In [ ], there are no particular restrictions on the distribution (arrangement order) of EO and PO, EO and BO, or EO, ​​PO and BO; they may be arranged in blocks or randomly. Also, if EO is "R 15 -X-" may be added, or PO or BO may be "R 15 It may be combined with "-X-". If q is not 0, compound (a3) ​​preferably has EO and PO, or EO and BO.

[0031] (A) Component (A) preferably contains one or both of compound (a1) and compound (a3) ​​and compound (a2), and more preferably contains compound (a1) and compound (a2), from the viewpoint of excellent low-temperature stability.

[0032] <(B) component> (B) Component is a non-soap-based anionic surfactant. A "non-soap-based anionic surfactant" is an anionic surfactant that excludes higher fatty acids or their salts (so-called soaps). (B) Component may be one type or a combination of two or more types.

[0033] (B) Examples of component (B) include carboxylic acid-type anionic surfactants such as linear alkylbenzene sulfonic acid or its salt (LAS), α-olefin sulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt (AS), polyoxyalkylene alkyl (alkenyl) ether sulfate ester or its salt (AES), alkyl group-containing alkane sulfonic acid or its salt, α-sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS), hydroxyalkane 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 its salt; and phosphate ester-type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, glycerin fatty acid ester monophosphate ester or its salt. Examples of salt forms of anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.).

[0034] As anionic surfactants, LAS, AOS, AS, and AES are preferred, and among these, LAS and AES are more preferred from the viewpoint of providing higher cleaning power. Liquid detergents preferably contain at least AES, and more preferably contain both LAS and AES.

[0035] Polyoxyalkylene alkyl (alkenyl) ether sulfates or their salts (AES) are represented by the following general formula (b1). R 17 -O-[(EO) m (PO) n ]-SO3 - 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 greater than or equal to 0.1 representing the average number of repeats of EO. n is a number between 0 and 6 representing the average number of repeats of PO. [(EO) m (PO) n ] indicates that there is no restriction on the order of the sequences of EO and PO, M + (This is a counter-cation.)

[0036] The AES is preferably one having a linear or branched alkyl or alkenyl group with 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, a linear alkyl group with 10 to 20 carbon atoms is preferred, and a linear alkyl group with 12 to 14 carbon atoms is more preferred. Specifically, examples include dodecyl groups, tridecyl groups, and tetradecyl groups.

[0037] m is preferably 0.1 to 5, more preferably 0.1 to 3, even more preferably 0.5 to 2, and particularly preferably 0.5 to 1.5. n is between 0 and 6, preferably between 0 and 3, and more preferably 0. m+n is preferably greater than 0, and more preferably between 1 and 5.

[0038] If n is not 0, that is, if AES has EO and PO, then [(EO) m (PO) n In [], there are no particular restrictions on the distribution (order of arrangement) of EO and PO; they may be arranged in blocks or randomly. Also, if EO is "R 17 -O-" can be added, or PO can be added to "R 17 It may be combined with "-O-". Methods for arranging EO and PO in a block-like manner include, for example, introducing ethylene oxide followed by propylene oxide, introducing propylene oxide followed by ethylene oxide, introducing ethylene oxide followed by propylene oxide, and then introducing ethylene oxide again. Furthermore, it is preferable that the compounds with m=0 and n=0 in formula (b1) are present in an amount of 35 to 55% by mass relative to the total mass of the compounds represented by formula (b1).

[0039] <(C) component> Component (C) is a compound represented by the following formula 1, and is phenylboronic acid or a derivative of phenylboronic acid. R in formula 1 1 , R 2 , R 3 Each of these is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methoxy group. (C) Component may be one type or a combination of two or more types.

[0040] [ka]

[0041] (C) Components 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-butyl Examples include phenylboronic 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. Among 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 preferred, and 2-methylphenylboronic acid, 3-methylphenylboronic acid, and 4-methylphenylboronic acid are most preferred.

[0042] <(D) component> (D) Component is an enzyme. Examples of enzymes include proteases, amylases, lipases, cellulases, mannanases, and pectinases. One type of enzyme may be used, or two or more may be combined. These enzymes are generally sold commercially as enzyme-containing preparations (enzyme preparations). They are typically incorporated in the form of enzyme preparations when preparing liquid detergents.

[0043] As for the protease, a protease having serine, histidine, and aspartic acid in its molecule, such as a serine protease, is preferred. Examples of protease-containing preparations (protease preparations) include, for example, the following products available from Novozymes: 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 Uno 101L; and the following products available from Genencor: Purafect L, Purafect OX, and Properase L.

[0044] Examples of amylase-containing preparations (amylase preparations) include the following products available from Novozymes: Terhamyl 300L, Terhamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, and Amplify Prime; Maxamyl from Genencore; Pullulanase Amano from Amano Enzyme Co., Ltd.; and DB-250 from Seikagaku Kogyo Co., Ltd.

[0045] Examples of lipase-containing preparations (lipase preparations) include Lipex 100L and Lipolase 100L, both available from Novozymes.

[0046] Examples of cellulase-containing preparations (cellulase preparations) include the following products available from Novozymes: Carezyme 4500L, Carezyme Premium 4500L, Endolase 5000L, and Cellclean 4500T.

[0047] Examples of preparations containing mannanase (mannanase preparations) include the product names Mannaway 4L and Mannaway 200L, which are available from Novozymes.

[0048] Examples of preparations containing pectinase (pectinase preparations) include Pectawash, Pectaway, and XPect, which are available from Novozymes. These enzyme preparations may be used individually or in combination of two or more.

[0049] <(E) component> (E) Component is water. There are no particular restrictions on the type of water used; examples include purified water, distilled water, deionized water, and tap water. These waters may be used individually or in combination of two or more types.

[0050] <(F) component> Component (F) is monoethanolamine (also known as 2-aminoethanol). Monoethanolamine contributes to improved low-temperature stability.

[0051] <Other optional ingredients> The liquid detergent may contain, as an optional component other than the components (A) to (F) above, components known in the field of liquid detergents for textile products, to the extent that they do not impair the effects of the present invention. Optional ingredients include, for example, higher fatty acids or their salts (so-called soap), other surfactants other than components (A) and (B) (excluding higher fatty acids or their salts), enzyme stabilizers other than component (C) (e.g., sodium lactate), hydrotropes (e.g., aromatic sulfonic acid or its salts), chelating agents, cleaning builders, stabilizers, alkaline agents other than monoethanolamine (e.g., alkanolamines such as diethanolamine and triethanolamine), metal ion scavengers, texture enhancers such as silicone, preservatives, fluorescent agents, color transfer inhibitors, pearlescent agents, antioxidants, antibacterial agents, general-purpose dyes or pigments as colorants, emulsifiers, fragrances, pH adjusters, and the like.

[0052] Other surfactants besides components (A) and (B) include cationic surfactants, semipolar surfactants, amphoteric surfactants, etc. Examples of pH adjusting agents include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines other than monoethanolamine, and ammonia.

[0053] <Content> The content of component (A) is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, and most preferably 35 to 45% by mass, relative to the total mass of the liquid detergent. If the value is above the lower limit of the above range, the enzyme stability is excellent; if it is below the upper limit, the low-temperature stability is excellent.

[0054] The content of compound (a1) is preferably 1 to 55% by mass, more preferably 10 to 50% by mass, and most preferably 20 to 45% by mass, relative to the total mass of the liquid detergent. If the content is above the lower limit of the above range, the enzyme stability is excellent, and if it is below the upper limit, the low-temperature stability is excellent. The content of compound (a2) is preferably 1 to 40% by mass, more preferably 10 to 35% by mass, and most preferably 15 to 30% by mass, relative to the total mass of the liquid detergent. If the content is above the lower limit of the above range, the enzyme stability is excellent, and if it is below the upper limit, the low-temperature stability is excellent. The content of compound (a3) ​​is preferably 1 to 55% by mass, more preferably 10 to 50% by mass, and most preferably 20 to 45% by mass, relative to the total mass of the liquid detergent. If the content is above the lower limit of the above range, the enzyme stability is excellent, and if it is below the upper limit, the low-temperature stability is excellent.

[0055] In liquid detergents, the mass ratio of the total content of compounds (a1) and (a3) ​​to the content of compound (a2), (a1+a3) / (a2), is preferably 0.1 or higher, more preferably 0.1 to 10, even more preferably 1 to 10, and most preferably 1 to 5. If it is above the lower limit of the above range, the enzyme stability is excellent. If it is below the upper limit, the sebum cleansing power is excellent, and high cleansing power can be achieved with a small amount of use.

[0056] The content of component (B) is preferably 2 to 31% by mass, more preferably 4 to 26% by mass, and most preferably 6 to 21% by mass, relative to the total mass of the liquid detergent. If the value is above the lower limit of the above range, the enzyme stability is excellent; if it is below the upper limit, the color stability at high temperatures is excellent.

[0057] 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, relative to the total mass of the liquid detergent. If the value is above the lower limit of the above range, the enzyme stability is excellent, and if it is below the upper limit, the color stability at high temperatures is excellent. The AES content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and most preferably 10 to 20% by mass, relative to the total mass of the liquid detergent. Values ​​above the lower limit of the above range provide excellent enzyme stability, while values ​​below the upper limit provide excellent low-temperature stability.

[0058] In liquid detergents, the LAS / AES ratio, which represents the mass ratio of LAS content to AES content, is preferably 0.1 or higher, more preferably 0.1 to 20, even more preferably 0.5 to 20, and most preferably 0.5 to 10. A value above the lower limit of the above range provides excellent low-temperature stability. A value below the upper limit provides excellent color stability at high temperatures.

[0059] In liquid detergents, the mass ratio of the content of component (A) to the content of component (B), (A) / (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. If the value is above the lower limit of the above range, the enzyme stability is excellent. If the value is below the upper limit, the low-temperature stability is excellent.

[0060] The total content of component (A), component (B), and other surfactants (hereinafter also referred to as "total surfactant content") is preferably 40% by mass or more, more preferably 40-70% by mass, and most preferably 40-60% by mass, relative to the total mass of the liquid detergent. If the content is above the lower limit of the above range, it exhibits excellent sebum cleansing power and high cleaning power with a small amount of use. If the content is below the upper limit, it exhibits excellent color stability at high temperatures.

[0061] 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, relative to the total mass of the liquid detergent. If the content is above the lower limit of the above range, it has an excellent effect on improving enzyme stability, and if it is below the upper limit, it does not easily reduce low-temperature stability.

[0062] In liquid detergents, the mass ratio of component (A) to component (C), expressed as (A) / (C), is preferably 70 or higher, more preferably 70 to 120, and most preferably 80 to 100. If the value is above the lower limit of the above range, enzyme stability is excellent. If the value is below the upper limit, color stability at high temperatures is excellent.

[0063] In liquid detergents, the mass ratio of the content of component (B) to the content of component (C), (B) / (C), is preferably 10 or more, more preferably 10 to 100, even more preferably 15 to 50, and most preferably 15 to 40. If it is above the lower limit of the above range, the enzyme stability is excellent. If it is below the upper limit, the color stability at high temperatures is excellent.

[0064] In liquid detergents, the mass ratio of the content of component (E) to the content of component (C), (E) / (C), is preferably 20 to 70, more preferably 25 to 60, and most preferably 40 to 60. If it is above the lower limit of the above range, the color change of the liquid detergent is less likely to occur, and if it is below the upper limit, the cleaning performance is less likely to deteriorate.

[0065] In terms of minimizing color changes in the liquid detergent, it is preferable that the liquid detergent does not contain phenylboronic acid derivatives other than component (C) (for example, 4-formylphenylboronic acid, etc.), or if it does contain them, only in small amounts. For example, the content of phenylboronic acid derivatives other than component (C) relative to the total mass of the liquid detergent is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less. It may also be zero.

[0066] The content of component (D) is preferably 0.1 to 7% by mass, more preferably 0.3 to 6% by mass, and most preferably 0.5 to 5% by mass, relative to the total mass of the liquid detergent. If it is above the lower limit of the above range, the cleaning power is excellent, and if it is below the upper limit, the low-temperature stability is excellent.

[0067] 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, relative to the total mass of the liquid detergent. Furthermore, 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, relative to the total mass of the liquid detergent. In other words, 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, relative to the total mass of the liquid detergent. (E) If the content of component is below the above upper limit, it is easier to miniaturize the container of the liquid detergent.

[0068] When component (F) is incorporated into a liquid detergent, the content of component (F) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of the liquid detergent, in terms of its excellent effect in improving low-temperature stability. On the other hand, in terms of minimizing color changes in the liquid detergent, the content of component (F) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total mass of the liquid detergent. In other words, the content of component (F) is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 30% by mass, relative to the total mass of the liquid detergent.

[0069] <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 detergent can be adjusted by adding a pH adjuster as needed. pH is the value measured using a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) with the sample temperature set at 25°C.

[0070] <Manufacturing method> The liquid detergent of the present invention can be manufactured in accordance with conventionally known methods for manufacturing liquid detergents. For example, it can be manufactured by adding each component except the pH adjuster to a portion of water and mixing, then adding the pH adjuster as needed to adjust the pH, and finally adding the remaining water to bring the total volume to 100% by mass. The obtained liquid detergent is preferably contained in a container such as a bottle, squeeze container, or pouch container to produce a liquid detergent product in a container.

[0071] One form of container for a liquid detergent product can be a plastic container comprising a plastic container body and a plastic cap. The container body has an opening, and the cap is configured to be detachably attached to the opening. The material of the container body is preferably a transparent or semi-transparent synthetic resin such as polyethylene resin, polypropylene resin, or polyethylene terephthalate (PET). A possible molding method for the container body is, for example, biaxial stretch blow molding. The cap is preferably a cap with a measuring cylinder portion that can measure 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 molding method for the cap is injection molding. The shape of the measuring cap can be a known shape. For example, it can be a shape such as that described in Japanese Patent Application Publication No. 2020-200095, which has a measuring cylinder portion extending in the axial direction and a tongue-shaped portion provided at the axial end of the measuring cylinder portion in a part of the circumferential direction centered on the axis and protruding in the axial direction.

[0072] <How to use> Methods of using liquid detergents include, for example, putting the liquid detergent into the detergent dispenser of the washing machine and then starting the washing machine; adding the liquid detergent to the water along with the items to be washed during the wash cycle; immersing the items to be washed in a detergent solution prepared by dissolving the liquid detergent in water beforehand; and applying the liquid detergent directly to the items to be washed, leaving it for, for example, 3 minutes to 24 hours, and then performing a normal wash.

[0073] Furthermore, it is preferable to use a washing machine equipped with an automatic detergent dispensing function, which has become practical in recent years. The automatic detergent dispensing function automatically dispenses detergent from a detergent tank into the washing tub via a dispensing pipe. A measuring device, such as a syringe pump, is installed along the dispensing pipe, allowing a set amount of detergent, depending on the amount of laundry, to be transferred from the tank to the washing tub.

[0074] Using the automatic detergent dispensing function not only eliminates the hassle of measuring, but also prevents liquid detergent from getting on your hands or spilling and staining the washing machine or surrounding area during measurement. Furthermore, because the liquid detergent of the present invention is concentrated, the amount used per wash may be very small, around 10 mL. Such small amounts of liquid detergent are difficult to measure accurately with a cap or similar device, making it easy to end up with insufficient or excessive liquid. Using an automatic detergent dispenser allows for accurate measurement of even small amounts of liquid detergent, ensuring sufficient cleaning power and avoiding waste due to overuse, which is preferable.

[0075] Furthermore, it is preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. Using an automatic dispenser is also preferable because it allows for accurate measurement of even small amounts of liquid cleaning agent, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse. Some automatic dispensers utilize infrared sensors or other technologies to dispense liquids automatically without requiring the user to touch any switches. Using such an automatic dispenser allows users to measure out liquid detergent simply by holding a container in one hand, significantly reducing the burden on the user.

[0076] Furthermore, when using an automatic dispenser, it is preferable to receive the liquid detergent dispensed into a flexible container and then place that flexible container directly into the washing machine. This ensures that the entire amount of the dispensed liquid detergent is reliably dissolved in the washing solution. Examples of materials for flexible containers that can be directly put into a washing machine include silicone resin, polyvinyl chloride, elastomer, flexible polyester, flexible polypropylene, and polyurethane.

[0077] Examples of items to be washed include clothing, dishcloths, towels, sheets, curtains, and other textile products. The material of the textile products is not particularly limited and may be any of the following: natural fibers such as cotton, silk, and wool, or synthetic fibers such as polyester and polyamide. When using a liquid cleaning agent dissolved in water, it is preferable to dilute it, for example, 5 to 5000 times (by volume). The bath ratio (mass of washing solution / mass of clothing), which is the amount of water per unit of clothing, is preferably 5 or higher for drum-type washing machines and 10 or higher for top-loading washing machines. The amount of liquid detergent used in the washing process is preferably such that the ratio of the total mass of the items to be washed (amount of cloth) to the total mass of the liquid detergent is 10 to 500, more preferably 10 to 300, and even more preferably 10 to 100. Liquid detergents are suitable as detergents for textile products.

[0078] The liquid detergent of the present invention is a concentrated liquid detergent containing enzymes, and can exhibit high cleaning power with a small amount of use. Furthermore, despite having a high surfactant concentration and being highly concentrated, it exhibits excellent enzyme stability, low-temperature stability, and color stability at high temperatures. In particular, since amylase is easily deactivated, the present invention is highly effective when applied to concentrated liquid detergents containing amylase. Furthermore, as shown in the examples described later, when 4-formylphenylboronic acid is added to a concentrated liquid detergent containing an enzyme, enzyme stability is achieved, but the liquid detergent is prone to yellowing when exposed to high temperatures. In contrast, the liquid detergent of the present invention incorporates component (C) having a specific molecular structure, and by setting a specific balance between (A) and (B), it is possible to simultaneously achieve enzyme stability, color stability at high temperatures, and low-temperature stability.

[0079] Washing machines equipped with an automatic detergent dispensing function tend to experience a rise in temperature inside the detergent tank during the drying cycle. Furthermore, because the detergent is transferred by suction using a syringe pump or similar device, the tank is not completely sealed. As shown in the embodiments described later, storing liquid detergent in the tank of a washing machine equipped with an automatic detergent dispensing function tends to reduce the enzyme retention rate. The liquid detergent of the present invention exhibits excellent color stability and enzyme stability at high temperatures, making it suitable as a liquid detergent for automatic detergent dispensing, to be stored in the tank of a washing machine equipped with an automatic detergent dispensing function. In addition, because it is a concentrated liquid detergent that can exhibit high cleaning power with a small amount of use, it is also suitable as a liquid detergent for automatic detergent dispensing because it allows for a large number of washes using the capacity of the washing machine's tank.

[0080] A preferred embodiment of the liquid detergent of the present invention is, for example, the following embodiment I. (Pattern I) The liquid detergent contains component (A), component (B), component (C), component (D), component (E), and component (F). Component (A) contains one or more polyoxyalkylene-type nonionic surfactants (A1) having EO, and the average number of moles of EO added per mole of component (A1) is 7 to 15 moles. (B) Component comprises either LAS and AES or both, (C) component is one or more selected from 2-methylphenylboronic acid, 3-methylphenylboronic acid, and 4-methylphenylboronic acid (C1), (D) The component is either a protease or amylase or both (D1), (E) The content of component is 30% by mass or less relative to the total mass of the liquid detergent. (F) The content of component is 1% by mass or more relative to the total mass of the liquid detergent. The mode in which (A) / (B) is 1 or greater. In this invention, the total content of each component of the liquid detergent does not exceed 100% by mass.

[0081] In embodiment I, the ratio of the total mass of component (A1) to the total mass of 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 also be 100% by mass. In embodiment I, the ratio of the sum of LAS and AES to the total mass of component (B) 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 also be 100% by mass. In embodiment I, the ratio of the total mass of component (C1) to the total mass of 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 also be 100% by mass. In embodiment I, the ratio of the total mass of component (D1) to the total mass of component (D) 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 also be 100% by mass. In embodiment I, the liquid detergent is preferably a liquid detergent for automatic detergent dispensing, which is contained in the tank of a washing machine equipped with an automatic detergent dispensing function. [Examples]

[0082] 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 embodiment are as shown in the <Raw Materials Used> section below.

[0083] <Raw materials used> [(A) component] • Linear AE(20EO): A primary alcohol (mass ratio of C12 alcohol / C14 alcohol = 7 / 3) to which 20 moles of ethylene oxide are added. In formula (a1), R 11 This consists of a C12 alkyl group and a C14 alkyl group (C14) (mass ratio of C12:C14 = 70:30), R 12 R that bonds to the hydrogen atom and -O- 11 A compound in which the carbon atoms are primary carbon atoms, with s = 20, t = 0, and u = 0. • Linear AE(15EO): In the above "Linear AE(20EO)", the amount of ethylene oxide added to 1 mole of the primary alcohol is changed to the equivalent of 15 moles, and s in formula (a1) is changed to 15. • Linear AE(12EO): In the above "Linear AE(20EO)", the amount of ethylene oxide added to 1 mole of the primary alcohol is changed to the equivalent of 12 moles, and s in formula (a1) is changed to 12. · Linear AE(9EO): In the above-mentioned "linear AE(20EO)", the ethylene oxide added to 1 mole of the primary alcohol is changed to 9 moles, and s in the formula (a1) is changed to 9. · Linear AE(7EO): In the above-mentioned "linear AE(20EO)", the ethylene oxide added to 1 mole of the primary alcohol is changed to 7 moles, and s in the formula (a1) is changed to 7. · Linear AE(5EO): In the above-mentioned "linear AE(20EO)", the ethylene oxide added to 1 mole of the primary alcohol is changed to 5 moles, and s in the formula (a1) is changed to 5.

[0084] · 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 (ethylene oxide equivalent to 7 moles is added to an alcohol having 13 carbon atoms). In the general formula (a2), R 13 is a branched-chain 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 (compound (a2)). It is synthesized by the following synthesis method. · Primary branched AE(10EO): Ethylene oxide equivalent to 10 moles is added to a C10 alcohol obtained by subjecting pentanol to a Garbett reaction. · Secondary branched (7EO): Ethylene oxide equivalent to 7 moles is added to 1 mole of a secondary alcohol. In the 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): A secondary alcohol prepared by adding 12 moles of ethylene oxide to 1 mole of secondary alcohol. In formula (a2), R 13 R is an alkyl group with 12 to 14 carbon atoms. 14 R that bonds to the hydrogen atom and -O- 13 A compound in which the carbon atoms are secondary carbon atoms, v is 7, w is 0, and x is 0.

[0085] [(B) Component] • LAS: A linear alkylbenzene sulfonate having an alkyl group with 10 to 14 carbon atoms, manufactured by Lion Corporation, trade name "Lypon (registered trademark) LH-200". AES: Polyoxyalkylene alkyl ether sulfate (a mixture of polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene myristyl ether sodium sulfate, with an average number of moles of EO added of 1). R in equation (b1) 17 The compound is a linear alkyl group having 12 and 14 carbon atoms, m is 1, n is 0, and M is sodium, with the proportion of the compound where m is 0 and n is 0 relative to the total AES being 43% by mass. It was synthesized by the method of Preparation Example 1 below. [(C) component] • C-1:4-methylphenylboronic acid: • C-2:4-methoxyphenylboronic acid: • Comparative component 1: 4-formylphenylboronic acid [(D) component] • Protease 1: Product name "ProgressUno", manufactured by Novozymes Japan. • Amylase 1: Product name "Amplify Prime100L", manufactured by Novozymes Japan. • Mannanase 1: Product name "Mannaway200L", manufactured by Novozymes Japan. • Cellulase 1: Product name "Carezyme Premium 4500L", manufactured by Novozymes Japan. • Pectinase 1: Product name "Xpect1000L", manufactured by Novozymes Japan. [(E) component]: • Water: Product name "Purified Water," manufactured by Kanto Chemical Co., Ltd. [(F) component] • Monoethanolamine: Product name "Monoethanolamine", manufactured by Nippon Shokubai Co., Ltd.

[0086] [Optional ingredients] • Polyethylene glycol: Manufactured by Junsei Chemical Co., Ltd., product name "PEG#1000", mass-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 Research Institute, product name "Sodium Lactate 60E"). • Paratoluenesulfonic acid: Hydrotropic agent (manufactured by Kyowa Hakko Kirin Co., Ltd., product name "PTS acid"). • Citric acid: (Manufactured by Ipposha Oil & Fat Industry Co., Ltd., product name "Liquid Citric Acid"). • Dichrosan: 4,4'-dichloro-2-hydroxydiphenyl ether (manufactured by BASF, trade name "TINOSAN HP100"). • BIT: 1,2-Benzisothiazolin-3-one (manufactured by Clariant Japan, product name "NIPACIDE BIT20"). • BHT: Antioxidant, dibutylhydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd., product name "SUMILZER BHT-R"). • Fragrance: Fragrance composition A as described in Tables 11-18 of Japanese Patent Publication No. 2002-146399. ·Pigment: Manufactured by Kinmi Kasei Co., Ltd., product name "Green No. 3". • NaOH: Sodium hydroxide, pH adjuster (manufactured by Toagosei Co., Ltd., product name "Sodium Hydroxide").

[0087] [Preparation Example 1: Synthesis of AES] In a 4L autoclave, 400g of Procter & Gamble's product name CO1270 alcohol (a mixture of C12 alcohol and C14 alcohol in a mass ratio of 75 / 25) and 0.8g of potassium hydroxide catalyst were charged as the raw material alcohol. After purging the autoclave with nitrogen, the temperature was increased while stirring. Next, 91 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180°C and the pressure at 0.3 MPa or less to obtain an alcohol ethoxylate. Analysis using a gas chromatograph (Hewlett-Packard GC-5890), a flame ionization detector (FID), and an Ultra-1 column (HP, L25m × φ0.2mm × T0.11μm) revealed that the obtained alcohol ethoxylate had an average number of ethylene oxide additions of 1.0. Furthermore, the amount of the compound without ethylene oxide addition (which ultimately becomes component (a-0)) was 43% by mass of the total obtained alcohol ethoxylate. Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, purged with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. After the addition was complete, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Subsequently, this was neutralized with an aqueous sodium hydroxide solution to obtain AES.

[0088] <Storage container> The container used to store the liquid detergent was either container A or container B shown below. Container A: A container for a liquid detergent product, comprising a transparent plastic container body (capacity 500 mL, wall thickness 0.05~1.2 mm, maximum wall thickness 1.2 mm) made of biaxially stretched blow-molded polyethylene terephthalate (PET) resin, and a transparent plastic measuring cap made of injection-molded polypropylene (PP) resin. Container B: A washing machine tank with an automatic detergent dispensing function. The automatic detergent dispensing tank (part number BD-SX110CL-002, capacity: approximately 1000mL, non-sealed container) included with a Hitachi drum-type washing machine (BD-SX110E) was used.

[0089] <Examples 1-24, Comparative Examples 1-7> Liquid detergents were manufactured according to the formulations shown in Tables 1-6. The formulations of optional components are shown in Table 7. The content shown in Table 7 is the percentage (mass %) of 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.). Then, component (C) was added and dissolved. Subsequently, components (F) and (D) were added and stirred thoroughly again. Next, an appropriate amount of NaOH was added to achieve a pH of 7.7 at 25°C, and then water was added to make the total volume 100% by mass to obtain a liquid detergent.

[0090] The obtained liquid detergents were evaluated for their cleaning power (sebum cleaning power), color stability at high temperatures, enzyme stability, and low-temperature stability using the evaluation methods described below. The evaluation results are shown in Tables 1 to 6. For each stability evaluation, storage container A or B as shown in the table was used. Storage container A was sealed with 400 mL of liquid detergent, and storage container B was sealed with 400 mL of liquid detergent. Note that the unit of the blending amount in the table is "mass %", indicating the amount on a pure content basis. Also, a blank space for the blending amount means that the ingredient is not included (bleeding amount 0 mass %). The appropriate amount of NaOH refers to the amount necessary and sufficient to bring the pH of the liquid detergent to 7.7. Furthermore, the amount of water used is calculated assuming that the amount of NaOH is zero. The actual amount of water used is the amount that makes the total amount (mass%) of all components, including NaOH, equal 100% by mass.

[0091] <Evaluation Method> [Method for evaluating the stability of enzymes (amylase)] Since amylase is particularly susceptible to inactivation, the enzyme stability of amylase was evaluated as an indicator of the enzyme stability of liquid detergents containing amylase. Specifically, after manufacturing each example of the liquid detergent, it was placed in a storage container and stored for two weeks at 40°C and 5°C, respectively. The amylase activity of the liquid detergent stored at 40°C for two weeks (40°C stored product) and the liquid detergent stored at 5°C for two weeks (5°C stored product) was measured as described below.

[0092] As the amylase substrate, we used "Fadebas Amylase Test 50T" (manufactured by 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 form a blue solution, and the amylase activity can be determined by measuring its absorbance (620 nm).

[0093] (Preparation of buffer solution) 20.0 g of sodium sulfite (manufactured by Junsei Chemical Co., Ltd., 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 dodecahydrate (manufactured by Kanto Chemical Co., Ltd., special grade, etc.), 0.015 g of calcium chloride dihydrate (manufactured by Kanto Chemical Co., Ltd., first grade, etc.), and 0.75 mL of Brij 35 (30% aqueous solution, manufactured by MERCK) were accurately weighed, dissolved in deionized water, and diluted to 1 L to prepare a buffer solution. For each example, 0.1 g of the product stored at 40°C and the product stored at 5°C were diluted with the above buffer solution to create the sample solution.

[0094] To 1 g of the sample solution, 5 mL of the above buffer and 1 tablet of the above "Fadebas Amylase Test 50T" were added, and the mixture was stirred with a vortex mixer for 10 seconds. The mixture was then allowed to stand at 40°C for 5 minutes to allow the enzymatic reaction to proceed. Subsequently, 1 mL of 1 mol / L (1N) sodium hydroxide solution (manufactured by Kanto Chemical Co., Ltd.), an enzyme reaction stopper, was added to the solution, and the mixture was stirred with a vortex mixer for 10 seconds to stop the reaction. After that, any unreacted substrate remaining in the solution was removed with filter paper, and the filtrate was collected. The absorbance of the recovered filtrate at a wavelength of 620 nm (absorbance A) was measured using a Shimadzu UV-Vis spectrophotometer UV-160.

[0095] To eliminate the influence of absorption of components other than the target component, 1 mL of 1 mol / L (1N) sodium hydroxide solution, an enzyme reaction inhibitor, was added to 1 g of each sample solution and mixed with a vortex mixer for 10 seconds. Then, 1 tablet of the above-mentioned "Fadebas Amylase Test 50T" was added and mixed with a vortex mixer for 10 seconds, and the mixture was allowed to stand at 40°C for 15 minutes. After that, insoluble components were removed using a 0.45 μm filter and the filtrate was collected. Subsequently, the absorbance of the filtrate at a wavelength of 620 nm (absorbance B) was measured using UV-160. A larger difference between absorbance A and absorbance B indicates a greater amount of substrate decomposition products present in the filtrate.

[0096] Based on the above results of amylase activity measurement, the remaining amylase activity percentage (%) was calculated using the following formula (i). Amylase activity retention rate = (Absorbance A of product stored at 40°C - Absorbance B of product stored at 40°C) / (Absorbance A of product stored at 5°C - Absorbance B of product stored at 5°C) × 100 ... (i)

[0097] The remaining amylase activity percentage (%) was used as an indicator to evaluate enzyme stability based on the following criteria, and "◎" and "○" were considered acceptable. <Evaluation Criteria> ◎: Enzyme residual rate 80% or more and 100% or less. ○: Enzyme retention rate of 60% or more but less than 80%. △: Enzyme retention rate 40% or more but less than 60%. ×: Enzyme retention rate 0% or more and less than 40%.

[0098] [Method for evaluating color stability at high temperatures] The liquid cleaning agent was placed in either storage container A or B and stored in a constant temperature bath at 50°C for 7 days. To evaluate the change in color tone before and after storage, the absorbance of the liquid detergent at a wavelength of 420 nm was measured using a Shimadzu UV-Vis spectrophotometer UV-160. Based on the absolute value of the difference in absorbance before and after storage, the change in color tone was evaluated according to the following evaluation criteria, with "◎" and "○" being considered passing grades. <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 less than or equal to 0.30. △: The absolute value of the difference in absorbance is greater than 0.30 and less than or equal to 0.50. ×: The absolute value of the difference in absorbance exceeds 0.50.

[0099] [Method for evaluating low-temperature stability] The liquid detergent was placed in either storage container A or B and stored in a constant temperature bath at 5°C for 7 days. After storage, the appearance of the liquid inside the storage container was visually observed, and its low-temperature stability was evaluated according to the evaluation criteria below. "◎" and "○" were considered acceptable. <Evaluation Criteria> ◎: The liquid is clear, no precipitates or other substances are observed, and the liquid has high fluidity. ○: The liquid is clear, no precipitates or other substances are observed, and the liquid has low fluidity. △: The liquid is cloudy, but it is still fluid. ×: The liquid is cloudy and lacks fluidity.

[0100] [Method for evaluating cleaning power] The soiled cloth was made by impregnating oil-based cloth (unstained cloth) with artificial stains (manufactured by the Japan Laundry Science Association), and then cutting it into 5cm x 5cm pieces. A Terg-O-tometer (manufactured by UNITED STATES TESTING) was used as the cleaning test device. As the washing solution, a liquid detergent was added to 900 mL of water (25°C, 5°DH) to a concentration of 200 ppm, and the mixture was stirred for 30 seconds. The cleaning solution, 10 of the aforementioned soiled cloths, and the cleaned knitted cloth were placed in a cleaning tester, and the cloths were washed for 10 minutes at 120 rpm and 25°C, with a bath ratio of 20:1. Afterwards, they were transferred to a twin-tub washing machine (Mitsubishi Electric, product name "CW-C30A1-H1"), spun dry for 1 minute, rinsed in 30L of water (25°C, 5°DH) for 3 minutes, and air-dried. The reflectance of unstained cloth and soiled cloth before and after washing was measured using a colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700"), and the washing rate (%) was calculated using 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 reflectance (%). For 10 soiled cloths, the cleaning rate (%) was calculated and the average value was determined. Using the average cleaning rate (%) as an indicator, the sebum cleansing power was evaluated based on the following criteria, with "◎" and "○" being considered passing grades. <Evaluation Criteria> ◎: The average cleaning rate is between 80% and 100%. ○: The average cleaning rate is between 60% and 80%. △: The average cleaning rate is between 40% and 60%. ×: The average cleaning rate is between 0% and 40%.

[0101] [Table 1]

[0102] [Table 2]

[0103] [Table 3]

[0104] [Table 4]

[0105] [Table 5]

[0106] [Table 6]

[0107] [Table 7]

[0108] As shown in the results in Tables 1-6, the liquid detergents of Examples 1-24 exhibited high cleaning power with small amounts of use, and also showed good enzyme stability, color stability at high temperatures, and low-temperature stability.

[0109] Examples 1 and 20 are examples where the liquid detergent composition is the same, but the storage container is different. In Example 20, where the liquid detergent was stored in the tank of a washing machine equipped with an automatic detergent dispensing function (storage container B), the enzyme retention rate was lower compared to Example 1, where it was stored in a sealed container, storage container A.

[0110] Comparing Example 1 with Comparative Example 1, Comparative Example 1, which did not contain component (C), showed the same color stability at high temperatures and low temperature stability as Example 1, but its enzyme stability was significantly inferior. Comparative Example 2 uses the same type and total amount of surfactant as Example 1, but with a smaller mass ratio of (A) / (B). Compared to Example 1, it exhibited inferior color stability at high temperatures and low-temperature stability. Comparative Example 3 had the same types of ingredients as Example 1, but the proportion of water was higher and the proportion of nonionic surfactant was lower, resulting in inferior cleaning power. In other words, because Comparative Example 3 was not a concentrated type, it could not exert sufficient cleaning power with a small amount of use. Comparative Example 4 is an example in which 4-formylphenylboronic acid, comparative component 1, is used instead of component (C) of Comparative Example 3. However, because it is not a concentrated type, no yellowing occurred even when exposed to high temperatures.

[0111] Comparing Example 1 with Comparative Example 5, Comparative Example 5, which contained comparative component 1, 4-formylphenylboronic acid, instead of component (C), achieved a similar level of enzyme stability as Example 1, but the liquid detergent underwent yellowing when exposed to high temperatures. Comparing Example 20 with Comparative Examples 6 and 7, Comparative Example 6, which did not contain component (C), showed comparable color stability at high temperatures and low temperature stability to Example 20, but its enzyme stability was significantly inferior. Furthermore, Comparative Example 7, which contained comparative component 1, 4-formylphenylboronic acid, instead of component (C), achieved enzyme stability comparable to Example 20, but the liquid detergent yellowed when exposed to high temperatures.

Claims

1. (A) a nonionic surfactant, (B) a non-soap-based anionic surfactant, (C) a compound represented by the following formula 1, (D) an enzyme, and (E) water, The content of component (C) is 0.05% by mass or more and 0.7% by mass or less, The content of component (E) is 40% by mass or less, A liquid detergent composition for textile products, wherein the mass ratio (A) / (B), which represents the mass ratio of the content of component (A) to the content of component (B), is 2.5 or more and 25 or less. 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a methoxy group.

2. The liquid detergent composition for textile products according to Claim 1, wherein component (B) comprises one or more selected from the group consisting of polyoxyalkylene alkyl ether sulfates and salts thereof, and polyoxyalkylene alkenyl ether sulfates and salts thereof.

3. The component (A) comprises one or both of the compound (a1) represented by the following general formula (a1) and the compound (a3) ​​represented by the following general formula (a3), and the compound (a2) represented by the following general formula (a2), The liquid detergent composition for textile products according to claim 1, wherein (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 0.1 or more and 10 or less. 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 repeating number of EO, A 11 O is at least one of PO (oxypropylene group) and BO (oxybutylene group), t is a number from 0 to 6 indicating the average repeating number of A 11 O, and u is a number from 0 to 20 representing the average repeating number of EO.) R 13 -O- [(EO) v / (A 12 O) w ] - (EO) x -R 14 ... (a2) (In general formula (a2), R 13 is a branched 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 repeating number of EO, A 12 O is at least one of PO (oxypropylene group) and BO (oxybutylene group), w is a number from 0 to 6 indicating the average repeating number of A 12 O, and x is a number from 0 to 20 representing the average repeating number of EO.) 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 repeating number of EO, A 13 is at least one of PO (oxypropylene group) and BO (oxybutylene group), q is a number from 0 to 6 indicating the average repeating number of A 13 O, and r is a number from 0 to 20 representing the average repeating number of EO.)

4. The liquid detergent composition for textile products according to Claim 1, wherein the mass ratio of the content of component (B) to the content of component (C), (B) / (C), is 10 or more and 100 or less.

5. The liquid detergent composition for textile products according to any one of claims 1 to 4, further comprising (F) monoethanolamine.

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