Liquid detergent composition for textile product

Abstract

To provide a liquid detergent composition for a textile product excellent in detergency, enzyme stability, and liquid stability at a low temperature.SOLUTION: A liquid detergent composition for a textile product includes: constituent (A) at least one selected from the group consisting of amylase and mannanase; constituent (B) protease; constituent (C) an antioxidant; constituent (D) a chelate agent; constituent (E) at least one selected from the group consisting of a solvent expressed by the following formula (E1), and a solvent expressed by the following formula (E2); and constituent (F) a non-soap based surface active agent, where the content of the constituent (C) is 0.05 mass% or more, the content of the constituent (D) is 0.02 mass% or more, and the mass ratio expressed by the constituent (D) / the constituent (C) is 60 or under. R4(OR5)yOH (E1), CH3OCR6(CH3)CHR7CHR8OR9 (E2).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] There are two types of detergent compositions generally used for textile products, namely, powder detergent compositions and liquid detergent compositions, for cleaning clothing, etc. Demand for liquid detergent compositions is increasing because there is no concern about residual detergent and they can be applied to clothing, etc. In detergent compositions, surfactants act as the main cleaning components, and various components such as enzymes are blended. Enzymes play an important role as components that exhibit various performances in small amounts. On the other hand, when enzymes are blended into liquid detergent compositions, they may precipitate or denature. To address this problem, Patent Document 1 proposes the use of amylase in combination with an antioxidant. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-084141 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, when an antioxidant is contained in a liquid detergent composition together with an enzyme, the liquid stability at low temperatures may decrease. In addition, when the content of enzymes is increased to improve cleaning power, the stability of the enzymes may be insufficient even when antioxidants are used in combination. In particular, when the content of proteases is increased, other enzymes (e.g., amylase or mannanase) are easily inactivated. In recent years, washing machines with an automatic detergent dispenser function have become widespread. In such washing machines, a tank inside the washing machine is filled with a liquid detergent in an amount sufficient for multiple washes, and the liquid detergent is stored in the tank during washes. The tank is generally not sealed and is exposed to heat generated by the washing machine. Therefore, the inside of the tank is prone to evaporation of water and solvents in the liquid detergent and thermal denaturation of the liquid detergent, creating a harsh environment for enzyme stability.

[0005] An object of the present invention is to provide a liquid detergent composition for textile products which has excellent detergency, enzyme stability, and liquid stability at low temperatures. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] Component (A): at least one selected from the group consisting of amylase and mannanase; (B) component: a protease; (C) component: antioxidant, (D) component: a chelating agent, Component (E): at least one selected from the group consisting of a solvent represented by the following formula (E1) and a solvent represented by the following formula (E2), (F) component: a non-soap surfactant, Contains The content of the (C) component is 0.05% by mass or more, The content of the (D) component is 0.02% by mass or more, A liquid detergent composition for textile products, in which the mass ratio of the component (D) to the component (C) is 60 or less. R 4 (OR 5 ) y OH (E1) CH3OCR 6 (CH3)CHR 7 CHR 8 OR 9 (E2) However, R 4 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 5is an alkylene group having 2 to 4 carbon atoms, and y is OR 5 is a number between 1 and 5 that represents the average number of repetitions of R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 9 is a hydrogen atom or an acetyl group. [2] A liquid detergent composition for textile products according to [1], having a water content of 45% by mass or less. [3] Component (G): A liquid detergent composition for textile products according to [1] or [2], further comprising a glycol-based solvent. [4] The liquid detergent composition for textile products according to any one of [1] to [3], which is for use in a washing machine equipped with an automatic detergent dispensing function. Effect of the Invention

[0007] According to the present invention, it is possible to provide a liquid detergent composition for textile products which has excellent detergency, enzyme stability, and liquid stability at low temperatures. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] A liquid detergent composition for textile products according to one embodiment of the present invention (hereinafter also simply referred to as the "liquid detergent composition") contains components (A), (B), (C), (D), (E) and (F).

[0009] <Component (A)> The component (A) is at least one selected from the group consisting of amylase and mannanase. Component (A) contributes to improving detergency.

[0010] Amylase is generally commercially available as a preparation containing amylase (amylase preparation). When preparing a liquid detergent composition, it is usually incorporated in the form of an amylase preparation. Examples of amylase preparations include those available from Novozymes under the trade names Termamyl (registered trademark) 300L, Termamyl Ultra 300L, Duramyl (registered trademark) 300L, Duramyl 16L, Stainzyme (registered trademark) 12L, Stainzyme Plus 12L, Amplify (registered trademark) 12L, Amplify Prime 100L, and Medley (registered trademark) Core 210L; those available from Genencor under the trade name Maxamyl; those available from Amano Enzyme Inc. under the trade name Pullulanase Amano; those available from Seikagaku Corporation under the trade name DB-250; and those available from Danisco Japan Co., Ltd. under the trade name PREFERENZ (registered trademark) S210.

[0011] Mannanase is generally commercially available as a preparation containing mannanase (mannanase preparation). When preparing a liquid detergent composition, it is usually formulated in the form of a mannanase preparation. Examples of mannanase preparations include those available from Novozymes under the trade names Mannaway 4L and Mannaway 200L.

[0012] <(B) component> Component (B) is a protease. Component (B) contributes to improving detergency.

[0013] Proteases are generally commercially available as preparations containing proteases (protease preparations). When preparing liquid detergent compositions, they are usually formulated in the form of protease preparations. As the protease preparation, an enzyme preparation containing component (A) together with protease can also be used. Examples of protease preparations include those available from Novozymes under the trade names Progress Uno (registered trademark) 100L, Progress Uno (registered trademark) 101L, Medley (registered trademark) Core 210L, Savinase (registered trademark) 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase (registered trademark) 16L TypeEX, Everlase 16L, Everlase Ultra 16L, Esperase (registered trademark) 8L, Alcalase (registered trademark) 2.5L, Alcalase Ultra 2.5L, Liquanase (registered trademark) 2.5L, Liquanase (registered trademark) Ultra 2.5L, Liquanase Ultra 2.5XL, and Coronase (registered trademark) Evity 48L; and those available from Genencor under the trade names Purafect (registered trademark) L, Purafect OX, and Properase. L; Examples of the product names available from Danisco Japan Co., Ltd. include PREFERENZ (registered trademark) P200 and PREFERENZ P300.

[0014] <(C) component> Component (C) is an antioxidant. The component (C) contributes to improving the enzyme stability.

[0015] Examples of component (C) include dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), distyrenated cresol, vitamin E (tocopherol), sodium erythorbate, ascorbic acid, methoxyphenol, sodium sulfite, sodium bisulfite, sulfur dioxide, coffee bean extract (chlorogenic acid), green tea extract (catechin), and rosemary extract. Among the above, component (C) preferably contains at least one selected from the group consisting of BHT, BHA, distyrenated cresol, ascorbic acid, sodium sulfite, and sodium hydrogen sulfite, more preferably contains at least one selected from the group consisting of BHT, BHA, and ascorbic acid, and particularly preferably contains BHT. BHT has excellent enzyme stabilizing ability, and furthermore, when the liquid detergent composition is stored in a pouch or bottle, it can suppress a decrease in oxygen concentration in the head space and fading of the colorant in the liquid detergent composition.

[0016] <(D) component> The component (D) is a chelating agent. The component (D) contributes to improving the liquid stability at low temperatures. Conventionally, one of the reasons for the low liquid stability at low temperatures is thought to be that the metal ions contained in the raw materials turn into metal salts at low temperatures and precipitate. It is speculated that component (D) enhances liquid stability by aiding the dissolution of metal ions in the liquid detergent composition at low temperatures with its metal sequestering ability, and inhibiting the metal ions from turning into metal salts.

[0017] Examples of the component (D) include acids and salts thereof such as citric acid, succinic acid, ethylenediaminetetraacetic acid (EDTA), triethylenetetraacetic acid (TTHA), methylglycine diacetic acid (MGDA), 1,3-propane-2-diaminetetraacetic acid (PDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), hydroxyethyliminodiacetic acid (HIDA), hydroxyiminodisuccinic acid (HIDS), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), N,N,N',N'-tetrakis(phosphonomethyl)ethylenediamine (EDTMP), and diethylenetriaminepentakis(methylphosphonic acid) (DTPMP). Examples of the salts include sodium, potassium, calcium, and magnesium. These chelating agents may be used alone or in combination of two or more. Of the above, component (D) preferably contains at least one selected from the group consisting of citric acid, MGDA, HEDP, and salts thereof, and more preferably contains at least one selected from the group consisting of citric acid, MGDA, and salts thereof.

[0018] <(E) component> The component (E) is at least one selected from the group consisting of a solvent represented by the following formula (E1) (hereinafter also referred to as "solvent (E1)") and a solvent represented by the following formula (E2) (hereinafter also referred to as "solvent (E2)"). The component (E) contributes to improving the liquid stability of the liquid detergent composition, particularly at low temperatures.

[0019] R 4 (OR 5 ) y OH (E1) CH3OCR 6 (CH3)CHR 7 CHR 8 OR 9 (E2) However, R 4 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 5 is an alkylene group having 2 to 4 carbon atoms, and y is OR 5 is a number between 1 and 5 that represents the average number of repetitions of R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 9 is a hydrogen atom or an acetyl group.

[0020] Examples of the solvent (E1) include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether (phenoxyethanol), propylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether (also known as butyl carbitol).

[0021] Examples of the solvent (E2) include 3-methoxymethanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy-1-propylbutanol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl acetate, 3-methoxy-2-ethylbutyl acetate, 3-methoxy-2-propylbutyl acetate, 3-methoxy-1-methylbutyl acetate, 3-methoxy-1-ethylbutyl acetate, and 3-methoxy-1-propylbutyl acetate.

[0022] The component (E) may use one type alone, or two or more types in combination. From the viewpoints of enzyme stability and solution stability, the component (E) preferably contains at least one member selected from the group consisting of diethylene glycol monobutyl ether and 3-methoxy-3-methyl-1-butanol.

[0023] <(F) Component> Component (F) is a non-soap surfactant. The component (F) contributes to improving the cleaning power. Examples of the component (F) include nonionic surfactants, non-soap anionic surfactants, amphoteric surfactants, etc. As these surfactants, known surfactants can be used.

[0024] From the viewpoint of liquid stability of the liquid detergent composition, the (F) component preferably contains at least one selected from the group consisting of the nonionic surfactant (F1) and the nonionic surfactant (F2) shown below, and a non-soap anionic surfactant, and more preferably contains the nonionic surfactant (F1), the nonionic surfactant (F2), and a non-soap anionic surfactant.

[0025] [Nonionic surfactant (F1)] The nonionic surfactant (F1) is a nonionic surfactant represented by the following formula (F1). R 11 -O-[(EO) s / (A 11 O) t ]-(EO) u -R 12 (F1) However, R 11 is a straight-chain hydrocarbon group having 8 to 22 carbon atoms, and R 12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an oxyethylene group; s is a number of 3 to 25 indicating the average number of EO repeats; A 11 O is at least one of an oxypropylene group and an oxybutylene group, and t is A 11 is a number from 0 to 6 indicating the average number of repetitions of O, and u is a number from 0 to 20 indicating the average number of repetitions of EO.

[0026] In formula (F1), R 11 The hydrocarbon group has a carbon number of 8 to 22, preferably 10 to 18, and more preferably 12 to 18. 11 The hydrocarbon group of R is linear. 11 The hydrocarbon group may or may not have an unsaturated bond. R bonded to -O- 11 The carbon atom of the -O- bonded R may be a primary or secondary carbon atom. 11 If the carbon atom in is a primary carbon atom, -O- is 11 The R bonded to the carbon atom at the end of the straight chain. 11 If the carbon atom in is a secondary carbon atom, -O- is 11 It bonds to a carbon atom that is not at the end of the straight chain among the carbon atoms that make up the straight chain.

[0027] R 12 When the group is an alkyl group, it has 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms. R12 When 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.

[0028] s is an integer of 3 to 25, preferably 5 to 25, more preferably 7 to 20, further preferably 7 to 18, and particularly preferably 7 to 15. t is an integer of 0 to 6, preferably 0 to 3, and more preferably 0. u is an integer of 0 to 20, preferably 0 to 15, and more preferably 0 to 10. s+u is preferably 3 to 30, more preferably 5 to 25, further preferably 5 to 20, particularly preferably 7 to 20, and most preferably 7 to 15.

[0029] When t is not 0, that is, when the nonionic surfactant (F1) has EO and an oxypropylene group (hereinafter also referred to as "PO"), EO and an oxybutylene group (hereinafter also referred to as "BO"), or EO, ​​PO and BO, [(EO) s / (A 11 O) t In the above, there is no particular limitation on the distribution (arrangement order) of EO and PO, EO and BO, or EO, ​​PO and BO. These may be arranged in a block form or random form. 11 -O-" or PO or BO may be bonded to "R 11 -O-" may be bonded. When t is not 0, the nonionic surfactant (F1) preferably has EO and PO, or EO and BO.

[0030] [Nonionic surfactant (F2)] The nonionic surfactant (F2) is a Guerbet alcohol type nonionic surfactant represented by the following formula (F2). R 1 -CHR 2 -CH2-O-(R 3 O) p -H (F2) However, R 1 and R 2are each independently a linear monovalent hydrocarbon group, R 1 and R 2 The total number of carbon atoms is 4 to 16. 3 is a hydrocarbon group having 1 to 3 carbon atoms, and p is R 3 A number between 1 and 20 indicating the average number of O repeats.

[0031] The nonionic surfactant (F2) has a hydrophobic part (R 1 -CH(R 2 )-CH2-) structure is bulky. This easily disrupts the arrangement of the active agent in a concentrated liquid detergent composition that contains little water, and compared with general branched nonionic surfactants that are not Guerbet alcohol type, the liquid detergent composition is less likely to solidify when placed at low temperatures. In addition, the bulky structure of the hydrophobic part of the nonionic surfactant (F2) reduces the total amount of active agent aligned at the soil interface when the nonionic surfactant (F2) is adsorbed to a hydrophobic substance such as sebum soil, while increasing the interfacial tension reducing ability, thereby exerting a high sebum detergency.

[0032] In formula (F2), R 1 and R 2 R is independently a linear monovalent hydrocarbon group. 1 and R 2 The total number of carbon atoms is 4 to 16, preferably 4 to 14, more preferably 6 to 14, and even more preferably 6 to 12. R 1 and R 2 The chain-like monovalent hydrocarbon group in may be linear or branched. The chain-like monovalent hydrocarbon group may or may not have an unsaturated bond. The chain-like monovalent hydrocarbon group is preferably an alkyl group or an alkenyl group. R 1 The number of carbon atoms and R 2 If the number of carbon atoms in R is different from that in 1 and R 2 The one having the fewer carbon atoms preferably has 2 to 7 carbon atoms, and the one having the greater carbon number preferably has 4 to 14 carbon atoms.

[0033] R in formula (F2) 1 -CHR2 -CH2- is Guerbet alcohol (R 1 -CHR 2 It is a residue formed by removing one hydroxyl group from --CH2--OH. Guerbet alcohol is an alcohol obtained by subjecting a raw material alcohol to the Guerbet reaction. In the Guerbet reaction, two molecules of the raw material alcohol are condensed to form a dimer. For example, if the raw material alcohol is R 4 -CH2-CH2-OH (where R 4 is a linear monovalent hydrocarbon group having 1 to 7 carbon atoms. 4 -CH2-CH2-CHR 4 The resulting alcohol is represented by the formula -CH2-OH. The two molecules of alcohol that form the alcohol may be different. When the two molecules of alcohol are the same, R 1 The number of carbon atoms and R 2 The difference in the number of carbon atoms between these is 2. R 1 -CH(R 2 Specific examples of -CH2- include a 2-ethylhexyl group and a 2-propylheptyl group.

[0034] p is an integer of 1 to 20, preferably 3 to 14, more preferably 4 to 12, and most preferably 5 to 10. R 3 R is an alkylene group having 1 to 4 carbon atoms. 3 is preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. That is, R 3 O is preferably at least one of EO and PO, and more preferably EO. (R 3 O) p EO and PO may be mixed in. When EO and PO are mixed, they may be mixed in a random manner or in a block manner.

[0035] Specific examples of the nonionic surfactant (F2) include 2-ethylhexyl alcohol alkoxylates such as 2-ethylhexyl alcohol ethoxylate, and 2-propylheptyl alcohol alkoxylates such as 2-propylheptyl alcohol ethoxylate. Among these, 2-propylheptyl alcohol ethoxylate is preferred. The average number of moles of ethylene oxide added is preferably 3 to 14, more preferably 4 to 12, and most preferably 5 to 10.

[0036] The nonionic surfactant (F2) may be a commercially available product, or may be one produced by a known production method. For example, a commercially available product of 2-ethylhexyl alcohol ethoxylate is Newcol 1008 manufactured by Nippon Nyukazai Co., Ltd., etc., and a commercially available product of 2-propylheptyl alcohol ethoxylate is Lutensol XP-100, Lutensol XP-80, Lutensol XP-50, etc. manufactured by BASF Corporation. As a method for producing the nonionic surfactant (F2), for example, a method of adding 1 to 20 moles of alkylene oxide to Guerbet alcohol having 8 to 18 carbon atoms can be mentioned. The Guerbet alcohol may be produced by subjecting the raw material alcohol as described above to the Guerbet reaction, or a commercially available product may be used. For example, 2-propylheptyl alcohol can be obtained by subjecting pentanol to the Guerbet reaction.

[0037] [Non-soap anionic surfactants] The term "non-soap anionic surfactant" refers to an anionic surfactant other than higher fatty acids or their salts (so-called soaps). Higher fatty acids are typically fatty acids having 8 to 22 carbon atoms. Examples of non-soap anionic surfactants 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 (or alkenyl) ether sulfate ester or its salt (AES), alkane sulfonic acid or its salt, α-sulfofatty 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, and acylamino carboxylic 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, and glycerin fatty acid ester monophosphate ester or its salt. Examples of the salt form of these anionic surfactants include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.), and the like. Among these, LAS, AOS, AS and AES are preferred. The non-soap anionic surfactants may be used alone or in combination of two or more.

[0038] Among the above, the non-soap anionic surfactant preferably contains either one or both of LAS and AES, and more preferably contains both LAS and AES, from the viewpoint of further enhancing the detergency. The inclusion of LAS tends to improve low temperature stability, and the inclusion of AES tends to improve sebum detergency. As the LAS, those having a linear alkyl group with 8 to 22 carbon atoms are preferred.

[0039] AES is represented by the following formula (F3). R 17 -O-[(EO)m / (PO) n ]-SO3 - M + (F3) However, 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. M + is the counter cation.

[0040] In formula (F3), R 17 The alkyl group or alkenyl group preferably has 10 to 20 carbon atoms, and more preferably has 12 to 14 carbon atoms. R 17 As the alkyl group, a linear alkyl group having 10 to 20 carbon atoms is preferable, and a linear alkyl group having 12 to 14 carbon atoms is more preferable. Specific examples thereof include a dodecyl group, a tridecyl group, and a tetradecyl group.

[0041] 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. m+n is 0.1 or more, preferably 0.5 to 10, and more preferably 1 to 5.

[0042] If n is not 0, that is, if AES has EO and PO, then [(EO) m / (PO) n There is no particular limitation on the distribution (arrangement order) of EO and PO in "R". They may be arranged in a block form or randomly. 17 -O-" or PO may be bonded to "R 17 -O-" may be bonded. Examples of methods 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 then ethylene oxide.

[0043] M + For example, Na + , K + , H + Examples include:

[0044] As for AES, in terms of sebum cleansing power, R 17 is a linear or branched alkyl group having 10 to 20 carbon atoms or a linear or branched alkenyl group having 10 to 20 carbon atoms, and m+n is preferably 1 to 5. In the AES, from the viewpoint of storage stability, the proportion of the compound represented by formula (F3) where m=0, n=0 is preferably 35 to 55% by mass relative to the total mass of the compound represented by formula (F3).

[0045] <(G) component> The liquid detergent composition may further contain a component (G). Component (G) is a glycol solvent. The combined use of components (E) and (G) reduces the viscosity of the liquid detergent composition, improving its ease of handling and usability in washing machines with automatic detergent dispenser functions. In addition, the liquid stability is improved under high temperature and semi-open conditions.

[0046] Examples of the (G) component include glycols such as propylene glycol (PG), butylene glycol, and hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of about 200 to 1000, and dipropylene glycol. Among these, propylene glycol and polyethylene glycol having a molecular weight of about 200 to 1000 are preferred. These glycol solvents may be used alone or in combination of two or more.

[0047] <Water> The liquid cleaning composition may further contain 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.

[0048] <Other ingredients> The liquid detergent composition may contain components other than the components (A), (B), (C), (D), (E), (F), (G) and water, within the range that does not impair the effects of the present invention. Examples of other components include components that are commonly used in liquid detergents, such as enzymes other than components (A) and (B), organic solvents other than component (E), surfactants other than component (F) (e.g., higher fatty acids and their salts), hydrotropes (e.g., aromatic sulfonic acids and their salts, such as paratoluenesulfonic acid), detergent builders, stabilizers, alkalis (e.g., alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine), texture improvers (e.g., silicones), preservatives, fluorescent agents, dye transfer inhibitors, pearlescent agents, antibacterial agents, general-purpose dyes or pigments as colorants, emulsifiers, fragrances, pH adjusters, and the like.

[0049] Examples of enzymes other than components (A) and (B) include lipase, cellulase, pectinase, and the like. These enzymes are generally commercially available as enzyme-containing preparations (enzyme preparations), and when preparing liquid detergent compositions, they are usually incorporated in the form of enzyme preparations. Examples of preparations containing lipase (lipase preparations) include those 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, Endolase 5000L, and Celluclean 4500T. Examples of preparations containing pectinase (pectinase preparations) include Pectawash, Pectaway, XPect1000L, and the like available from Novozymes. These enzyme preparations may be used alone or in combination of two or more.

[0050] <Content> From the viewpoint of detergency, the content of component (A) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, based on the total mass of the liquid detergent composition, and from the viewpoint of the balance with components other than component (A), the content is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The lower limit value and the upper limit value can be appropriately combined. The content (mass%) of component (A) is the amount as an enzyme preparation (total of amylase preparation and mannanase preparation).

[0051] When the (A) component contains amylase, the content of amylase is preferably such that the amylase activity of the liquid detergent composition is 0.01 SNU(CP) / g or more from the viewpoint of detergency. The amylase activity of the liquid detergent composition is more preferably 0.02 SNU(CP) / g or more, and even more preferably 0.03 SNU(CP) / g or more. The higher the amylase activity of the liquid detergent composition, the more preferable it is. The upper limit is not particularly limited, but is, for example, 1 SNU(CP) / g. The amylase activity of the liquid detergent composition is measured by the method described in the Examples below. Here, the unit of amylase activity SNU(CP) means a value converted from an absorbance calibration curve created using the standard enzyme "Standard Amylase" manufactured by Novozymes Japan, and / g means a value relative to unit mass of the liquid detergent composition.

[0052] When the (A) component contains mannanase, the content of mannanase is preferably such that the mannanase activity of the liquid detergent composition is 0.001 MIU(S) / g or more from the viewpoint of detergency. The mannanase activity of the liquid detergent composition is more preferably 0.003 MIU(S) / g or more, and even more preferably 0.005 MIU(S) / g or more. The higher the mannanase activity of the liquid detergent composition, the more preferable it is. The upper limit is not particularly limited, but is, for example, 1 MIU(S) / g. The mannanase activity of the liquid detergent composition is measured by the method described in the Examples below. Here, the unit of mannanase activity MIU(S) means that it is a value converted from an absorbance calibration curve created using the standard enzyme "Standard Mannaway" manufactured by Novozymes Japan, and / g means that it is a value relative to the unit mass of the liquid cleaning composition.

[0053] From the viewpoint of detergency, the content of the (B) component is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and most preferably 2% by mass or more, based on the total mass of the liquid detergent composition, and from the viewpoint of stabilizing the (A) component, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. The above lower limit value and the above upper limit value can be appropriately combined. The content (mass %) of component (B) is the amount as an enzyme preparation (protease preparation). When an enzyme preparation containing component (A) and component (B) is used, the amount of component (A) is determined by multiplying the amount of the enzyme preparation by the mass ratio of component (A) to the total of components (A) and (B), and the amount of component (B) is determined by multiplying the amount of component (A) by the mass ratio of component (B) to the total of components (A) and (B).

[0054] The content of the (B) component is preferably an amount that results in a protease activity of the liquid detergent composition of 0.1 PRMU(U) / g or more from the viewpoint of cleaning power. The protease activity of the liquid detergent composition is more preferably 0.5 PRMU(U) / g or more, and even more preferably 0.8 PRMU(U) / g or more. Moreover, the protease activity of the liquid detergent composition is preferably 5 PRMU(U) / g or less, more preferably 4 PRMU(U) / g or less, and even more preferably 3 PRMU(U) / g or less from the viewpoint of stabilizing the (A) component. The lower limit value and the upper limit value can be appropriately combined. The protease activity of the liquid detergent composition is measured by the method described in the Examples below. Here, protease activity unit PRMU (U) means a value converted from an absorbance calibration curve prepared using the standard enzyme "Standard Protease" manufactured by Novozymes Japan, and / g means a value relative to unit mass of the liquid detergent composition.

[0055] The mass ratio of component (A) / component (B) (hereinafter also referred to as "(A) / (B)") is preferably 0.005 or more, more preferably 0.01 or more, even more preferably 0.05 or more, and is preferably 50 or less, more preferably 30 or less, and even more preferably 10 or less. The above lower limit and upper limit can be appropriately combined. When (A) / (B) is equal to or more than the above lower limit, inactivation of component (A) by component (B) can be suppressed, and enzyme stability is improved. When (A) / (B) is equal to or less than the above upper limit, cleaning power for proteins is improved.

[0056] The total content of components (A) and (B) is preferably 0.1 to 10 mass%, more preferably 0.1 to 7 mass%, and most preferably 0.1 to 5 mass%, based on the total mass of the liquid detergent composition. When the total content of components (A) and (B) is equal to or more than the lower limit, excellent detergency is achieved, and when it is equal to or less than the upper limit, liquid stability is improved.

[0057] The content of the (C) component is 0.05% by mass or more, preferably 0.06% by mass or more, and preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.15% by mass or less, based on the total mass of the liquid detergent composition. The lower limit and the upper limit can be appropriately combined. When the (C) component content is equal to or more than the lower limit, the enzyme stability is improved. When the (C) component content is equal to or less than the upper limit, the liquid stability at low temperatures is improved.

[0058] The content of component (D) is 0.02% by mass or more, preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total mass of the liquid detergent composition. The lower limit and the upper limit can be appropriately combined. When the content of component (D) is equal to or more than the lower limit, the liquid stability at low temperatures is improved. When the content of component (D) is equal to or less than the upper limit, the liquid stability at high temperatures is improved.

[0059] The mass ratio represented by the (D) component / the (C) component (hereinafter also referred to as "(D) / (C)") is 60 or less, preferably 30 or less, more preferably 10 or less, and preferably 0.1 or more, more preferably 0.3 or more. The lower limit and the upper limit can be appropriately combined. When (D) / (C) is less than the upper limit, the enzyme stability and the liquid stability at low temperatures are improved. When (D) / (C) is more than the lower limit, the liquid stability at high temperatures is improved.

[0060] The content of the (E) component is preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the liquid detergent composition. The lower limit and the upper limit can be appropriately combined. When the (E) component is at least the lower limit, the liquid stability at low temperatures is improved. When the (E) component is at most the upper limit, the liquid stability at high temperatures is improved.

[0061] The content of the (F) component is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 45% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, based on the total mass of the liquid detergent composition. The lower limit and the upper limit can be appropriately combined. When the content of the (F) component is equal to or more than the lower limit, the detergency is improved. When the content of the (F) component is equal to or less than the upper limit, the enzyme stability is improved.

[0062] When component (F) contains at least one nonionic surfactant selected from the group consisting of nonionic surfactants (F1) and nonionic surfactants (F2), and a non-soap anionic surfactant, the mass ratio represented by non-soap anionic surfactant / nonionic surfactant (hereinafter also referred to as "anionic / nonionic") is preferably 0.05 or more, more preferably 0.1 or more, and preferably 2 or less, more preferably 1 or less. The above lower limit and upper limit can be appropriately combined. When the anionic / nonionic ratio is equal to or more than the above lower limit, the liquid stability at low temperatures is improved and solidification is suppressed, and when it is equal to or less than the above upper limit, the sebum cleansing power and enzyme stability are improved.

[0063] The mass ratio represented by nonionic surfactant (F2) / nonionic surfactant (F1) (hereinafter also referred to as "(F2) / (F1)") is preferably 0.03 or more, more preferably 0.05 or more, and preferably 0.3 or less, more preferably 0.25 or less. The lower limit value and the upper limit value can be appropriately combined. When (F2) / (F1) is equal to or more than the lower limit value, the liquid stability at low temperatures is improved. On the other hand, when the liquid detergent composition is stored in the tank of a washing machine with an automatic dosing function, the heat generated from the washing machine may cause water and solvent to evaporate, resulting in a weight loss. When (F2) / (F1) is equal to or less than the upper limit value, the weight loss rate at high temperatures is reduced.

[0064] The content of component (G) is preferably 1% by mass or more, preferably 3% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the liquid detergent composition. The above lower limit and upper limit can be combined as appropriate. When the content of component (G) is equal to or more than the above lower limit, the viscosity reducing effect of the liquid detergent composition, the enzyme stabilizing effect, and the liquid stabilizing effect under high temperature / semi-open conditions are improved. When the content of component (G) is equal to or less than the above upper limit, the liquid stability at high temperatures is improved.

[0065] The mass ratio of component (G) to component (E) (hereinafter also referred to as "(G) / (E)") is preferably 0.1 or more, more preferably 1 or more, and preferably 5 or less. The lower limit value and the upper limit value can be combined as appropriate. When (G) / (E) is equal to or more than the lower limit value, the solubility of the liquid detergent composition in water is improved. When (G) / (E) is equal to or less than the upper limit value, the liquid stability at low temperatures is improved.

[0066] The water content may be, for example, 90% by mass or less, or even 75% by mass or less, based on the total mass of the liquid detergent composition. When the liquid detergent composition is a concentrated type, the water content is preferably 45% by mass or less, more preferably 40% by mass or less. The lower limit of the water content is not particularly limited, but is, for example, 10% by mass, based on the total mass of the liquid detergent composition. The total content of each component in the liquid detergent composition does not exceed 100% by mass.

[0067] <Physical Properties> The pH of the liquid detergent composition at 25°C is preferably 3-11, more preferably 6-8, and even more preferably 7-8. The pH of the liquid detergent composition can be adjusted, if necessary, by adding a pH adjuster. The pH value is measured at 25° C. using a pH meter (product name: HM-30G, manufactured by DKK-TOA Corporation).

[0068] <Manufacturing method> The liquid detergent composition of the present embodiment can be produced according to a conventional method for producing a liquid detergent composition. For example, the liquid detergent composition 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 rest of the water to make the total amount 100% by mass. The obtained liquid detergent composition 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.

[0069] 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 polyethylene resin, 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.

[0070] As another embodiment of the container for the packaged liquid detergent product, a pouch container can be used. The pouch container is configured to have a storage section in which the contents are stored, and a spout or a pouring outlet that communicates with the storage section and pours out the contents of the storage section. The container is formed by stacking a plurality of flexible films, and the periphery of each flexible film is sealed by heat sealing all or a part of the periphery of each flexible film, and a spout is attached to the part of the periphery of each flexible film that is not heat sealed. A bottom flexible film folded in half may be interposed between the two flexible films. In this case, by arranging the bottom flexible film so that its folded portion faces the inside of the storage section, the bottom flexible film is pushed outward by the weight of the contents stored in the storage section, allowing the pouch container to stand on its own. The flexible film constituting the storage section may be a laminated body formed by laminating at least a base material and a seal layer. Examples of the material of the base material include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, polyethylene terephthalate, nylon, ethylene-vinyl acetate copolymer or its saponification product. The flexible film may be unstretched, uniaxially stretched, or biaxially stretched. In the case of the material being nylon or polyethylene terephthalate, biaxially stretched film is preferable because it improves mechanical strength. Examples of the seal layer include materials such as polyethylene (low-density polyethylene, linear low-density polyethylene, high-density polyethylene) because of ease of heat sealing. In addition, in order to improve the gas barrier property of the storage section, the flexible film may be a laminated body in which metal vapor deposition or metal foil is further laminated in addition to the base material and the seal layer.

[0071] <How to use> Methods for using the liquid detergent composition include, for example, a method in which the liquid detergent composition is placed in a liquid detergent composition inlet of a washing machine and then the washing machine is operated, a method in which the liquid detergent composition is placed in water together with the items to be washed when washing, a method in which the liquid detergent composition is dissolved in water in advance and the items to be washed are immersed in a cleaning liquid prepared by this, a method in which the liquid detergent composition is directly applied to the items to be washed and left for, for example, 3 minutes to 24 hours, and then the items are washed as usual, and the like.

[0072] 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.

[0073] Using the automatic detergent dispensing function not only saves the trouble of measuring the amount of detergent, but also prevents the liquid detergent composition from sticking to your hands when measuring the amount, or from spilling and soiling the washing machine or surrounding area. In addition, the liquid detergent composition of the present embodiment may be used in an amount as small as about 10 mL per wash, for example, when the liquid detergent composition is a concentrated type with a water content of 45% by mass or less. Such a small amount of liquid detergent composition is difficult to accurately measure using a cap or the like, and the amount of liquid is likely to be insufficient or excessive. By using the automatic detergent dispenser function, even a small amount of liquid detergent composition can be accurately measured, making it easier to exert sufficient cleaning power and avoiding waste due to overuse, which is preferable.

[0074] It is also preferable to use an automatic dispenser capable of automatically discharging a predetermined amount of liquid. When an automatic dispenser is used, it is also preferable because even a small amount of the liquid detergent composition can be accurately measured, making it easier to exhibit 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.

[0075] In addition, when an automatic dispenser is used, it is also preferable to receive the liquid detergent composition discharged into a soft container and then directly put the soft container into the washing machine, so that the entire amount of the discharged liquid detergent composition 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.

[0076] 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 composition is used by dissolving it in water, it is preferably diluted, for example, 5 to 5000 times (by volume). The liquor ratio, which is the amount of water per mass of the item being washed (mass of cleaning liquid during washing / mass of the item being washed), is preferably 5 or more for drum-type washing machines and 10 or more for top-loading washing machines. The amount of the liquid detergent composition used in the cleaning treatment is preferably 10-500, more preferably 10-300, and even more preferably 10-100, in terms of the ratio of the mass of the article to be cleaned (mass of fabric) / the mass of the liquid detergent composition. The liquid detergent composition is suitable as a detergent composition for textile products.

[0077] The liquid detergent composition of this embodiment contains components (A), (B), (C), (D), (E) and (F), in which the content of component (C) is 0.05% by mass or more, the content of component (D) is 0.02% by mass or more, and the ratio (D) / (C) is 60 or less. Therefore, the liquid detergent composition has excellent detergency against various types of stains adhered to textile products, such as sauce stains, chocolate stains, protein stains, etc., as well as excellent enzyme stability and liquid stability at low temperatures. In particular, in the case of a concentrated liquid detergent composition having a water content of 45 mass % or less, cleaning power can be achieved with a small amount used.

[0078] In a washing machine equipped with an automatic detergent dispenser function, the temperature in the tank that contains the detergent is likely to rise during drying of clothes. In addition, the tank is not sealed because the detergent in the tank is sucked and transferred by a syringe pump or the like. Therefore, when a liquid detergent composition is stored in the tank of a washing machine equipped with an automatic detergent dispenser function, moisture and organic solvents tend to evaporate, and precipitation or sedimentation of enzymes and the like tends to occur. The liquid detergent composition of the present embodiment also has excellent high-temperature stability, and is therefore suitable as a liquid detergent for use in a washing machine equipped with an automatic detergent dispensing function, and which is contained in the tank of the washing machine equipped with an automatic detergent dispensing function. In particular, when the liquid detergent composition is a concentrated type, it is suitable as a liquid detergent for a washing machine equipped with an automatic detergent dispensing function, since it can be used for a large number of washes with the capacity of the washing machine tank. EXAMPLES

[0079] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0080] (Materials used) <(A) component, (B) component> Amylase: Product name "Amplify Prime 100L", manufactured by Novozymes Japan. Mannanase: Trade name "Mannaway 200L", manufactured by Novozymes Japan. Protease: Product name "Progress Uno 100L", manufactured by Novozymes Japan.

[0081] <(C) component> BHT: Dibutylhydroxytoluene, trade name "SUMILZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd. <(D) component> Citric acid: Product name: "Citric acid (anhydrous)", manufactured by Fuso Chemical Industry Co., Ltd.

[0082] <(E) component> -Solufit: 3-Methoxy-3-methylbutanol, trade name "Solufit", manufactured by Kuraray. <(G) component> PEG1000: Polyethylene glycol with a mass average molecular weight of 1000, product name "PEG#1000", manufactured by Junsei Chemical Co., Ltd.

[0083] <(F) Component> [Anionic surfactants] LAS: Linear alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms, product name "Lipon (registered trademark) LH-200", manufactured by Lion Corporation. AES: polyoxyalkylene alkyl ether sulfate (a mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, the average number of moles of EO added is 1. R in formula (F3) 17is a linear alkyl group having 12 and 14 carbon atoms, m is 1, n is 0, and M is sodium. The ratio of compounds in which m is 0 and n is 0 to the entire AES is 43% by mass, and was synthesized by the following synthesis method.

[0084] How to synthesize AES: Into a 4-L autoclave, 400 g of Procter & Gamble Co.'s CO1270 alcohol (a mixture of a carbon number 12 alcohol and a carbon number 14 alcohol in a mass ratio of 75 / 25) was charged as the raw material alcohol, and 0.8 g of potassium hydroxide catalyst was charged as the 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 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 (sulfan) 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. Next, this was neutralized with an aqueous sodium hydroxide solution to obtain AES.

[0085] [Nonionic surfactants] LMAO (15EO): Polyoxyethylene alkyl ether (a compound in which 15 moles of ethylene oxide are added to 1 mole of primary alcohol (mass ratio of carbon number 12 alcohol / carbon number 14 alcohol = 7 / 3). In formula (F1), R 11is 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, -O- is bonded to R 11 The carbon atom is a primary carbon atom, s is 15, t is 0, and u is 0), product name "LMAO-90", manufactured by Lion Corporation. XP-100: 2-Propylheptyl alcohol ethoxylate, trade name "Lutensol XP-100", manufactured by BASF.

[0086] <Other> ·MEA: Monoethanolamine (pH adjuster), manufactured by Nippon Shokubai. pTs: paratoluenesulfonic acid (hydrotrope agent), trade name "PTS acid", manufactured by Kyowa Hakko Kirin Co., Ltd. · Palm fatty acid: Product name "Palm Fatty Acid", manufactured by NOF Corporation. Dichlosan: 4,4'-dichloro-2-hydroxydiphenyl ether, trade name "TINOSAN HP100", manufactured by BASF. Lactic acid: Sodium lactate (stabilizer), product name "Sodium Lactate 60E", manufactured by Musashino Chemical Laboratory. -Pectinase: Product name "Xpect1000L", manufactured by Novozymes Japan. BIT: 1,2-Benzisothiazolin-3-one, trade name "NIPACIDE BIT20", manufactured by Clariant Japan. Fragrance: Any one of the following (1), (2), or (3). (1) Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399. (2) Fragrance composition 1 described in Table 1 below. (3) Fragrance composition 2 described in Table 1 below. ·Pigment: Product name: "Green No. 3", manufactured by Kinsumi Kasei Co., Ltd. -Pigment: Product name "Brilliant Orange", manufactured by Milliken Japan LLC. -Pigment: Product name "Violet FL", manufactured by Milliken Japan LLC. -Pigment: Product name "Violet SH", manufactured by Milliken Japan LLC. -Pigment: Product name "SeaGreen CC", manufactured by Milliken Japan LLC. Water: Product name: "Purified Water", manufactured by Kanto Chemical Co., Ltd.

[0087] [Table 1]

[0088] (Examples 1 to 13, Comparative Examples 1 to 5) According to the formulations in Tables 2 and 3, liquid detergent compositions were produced in the following manner. In a 500 mL beaker, the components (F), (E), and water were added and thoroughly stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Then, the components (C), (D), (A), (B), and other optional components were added and further thoroughly stirred. Next, MEA was added so that the pH at 25°C was 7.7, and water was added so that the total amount was 100% by mass, to obtain a liquid detergent composition. The blending amounts in the table are percentages (mass %) relative to the total mass of the liquid detergent composition.

[0089] The resulting liquid detergent composition was evaluated for protease activity, detergency (medium-thick sauce, chocolate ice cream, protein), low-temperature stability, high-temperature stability, and enzyme stability (amylase, mannanase) by the following evaluation methods. The evaluation results are shown in Tables 2 and 3.

[0090] <Method for evaluating protease activity> After producing each liquid detergent composition, the protease activity was measured according to the following procedure. Preparation of substrate: 1.2 g of Hamer casein (MERCK) or milk casein (CALBIOCHEM) was accurately placed in a 200 mL beaker, and 6 mL of 1 mol / L-NaOH was gradually added while quickly kneading with a glass rod to swell. Next, 160 mL of 0.05 mol / L boric acid solution was added, and the mixture was stirred with a stirrer to disperse. After adjusting the pH to 10.5 with 1 mol / L-NaOH, the mixture was diluted to 200 mL to prepare the substrate solution. The substrate solution was kept at a constant temperature of 37°C in a thermostatic bath. Preparation of standard curve solution: A solution of the standard enzyme Standard Protease [PRMU(U) / g] diluted with ion-exchanged water was used as the standard curve solution, and was prepared in a concentration range such that the enzyme concentration in the sample was in the interpolation region. Preparation of sample solution: The liquid detergent composition was diluted with ion-exchanged water to prepare a sample solution. The dilution was adjusted according to the enzyme activity in the formulation. Measurement: 5 mL of substrate solution was added to 1 g of sample solution, stirred with a vortex mixer for 10 seconds, and then reacted at 37°C for 30 minutes. Then, 5 mL of TCA solution adjusted to 0.44 mol / L was added and left to stand in a water bath at 37°C for 30 minutes, and the unreacted substrate remaining in the solution was removed with filter paper. The absorbance (absorbance A) of the recovered filtrate at a wavelength of 275 nm was measured using a Shimadzu UV-160 ultraviolet-visible spectrophotometer. In order to eliminate the influence of absorption by substances other than the target component, the reaction was stopped in advance in the above-mentioned reaction procedure, and the enzyme was inactivated, and then the substrate solution was added to prepare a blank sample. The absorbance at a wavelength of 275 nm (absorbance B) was measured using a Shimadzu UV-160 ultraviolet-visible spectrophotometer. The larger the difference between absorbance A and absorbance B, the greater the amount of substrate degradation products present in the filtrate. The influence of absorption by components other than the target components was eliminated by subtracting the OD value of the corresponding blank from the OD value of the sample, and the protease activity in the sample solution was then determined from the absorbance of the standard curve solution.

[0091] <How to evaluate cleaning power (medium-thick sauce)> A cloth tied to a glass rod was soaked in thick sauce (Otsuka Foods Co., Ltd.). The thick sauce soaked into the cloth was applied to a white cloth (cotton plain weave cloth, #100, 5 cm x 5 cm) and air-dried overnight to prepare a food-stained cloth. The cleaning tester used was a Terg-O-Tometer (manufactured by UNITED STATES TESTING). The liquid detergent composition was added to 900 mL of tap water (40° C., 4° DH) so as to give a final concentration of 200 ppm by mass, and the mixture was stirred for 30 seconds to prepare a cleaning liquid. The cleaning solution and 10 of the above soiled cloths were placed in a cleaning tester and washed for 10 minutes at 120 rpm. After dehydrating the soiled cloths, they were rinsed in 30 L of tap water (15°C, 4°DH) for 3 minutes and dried with an iron. The Z value (reflectance) of the original cloth before the soiling and the soiled cloth before and after the washing was measured using a colorimeter (SE2000 manufactured by Nippon Denshoku Co., Ltd.), and the cleaning rate (%) for medium-thick sauce stains was calculated using the following formula (s). 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) x 100 (s) However, "K / S" is (1-R / 100) 2 The value is calculated by / (2R / 100). R indicates the reflectance (%) of unsoiled cloth and soiled cloth before and after washing. Unsoiled cloth means the original white cloth (original cloth) that has not been soiled.

[0092] The average cleaning rate of 10 soiled cloths was calculated and evaluated according to the following criteria: "◎", "○", and "△" were considered to be acceptable. [Evaluation Criteria] ◎: Average cleaning rate is between 65% and 100%. Good: Average cleaning rate is between 55% and 65%. △: The average cleaning rate is between 50% and 55%. ×: The average cleaning rate was 0% or more and less than 50%.

[0093] <How to evaluate cleaning power (chocolate ice cream)> A piece of cloth tied to a glass rod was soaked in chocolate ice cream. The soaked piece of cloth was then spread onto a piece of white cloth (cotton plain weave cloth, #100, 5cm x 5cm) and air-dried overnight to create a food-stained cloth. The liquid detergent composition was added to 900 mL of tap water (40° C., 4° DH) so as to give a final concentration of 200 ppm by mass, and the mixture was stirred for 30 seconds to prepare a cleaning liquid. The cleaning solution and 10 of the above soiled cloths were placed in a cleaning tester and washed for 10 minutes at 120 rpm. After dehydrating the soiled cloths, they were rinsed in 30 L of tap water (15°C, 4°DH) for 3 minutes and dried with an iron. The Z value (reflectance) of the original cloth before the soiling and the soiled cloth before and after washing was measured using a colorimeter (SE2000 manufactured by Nippon Denshoku Co., Ltd.), and the cleaning rate (%) for chocolate ice cream stains was calculated using the above formula (s).

[0094] The average cleaning rate of 10 soiled cloths was calculated and evaluated according to the following criteria: "◎", "○", and "△" were considered to be acceptable. [Evaluation Criteria] ◎: The average cleaning rate is between 60% and 100%. Good: Average cleaning rate is between 55% and 60%. △: The average cleaning rate is between 50% and 55%. ×: The average cleaning rate was 0% or more and less than 50%.

[0095] <How to evaluate cleaning power (protein)> A commercially available protein-stained cloth (manufactured by Swissatest, product name "EMPA117") was cut into a size of 5 cm x 5 cm to serve as the soiled cloth. The cleaning tester used was a Terg-O-Tometer (manufactured by UNITED STATES TESTING). The liquid detergent composition was added to 900 mL of tap water (15° C.) so as to give a final concentration of 200 ppm by mass, and the mixture was stirred for 30 seconds to prepare a cleaning liquid. The cleaning solution, 10 of the above soiled fabrics, and the washed knitted fabric were placed in a cleaning tester and washed for 10 minutes at 120 rpm. After dehydrating the soiled fabrics, they were rinsed in 30 L of tap water (15°C, 4°DH) for 3 minutes and air-dried. The Z values ​​(reflectance) of the original fabric before soiling and the soiled fabric before and after washing were measured using a colorimeter (SE2000, manufactured by Nippon Denshoku Co., Ltd.), and the cleaning rate (%) for protein stains was calculated using the above formula (s).

[0096] The average cleaning rate of 10 soiled cloths was calculated and evaluated according to the following criteria: "◎", "○", and "△" were considered to be acceptable. [Evaluation Criteria] ◎: Average cleaning rate is between 40% and 100%. Good: Average cleaning rate is between 35% and 40%. △: The average cleaning rate is between 30% and 35%. ×: The average cleaning rate was 0% or more and less than 30%.

[0097] <Evaluation method for low temperature stability> A transparent glass bottle (wide-mouth standard bottle, PS-NO.11) was filled with 90 mL of the liquid detergent composition, and the lid was closed and sealed. In this state, the liquid detergent composition was left to stand in a thermostatic chamber at -5°C for one month (low-temperature storage). After such storage, the appearance of the liquid detergent composition was visually observed. In addition, the glass bottle was tilted to observe the fluidity of the liquid detergent composition. Thereafter, the glass bottle was allowed to stand at room temperature (25° C.) for 6 hours, and the appearance and fluidity of the liquid detergent composition were observed again. From the observation results, the liquid stability (low temperature stability) of the liquid detergent composition was evaluated according to the following evaluation criteria. "A", "B" and "C" were judged to be acceptable. [Evaluation Criteria] ⊚: The liquid detergent composition in the glass bottle after low-temperature storage was transparent with no visible precipitates and the liquid had high fluidity. ◯: Although precipitates and the like were observed in the liquid detergent composition in the glass bottle after low-temperature storage, they were small amounts and improved at room temperature, and the liquid had high fluidity. Δ: Precipitation was observed in the liquid detergent composition in the glass bottle after low-temperature storage, and the improvement at room temperature was poor. Alternatively, the fluidity of the liquid was low. ×: Precipitation was observed in the liquid detergent composition in the glass bottle after low-temperature storage, and this did not improve at room temperature. Alternatively, the liquid had lost fluidity and solidified.

[0098] <Method for evaluating high temperature stability> A transparent glass bottle (wide-mouth standard bottle, PS-No. 11) was filled with 90 mL of the liquid detergent composition, and the bottle was left to stand in a thermostatic chamber at 50° C. for one month with the lid open. After such storage, the appearance of the liquid detergent composition was visually observed. From the observation results, the liquid stability (high temperature stability) of the liquid detergent composition was evaluated according to the following evaluation criteria. "A", "B" and "C" were judged to be acceptable. [Evaluation Criteria] ◎: Transparent with no visible precipitates or the like. ◯: A very small amount of precipitate is observed, but the solution is transparent. △: Precipitation occurs but the solution is transparent. ×: Precipitation occurs and the sample becomes opaque, or separation occurs.

[0099] <Method for evaluating enzyme stability (amylase)> After preparation of each liquid detergent composition, it was filled into a transparent glass bottle (screw-cap bottle, S-5), sealed with a lid, and stored in that state for 6 weeks at 37° C. or −5° C. After storage, the liquid detergent composition (stored at 37° C. or −5° C.) was subjected to the measurement of amylase activity according to the following procedure.

[0100] [Amylase activity measurement] Preparation of buffer solution: 20.0 g of sodium sulfite, 6.15 g of potassium dihydrogen phosphate, 10.86 g of disodium hydrogen phosphate dodecahydrate, 0.015 g of calcium chloride dihydrate, and Brij 35 (30% aqueous solution), M 0.75 mL were precisely weighed and dissolved in ion-exchanged water, and the volume was adjusted to 1 L to prepare a buffer solution. Preparation of calibration curve solution: A solution of the standard enzyme Standard Amylase [SNU(CP) / g] diluted with the above buffer was used as the calibration curve solution, and was prepared in a concentration range such that the enzyme concentration in the samples was in the interpolation region. Preparation of sample solution: The liquid detergent composition after storage (stored at 37°C or -5°C) was diluted with the above-mentioned buffer solution to prepare a sample solution. The dilution was adjusted depending on the enzyme activity in the formulation. Measurement: 5 mL of buffer solution and 1 tablet of Phadebas Amylase Test (Magle) for measuring amylase activity were added to 1 g of sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37°C for 15 minutes to allow the enzyme reaction to proceed. Then, 1 mL of 1 mol / L sodium hydroxide solution was added to the solution to stop the enzyme reaction, and the reaction was stopped by stirring with a vortex mixer for 10 seconds. Unreacted substrates remaining in the solution were removed with filter paper. The absorbance (absorbance A) of the collected filtrate at a wavelength of 620 nm was measured using a UV-160 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. In order to eliminate the influence of absorption by components other than the target components, 1 mol / L sodium hydroxide solution (1N) was added to 1 g of each sample solution to stop the enzyme reaction, and then 1 tablet of Phadebas Amylase Test was added and stirred for 10 seconds with a vortex mixer. The reaction was stopped by stirring for 10 seconds with a vortex mixer, and unreacted materials were removed with filter paper in the same manner as the sample. The absorbance (absorbance B) of the collected filtrate at a wavelength of 620 nm was measured using a Shimadzu UV-160 ultraviolet-visible spectrophotometer. The larger the difference between absorbance A and absorbance B, the greater the amount of substrate degradation products present in the filtrate. The corrected OD value was calculated by subtracting the corresponding blank OD value from the sample OD value. A standard curve was created based on the results of the standard curve solution, with the corrected OD value on the horizontal axis and amylase activity on the vertical axis. The corrected OD value of the sample solution was substituted into this standard curve to calculate the amylase activity in the sample solution.

[0101] The amylase activity value of the sample stored at 37°C was defined as the enzyme residual rate when the amylase activity of the sample stored at -5°C was taken as 100%, and the enzyme residual rate was evaluated according to the following criteria. [Evaluation Criteria] ◎: Enzyme residual rate 50-100%. 〇: Enzyme residual rate 40% to 49%. △: Enzyme residual rate 20-39%. ×: Enzyme residual rate 0 to 19%.

[0102] <Method for evaluating enzyme stability (mannanase)> After preparing each liquid detergent composition, it was filled into a transparent glass bottle (screw-cap bottle, S-5) and sealed with a lid. It was stored in this state for 6 weeks at 37°C or -5°C. The mannanase activity of the liquid detergent composition after storage (stored at 37°C or -5°C) was measured by the following procedure.

[0103] [Measurement of mannanase activity] Preparation of substrate: 0.15 g of galactomannan was dissolved in ion-exchanged water to make 100 mL, and the solution was stirred in a 50°C warm bath until it became transparent and uniform to prepare a substrate solution. Preparation of buffer solution: 46.85 g of disodium hydrogen phosphate anhydrous and 9.40 g of sodium dihydrogen phosphate dihydrate were dissolved in ion-exchanged water to make a total volume of 1000 mL. Preparation of color reagent: Dissolve 0.552 g of bismuth(III) acetate, 2 g of p-hydroxybenzhydrazide, and 5 g of sodium potassium (+)-tartrate tetrahydrate in 0.5 mol / L NaOH to a total of 100 mL. Cover the whole with aluminum foil to block light and stir until the reagent is dissolved. Preparation of calibration curve solution: A solution obtained by diluting the standard enzyme Standard Mannaway [MIU(S) / g] with the above buffer was used as the calibration curve solution, and was prepared in a concentration range such that the enzyme concentration in the sample was in the interpolation region. Preparation of sample solution: The liquid detergent composition after storage (stored at 37°C or -5°C) was diluted with the above buffer solution to prepare a sample solution. The dilution was adjusted according to the enzyme activity in the formulation. Measurement: 5 mL of substrate solution was added to 2 g of sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then reacted at 50°C for 30 minutes. Then, 4 mL of color-developing reagent was added and the mixture was left to stand in a water bath at 70°C for 10 minutes. After the color-developing reaction, the mixture was left to stand in an ice bath, and the unreacted substrate remaining in the solution was removed with filter paper. The absorbance (absorbance A) of the collected filtrate at a wavelength of 405 nm was measured using a Shimadzu UV-160 ultraviolet-visible spectrophotometer. In order to eliminate the influence of absorption by components other than the target component, the color development step was carried out first in the above reaction procedure, and the enzyme was inactivated, and then the substrate solution was added to prepare a blank sample. The absorbance at a wavelength of 405 nm (absorbance B) was measured using a Shimadzu UV-160 ultraviolet-visible spectrophotometer. The larger the difference between absorbance A and absorbance B, the greater the amount of substrate degradation products present in the filtrate. The influence of absorption by components other than the target components was eliminated by subtracting the OD value of the corresponding blank from the OD value of the sample, and the mannanase activity in the sample solution was then determined from the absorbance of the standard curve solution.

[0104] The mannanase activity of the sample stored at 37°C was defined as the enzyme residual rate when the mannanase activity of the sample stored at -5°C was taken as 100%, and the enzyme residual rate was evaluated according to the following criteria. [Evaluation Criteria] ◎: Enzyme residual rate 85-100%. 〇: Enzyme residual rate 70% to 84%. △: Enzyme residual rate 40-69%. ×: Enzyme residual rate 0 to 39%.

[0105] [Table 2]

[0106] [Table 3]

[0107] The liquid detergent compositions of Examples 1 to 18 were excellent in detergency (semi-thick sauce, chocolate ice cream, protein), low temperature stability, high temperature stability, and enzyme stability (amylase, mannanase). On the other hand, the liquid detergent composition of Comparative Example 1, which did not contain the component (B), was inferior in detergency (medium-thick sauce, chocolate ice cream). The liquid detergent composition of Comparative Example 2, which did not contain the component (C), was inferior in detergency (protein). The liquid detergent composition of Comparative Example 3, which did not contain the component (D), was poor in low-temperature stability. The liquid detergent composition of Comparative Example 4, in which (D) / (C) was more than 60, was poor in enzyme stability (amylase, mannanase). The liquid detergent composition of Comparative Example 5, in which component (E) in Comparative Example 4 was replaced with component (G), had inferior enzyme stability (amylase, mannanase) as in Comparative Example 4, and further had lower low-temperature stability and high-temperature stability than Comparative Example 4.

Claims

1. Component (A): at least one selected from the group consisting of amylase and mannanase; (B) component: a protease; (C) component: antioxidant; (D) component: a chelating agent, Component (E): at least one selected from the group consisting of a solvent represented by the following formula (E1) and a solvent represented by the following formula (E2), Component (F): a non-soap surfactant, Contains The content of the (C) component is 0.05% by mass or more, The content of the (D) component is 0.02% by mass or more, A liquid detergent composition for textile products, in which the mass ratio of the (D) component to the (C) component is 60 or less. R ４ (OR ５ ) ｙ OH ・・・(E1) CH ３ OCR ６ (CH ３ )CHR ７ CHR ８ OR ９ ・・・(E2) However, R ４ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ５ is an alkylene group having 2 to 4 carbon atoms, and y is OR ５ is a number from 1 to 5 representing the average number of repetitions of R ６ , R ７ and R ８ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ９ is a hydrogen atom or an acetyl group.

2. 2. The liquid detergent composition for textile products according to claim 1, wherein the water content is 45% by mass or less.

3. 3. The liquid detergent composition for textile products according to claim 1, further comprising a glycol solvent as component (G).

4. 3. The liquid detergent composition for textile products according to claim 1, which is for use in a washing machine having an automatic detergent dispensing function.

Images