Liquid dishwashing detergent composition

Abstract

To provide a liquid dishwashing detergent composition that is excellent in detergency and capable of reducing the sliminess in rinsing.SOLUTION: A liquid dishwashing detergent composition contains: a component (A) comprising one or more selected from the group consisting of an alkyl ether sulfate, an alkanesulfonate, and an olefinsulfonate; a component (B) that is a semipolar surfactant; a component (C) that is a nonionic surfactant; a component (D) that is an enzyme; a component (E) comprising one or more selected from the group consisting of a specific isothiazolinone and a derivative thereof, and a specific phenylboronic acid and a derivative thereof; and a component (F) comprising one or more selected from the group consisting of lactic acid, malic acid, and salts thereof; wherein the content of the component (D) is 720 to 3000 mass ppm in terms of protein, and the mass ratio represented by the component (D) / the component (E) is in a specific range.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid dishwashing detergent composition. [Background technology]

[0002] In recent years, when washing dishes, there is a demand for detergents that can remove not only oily stains, but also complex stains such as starch and protein. The detergent's ability to remove various types of stains can be felt not only in its ability to remove the stains, but also in the fact that it does not leave any dirt or sticky feeling caused by the detergent when rinsing after washing.

[0003] 2. Description of the Related Art Liquid dishwashing detergent compositions containing enzymes have been proposed for the purpose of enhancing detergency. For example, Patent Document 1 proposes a liquid dishwashing detergent composition containing an anionic surfactant, an amine oxide surfactant, a nonionic surfactant, a protease, and an amylase. Patent Document 2 proposes a liquid dishwashing detergent composition that contains a protease and a specific anionic surfactant in a specific ratio, and also contains an amphoteric surfactant. According to the inventions described in Patent Documents 1 and 2, further improvements in cleaning power are achieved. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-63358 A [Patent Document 2] JP 2023-26447 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, if the enzyme content is increased in order to further improve the detergency, a slimy feeling derived from the liquid dishwashing detergent composition remains during rinsing. Therefore, an object of the present invention is to provide a liquid dishwashing detergent composition that has excellent detergency and can reduce slimy feeling during rinsing. [Means for solving the problem]

[0006] The present invention has the following aspects. <1> Component (A): one or more selected from alkyl ether sulfate salts, alkanesulfonates, and olefinsulfonates; (B) component: a semi-polar surfactant; (C) component: a nonionic surfactant, (D) component: an enzyme (excluding catalase); Component (E): at least one member selected from the group consisting of isothiazolinones and derivatives thereof represented by the following formula (e1) or (e2), and phenylboronic acid and derivatives thereof represented by the following formula (e3), [ka] [In formula (e1), R 1 is H or an alkyl group having 1 to 8 carbon atoms, R 2 is H, CH3, Cl, Br or NH2, R 3 is H, CH3, Cl or CH2NH2. [ka] [ka] [In formula (e3), R 4 , R 5 and R 6 are each independently H, a hydrocarbon group having 1 to 3 carbon atoms, Cl, Cl, F, OH, SCH3, NH2, or COH. (F) component: one or more selected from the group consisting of lactic acid, malic acid, and salts thereof; Including, The content of the component (D) is 720 to 3,000 ppm by mass in terms of protein, The mass ratio of the component (D) to the component (E) is 4 to 130. A liquid dishwashing detergent composition. <2> The mass ratio of the component (D) to the component (F) is 0.04 to 3. <1> The liquid dishwashing detergent composition according to claim 1. Effect of the Invention

[0007] The liquid dishwashing detergent composition of the present invention has excellent detergency and can reduce slimy feeling during rinsing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] (Liquid dishwashing detergent composition) The liquid dishwashing detergent composition of the present invention (hereinafter, sometimes simply referred to as "liquid detergent composition") contains components (A) to (F).

[0009] <Component (A)> The component (A) is at least one selected from alkyl ether sulfate salts, alkanesulfonates, and olefinsulfonates. The liquid detergent composition exhibits excellent detergency by including the component (A).

[0010] Examples of the alkyl ether sulfate ester salt include polyoxyethylene alkyl sulfate ester salts represented by the following formula (a1).

[0011] R 11 -O-(CH2CH2O) n -SO3 - 1 / X M + (a1) [In formula (a1), R 11 is a straight or branched alkyl group having 8 to 18 carbon atoms. R 11 R attached to the oxygen atom in -O- 11The carbon atom may be a primary carbon atom or a secondary carbon atom. n represents the average number of repetitions of the oxyethylene group, and is 0. <n≦4である。M + is a cation other than hydrogen ion. X is M + is the valence of .

[0012] (a1) In formula, R 11 R has 8 to 18 carbon atoms, preferably 10 to 14, and more preferably 12 to 14. 11 In terms of improving the cleaning power and reducing the environmental load, the alkyl group is preferably a linear alkyl group derived from a fat or oil raw material. Suitable fat or oil raw materials include palm kernel oil, coconut oil, etc.

[0013] In the formula (a1), M may be any element capable of forming a water-soluble salt, and examples of M include alkali metals, alkaline earth metals, ammonium, and alkanolamines. Examples of alkali metals include sodium and potassium. Examples of alkaline earth metals include calcium and magnesium. Examples of alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. When M is an alkaline earth metal, the alkaline earth metal ion (X=2) is an anion (R 11 -O-(CH2CH2O) n -SO3 - ) for every 1 mole of

[0014] The alkane sulfonate may be an alkane sulfonate having 10 to 20 carbon atoms, preferably an alkane sulfonate having 14 to 17 carbon atoms, and more preferably a secondary alkane sulfonate (SAS) having 14 to 17 carbon atoms. Examples of the alkane sulfonate include alkali metal salts, alkaline earth metal salts, alkanolamine salts, and ammonium salts. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the alkaline earth metal salt include magnesium salt and calcium salt. Examples of the alkanolamine salt include monoethanolamine salt (monoethanolamine), diethanolamine salt (diethanolamine), triethanolamine salt (triethanolamine), etc. Among them, the alkali metal salt is preferable as the alkane sulfonate, and the sodium salt and potassium salt are more preferable.

[0015] The olefin sulfonate may be an α-olefin sulfonate having 10 to 20 carbon atoms. Examples of α-olefin sulfonate include sodium salts and potassium salts. Examples of alkaline earth metal salts include magnesium salts and calcium salts. Examples of alkanolamine salts include monoethanolamine salts (monoethanolamine), diethanolamine salts (diethanolamine), and triethanolamine salts (triethanolamine). Among these, the alkane sulfonate is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

[0016] As the component (A), alkyl ether sulfates, alkanesulfone sulfates, and alkanesulfonates are preferred. The above-mentioned component (A) may be used alone or in combination of two or more kinds.

[0017] The content of component (A) is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, and even more preferably 5 to 10 mass%, based on the total mass of the liquid detergent composition. When the content of component (A) is equal to or more than the lower limit, the cleaning power can be further improved. When the content of component (A) is equal to or less than the upper limit, the sliminess during rinsing can be further reduced.

[0018] <(B) component> Component (B) is a semi-polar surfactant. By including component (B) in the liquid detergent composition, it is possible to enhance the cleaning power and reduce the slimy feeling during rinsing. A "semi-polar surfactant" is a surfactant that has semi-polar bonds (bonds with intermediate properties between non-polar and polar bonds). A "semi-polar surfactant" is cationic or non-polar depending on the pH of the solution in which it is dissolved or the dispersion in which it is dispersed. Examples of the component (B) include alkylamine oxide type semi-polar surfactants and alkylamidoamine oxide type semi-polar surfactants.

[0019] An example of the component (B) is a compound represented by the following formula (b1).

[0020] [ka]

[0021] In formula (b1), R 21 is a linear or branched alkyl group having 8 to 18 carbon atoms, or a linear or branched alkenyl group having 8 to 18 carbon atoms; R 22 , R 23 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, R 24 is an alkylene group having 1 to 4 carbon atoms. A is -CONH-, -NHCO-, -COO-, -OCO- or -O-, and r is the number 0 or 1.

[0022] The alkylamine oxide type semi-polar surfactant is preferably an alkyldimethylamine oxide having an alkyl group with a carbon number of 8 to 18, and more preferably an alkyldimethylamine oxide having an alkyl group with a carbon number of 12 to 14. Examples of the alkylamine oxide type semi-polar surfactant include lauryl dimethylamine oxide, myristyl dimethylamine oxide, coconut oil dimethylamine oxide, and the like. Among these components (B), alkylamine oxide-type semi-polar surfactants are preferred, lauryl dimethylamine oxide, myristyl dimethylamine oxide, and coconut oil dimethylamine oxide are more preferred, and lauryl dimethylamine oxide is even more preferred. These components (B) may be used alone or in combination of two or more.

[0023] The content of component (B) is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, and even more preferably 5 to 10 mass%, based on the total mass of the liquid detergent composition. When the content of component (B) is equal to or more than the lower limit, the stickiness during rinsing can be further reduced. When the content of component (B) is equal to or less than the upper limit, the cleaning power can be further improved.

[0024] The ratio of the mass of component (A) to the mass of component (B) (A / B ratio) is preferably 0.5 to 2, more preferably 0.7 to 1.5, and even more preferably 1 to 1.2. When the A / B ratio is equal to or greater than the lower limit, the cleaning power can be further increased. When the A / B ratio is equal to or less than the upper limit, the cleaning power can be further increased and the sliminess during rinsing can be further reduced.

[0025] <(C) component> The component (C) is a nonionic surfactant. By including the component (C), the liquid detergent composition can reduce sliminess during rinsing.

[0026] Examples of the component (C) include the following nonionic surfactants. (1) Polyoxyalkylene alkyl ether. (2) Polyoxyalkylene alkyl (or alkenyl) phenyl ethers. (3) Fatty acid alkyl ester alkoxylates in which alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters. (4) Polyoxyalkylene sorbitan fatty acid esters. (5) Polyoxyalkylene sorbite fatty acid ester. (6) Polyoxyalkylene fatty acid esters. (7) Polyoxyalkylene hydrogenated castor oil. (8) Glycerol fatty acid ester. (9) Alkyl polyglycosides.

[0027] As the component (C), polyoxyalkylene-added nonionic surfactants represented by formula (c1) (alcohol-type nonionic surfactants), nonionic surfactants represented by formula (c2), alkyl (poly)glycosides, sorbitan fatty acid esters, etc. are preferred. Among them, as the component (C), polyoxyalkylene (carbon number 2-3) alkyl (carbon number 8-15) ethers (average number of alkylene oxides added: 3-20) are more preferred.

[0028] R 16 -O-(R 17 O) t -H (c1)

[0029] (c1) where R 16 R is a hydrocarbon group having 8 to 18 carbon atoms. 16 The number of carbon atoms in R is preferably 10 to 18. 17 is a hydrocarbon group having 1 to 3 carbon atoms. t is R 17 A number between 1 and 20 that represents the average number of O repeats.

[0030] (c1) where R 16 The hydrocarbon group in R may be linear or branched. 16 The hydrocarbon group in preferably contains a branched chain. R 16 When R contains a branched hydrocarbon group, 16 The average number of side chains is preferably from 0.2 to 2, and more preferably from 0.5 to 1.5. R 16 The average number of side chains (hereinafter also referred to as the "average branch number") of component (C) is defined as the number of methyl groups in one molecule of component (C) minus 1. The average branch number is the statistical average value of the number of side chains (branch number) in component (C). The average number of methyl groups in component (C) is 1 The average branch number in this specification is calculated by the following formula (i). That is, the average branch number is 1This value is determined by dividing the signal area corresponding to the methyl proton (CH group) in the H-NMR spectrum by 3 and comparing this value with the signal area of ​​the methylene proton of the CH2-OH group divided by 2. Average branch number = {(integral value of the signal region corresponding to the methyl proton of the CH3 group / 3) - (integral value of the signal region corresponding to the methylene proton of the CH2-OH group / 2)} / (integral value of the signal region corresponding to the methylene proton of the CH2-OH group / 2) (i) In addition, 1 In the H-NMR spectroscopic analysis, the measurement target (component (C)) is dissolved in heavy water or heavy chloroform, and the sample concentration is set to 30 mass %. 1 The measurement is performed by H-NMR (for example, JEOL's product name "JNM-LA300 FT NMR SYSTEM").

[0031] R 16 The hydrocarbon group in is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. Also, R 16 may be derived from natural alcohol or synthetic alcohol. Suitable natural alcohols include, for example, coconut oil higher alcohol, CO1270A, etc. Suitable synthetic alcohols include, for example, commercially available synthetic alcohols such as Dobanol, Safol, Neodol, Dyadol, and Lutensol.

[0032] (c1) where R 17 The number of carbon atoms is preferably 2 to 3, and more preferably 2. (c1) where R 17 is preferably an alkylene group or an alkenylene group, more preferably an alkylene group, and more preferably an ethylene group. In formula (c1), t is a number from 1 to 20, and more preferably 3 to 10. If t is 2 or more, R is 2 or more 17 O may be the same or different. Two or more R 17 When O are different, they may be arranged in a block fashion or in a random fashion.

[0033] R 18 -C(=O)-NH-(R 19 O) u -H (c2)

[0034] (c2) where R 18 is a linear alkyl group having 5 to 19 carbon atoms, a branched alkyl group having 5 to 19 carbon atoms, a branched alkyl group having 5 to 19 carbon atoms, or a branched alkenyl group having 5 to 19 carbon atoms. R 19 is a hydrocarbon group having 2 to 4 carbon atoms. 19 It is a number between 1 and 20 that represents the average number of repeats of O.)

[0035] (c2) where R 18 The number of carbon atoms is preferably 9 to 13. (c2) where R 19 is preferably an alkylene group or an alkenylene group, more preferably an alkylene group, and further preferably an ethylene group. In the formula (c2), u is preferably 1 to 4.

[0036] As the (C) component, from the viewpoint of ease of achieving the effects of the present invention, a polyoxyalkylene-added nonionic surfactant represented by formula (c1) (component (c1)) or an alkyl (poly)glycoside is preferred, component (c1) is more preferred, Guerbet alcohol-type nonionic surfactants (e.g., Guerbet alcohol ethoxylate) are even more preferred, and 2-propylheptyl alcohol ethoxylate is particularly preferred. The average number of repetitions of the oxyethylene group in the component (c1) is preferably 6 to 14, more preferably 8 to 11, and particularly preferably 10. The above-mentioned component (C) may be used alone or in combination of two or more kinds.

[0037] The content of component (C) is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, and even more preferably 5 to 10 mass%, based on the total mass of the liquid detergent composition. When the content of component (C) is equal to or more than the lower limit, the stickiness during rinsing can be further reduced. When the content of component (C) is equal to or less than the upper limit, the cleaning power can be further improved.

[0038] <(D) component> The component (D) is an enzyme (excluding catalase). By including the component (D), the liquid detergent composition exhibits excellent detergency.

[0039] Examples of the component (D) include amylase, protease, mannanase, cellulase, lipase, etc., of which amylase and protease are preferred, and a combination of amylase and protease is more preferred. The component (D) may be used alone or in combination of two or more types.

[0040] The content of component (D) is preferably 720 to 3000 ppm by mass, more preferably 850 to 2400 ppm by mass, and even more preferably 1100 to 1650 ppm by mass, calculated as protein, based on the total mass of the liquid detergent composition. When the content of component (D) is equal to or greater than the lower limit, the cleaning power can be further improved. When the content of component (D) is equal to or less than the upper limit, sliminess can be further reduced.

[0041] The content of the (D) component as an enzyme preparation (formulation content) is preferably 0.35 to 1 mass % as the enzyme preparation, and more preferably 0.5 to 0.8 mass %, based on the total mass of the liquid detergent composition. When the (D) component content in the formulation is equal to or greater than the lower limit, the cleaning power can be further improved. When the (D) component content in the formulation is equal to or less than the upper limit, sliminess can be further reduced.

[0042] When component (D) contains amylase, the content of amylase is preferably an amount that results in an amylase activity of 0.44 to 1.25 U, more preferably an amount that results in an amylase activity of 0.63 to 1.00 U, as measured by the measurement method described in the Examples. When the amylase activity is equal to or higher than the lower limit, the cleaning power can be further improved. When the amylase activity is equal to or lower than the upper limit, sliminess can be further reduced.

[0043] When the (D) component contains amylase, the ratio of the content (mass) of the (D) component to the amylase activity (U) (D / amylase activity ratio) is preferably 0.15 to 0.21, more preferably 0.16 to 0.19. When the D / amylase activity ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the D / amylase activity ratio is equal to or less than the upper limit, sliminess can be further reduced.

[0044] When component (D) contains a protease, the content of the protease is preferably an amount that results in a protease activity of 0.18 to 0.45 U, more preferably 0.24 to 0.37 U, as measured by the measurement method described in the Examples. When the protease activity is equal to or higher than the lower limit, the cleaning power can be further improved. When the protease activity is equal to or lower than the upper limit, sliminess can be further reduced.

[0045] When the (D) component contains a protease, the ratio of the content (mass) of the (D) component to the protease activity (U) (D / protease activity ratio) is preferably 0.43 to 0.50, more preferably 0.44 to 0.47. When the D / protease activity ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the D / protease activity ratio is equal to or less than the upper limit, sliminess can be further reduced.

[0046] When component (D) contains lipase, the content of lipase is preferably an amount that results in a lipase activity of 0.2 to 0.6 U, more preferably an amount that results in a lipase activity of 0.25 to 0.55 U, as measured by the measurement method described in the Examples. When the lipase activity is equal to or higher than the lower limit, the cleaning power can be further improved. When the lipase activity is equal to or lower than the upper limit, sliminess can be further reduced.

[0047] When the (D) component contains lipase, the ratio of the content (mass) of the (D) component to the lipase activity (U) (D / lipase activity ratio) is preferably 0.30 to 0.38, more preferably 0.32 to 0.36. When the D / lipase activity ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the D / lipase activity ratio is equal to or less than the upper limit, sliminess can be further reduced.

[0048] When component (D) contains mannanase, the content of mannanase is preferably an amount that corresponds to 0.35 to 1.1 U of mannanase measured by the measurement method described in the Examples, and more preferably an amount that corresponds to 0.45 to 0.80 U of mannanase. When the mannanase activity is equal to or higher than the lower limit, the cleaning power can be further improved. When the mannanase activity is equal to or lower than the upper limit, sliminess can be further reduced.

[0049] When the (D) component contains mannanase, the ratio of the content (mass) of the (D) component to the mannanase (U) (D / mannanase activity ratio) is preferably 0.16 to 0.24, more preferably 0.18 to 0.22. When the D / mannanase activity ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the D / mannanase activity ratio is equal to or less than the upper limit, sliminess can be further reduced.

[0050] <(E) component> Component (E) is at least one member selected from the group consisting of isothiazolinones and their derivatives represented by the following formula (e1) or (e2), and phenylboronic acid and its derivatives represented by the following formula (e3). By including component (E), the liquid detergent composition can reduce sliminess during rinsing.

[0051] [ka]

[0052] [In formula (e1), R 1 is H or an alkyl group having 1 to 8 carbon atoms, R 2 is H, CH3, Cl, Br or NH2, R 3is H, CH3, Cl or CH2NH2.

[0053] [ka]

[0054] [ka]

[0055] [In formula (e3), R 4 , R 5 and R 6 are each independently H, a hydrocarbon group having 1 to 3 carbon atoms, Cl, Cl, F, OH, SCH3, NH2, or COH.

[0056] (e1) where R 1 is preferably CH3. (e1) where R 2 is preferably H. (e1) where R 3 is preferably H.

[0057] (e3) where R 4 , R 5 and R 6 When at least one of R is a hydrocarbon group, the hydrocarbon group may be saturated, unsaturated, linear, or branched. 4 , R 5 and R 6 Any of the above may be H.

[0058] Derivatives of the component (E) include methylisothiazolinone (MIT), chloromethylisothiazolinone (CMIT), 1,2-benzisothiazol-3-one (BIT), and 4-formylphenylboronic acid (4FPBA). As the component (E), one type may be used alone, or two or more types may be used in combination.

[0059] (E) is R in formula (e1). 1 CH3, R2 and R 3 isothiazolinone and its derivatives represented by the formula (e2); isothiazolinone and its derivatives represented by the formula (e3), 4 and R 5 is H and R 6 Phenylboronic acid having a formula of CHO and its derivatives are preferred, and isothiazolinone represented by formula (e2) and its derivatives are more preferred.

[0060] The content of component (E) is preferably 0.002 to 0.02 mass%, more preferably 0.005 to 0.018 mass%, and even more preferably 0.009 to 0.015 mass%, based on the total mass of the liquid detergent composition. When the content of component (E) is equal to or greater than the lower limit, the cleaning power can be further increased and sliminess during rinsing can be further reduced. When the content of component (E) is equal to or less than the upper limit, the cleaning power can be further increased.

[0061] The mass ratio of the (D) component to the (E) component (D / E ratio) is preferably 4 to 130, more preferably 6 to 40, and even more preferably 7 to 20. When the D / E ratio is equal to or greater than the lower limit, the cleaning power can be further increased. When the D / E ratio is equal to or less than the upper limit, the cleaning power can be further increased and the sliminess during rinsing can be further reduced.

[0062] <(F) Component> Component (F): one or more members selected from the group consisting of lactic acid, malic acid, and salts thereof. By including component (F), the liquid detergent composition can reduce sliminess during rinsing.

[0063] Examples of salts of the component (F) include alkali metal salts and alkaline earth metal salts. Examples of the alkali metal salt include sodium salt, potassium salt, etc. Examples of the alkaline earth metal salt include calcium salt, magnesium salt, etc. As the component (F), a lactate salt is preferred, and sodium lactate is more preferred.

[0064] The above-mentioned component (F) may be used alone or in combination of two or more.

[0065] The content of component (F) is preferably 0.1 to 2 mass%, more preferably 0.5 to 1.5 mass%, and even more preferably 1 to 1.5 mass%, based on the total mass of the liquid detergent composition. When the content of component (F) is equal to or more than the lower limit, sliminess during rinsing can be further reduced. When the content of component (F) is equal to or less than the upper limit, cleaning power can be further improved.

[0066] The mass ratio of the (D) component to the (F) component (D / F ratio) is preferably 0.04 to 3, more preferably 0.06 to 0.4, and even more preferably 0.07 to 0.2. When the D / F ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the D / F ratio is equal to or less than the upper limit, the sliminess during rinsing can be further reduced.

[0067] <Optional ingredients> The liquid detergent composition may contain components (optional components) other than the components (A) to (F). The optional components include surfactants (optional surfactants) other than the components (A) to (C), catalase, preservatives, inorganic builders, hydrotropes, fragrances, pH adjusters, water, colorants, etc. The total amount of components (A) to (F) and any optional components does not exceed 100% by mass (however, component (D) is the content in the formulation).

[0068] Optional Surfactant Optional surfactants include amphoteric surfactants and the like. Examples of the amphoteric surfactant include carboxylate-type amphoteric surfactants and sulfonate-type amphoteric surfactants. Examples of carboxylate-type amphoteric surfactants include betaine-type amphoteric surfactants such as lauryl dimethyl amino acetate betaine, coconut alkyl dimethyl amino acetate betaine, coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl dimethyl amino acetate betaine, coconut alkyl amidopropyl dimethyl amino acetate betaine, and lauryl dimethyl sulfobetaine. Examples of the sulfonate type amphoteric surfactant include betaine type amphoteric surfactants such as lauryl hydroxysulfobetaine. These optional surfactants may be used alone or in combination of two or more.

[0069] The liquid detergent composition may contain one or more selected from higher fatty acids (fatty acids having 8 to 22 carbon atoms) and their salts (i.e., soaps). Examples of higher fatty acid salts include alkali metal salts, alkaline earth metal salts, alkanolamine salts, and ammonium salts. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the alkaline earth metal salt include magnesium salt and calcium salt. Examples of the alkanolamine salt include monoethanolamine salt (monoethanolamine), diethanolamine salt (diethanolamine), triethanolamine salt (triethanolamine), etc. Among them, the higher fatty acid salt is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt. The content of the higher fatty acid or a salt thereof is preferably 0 to 3 mass % based on the total mass of the liquid detergent composition.

[0070] The total amount of surfactants including the components (A) to (C) and any optional surfactants is preferably from 5 to 50 mass %, more preferably from 15 to 25 mass %, based on the total mass of the liquid detergent composition. The total amount of the components (A) to (C) is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass, based on the total amount of the surfactants.

[0071] <Catalase> Catalase is used to remove hydrogen peroxide. The content of catalase in the formulation is, for example, 0.05 to 0.1% by mass based on the total mass of the liquid detergent composition.

[0072] <Inorganic Builder> Examples of the inorganic builder include metal oxides, such as zinc oxide and magnesium oxide. The content of the inorganic builder is preferably 0.05 to 0.5% by mass based on the total mass of the liquid detergent composition.

[0073] <Hydrotrope agent> Examples of hydrotropic agents include monohydric alcohols having 2 to 4 carbon atoms, dihydric alcohols having 2 to 4 carbon atoms, and glyceryl ethers having 4 to 10 carbon atoms. Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, n-propanol, and isopropanol. Examples of the dihydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, and diethylene glycol. Examples of the glyceryl ether having 4 to 10 carbon atoms include glycerin and hexyl glyceryl ether. The hydrotrope agent may be used alone or in combination of two or more kinds. The content of the hydrotrope agent is preferably 1 to 5% by mass based on the total mass of the liquid detergent composition.

[0074] <pH adjuster> Examples of the pH adjuster include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and isopropanolamine, sodium hydroxide, potassium hydroxide, and sulfuric acid. The pH adjusters may be used alone or in appropriate combination of two or more.

[0075] ≪Fragrance≫ As the fragrance, those usually used in liquid detergent compositions can be applied. Examples of the fragrance include blended fragrance compositions 1 to 4 described in Tables 1 to 8 of JP 2020-132680 A.

[0076] ≪Water≫ The water includes ion-exchanged water, pure water, and the like. The content of water is preferably 45 to 90% by mass based on the total mass of the liquid detergent composition.

[0077] <Physical Properties> The pH of the liquid detergent composition at 25°C is preferably 5-10, and more preferably 6-8. The pH of the liquid detergent composition is a value measured by a method conforming to JIS Z 8802:2011 "pH measurement method."

[0078] The viscosity (25°C) of the liquid detergent composition is preferably 30 to 300 mPa·s, more preferably 60 to 120 mPa·s. The viscosity (25°C) is a value measured at 25°C using a B-type viscometer with rotor number No. 1 and a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts to rotate.

[0079] (Manufacturing method) The liquid detergent composition of the present invention can be produced in accordance with a method for producing a liquid detergent composition known in the art. For example, the components (A) to (F) are added to water as a solvent, and optional components are added as necessary, followed by mixing.

[0080] (How to use) As a method for cleaning an object to be cleaned using the liquid detergent composition of the present invention, for example, the object may be scrubbed with a sponge or the like soaked in the undiluted liquid of the liquid detergent composition or a diluted solution thereof. Alternatively, the object may be immersed in the diluted solution and cleaned by scrubbing with a sponge or the like. In this case, since the liquid detergent composition of the present invention has excellent cleaning power, it can effectively remove dirt such as oils and fats, proteins, etc. adhering to the object to be cleaned. The object is then rinsed with water. In this case, the liquid detergent composition of the present invention is less likely to become slimy when diluted with rinsing water. Therefore, the user can visually confirm the removal of dirt while feeling the cleaning power of the composition because the sliminess during rinsing is suppressed. Examples of items to be washed include tableware such as plates, chopsticks, and spoons, cooking utensils such as pots, knives, and cutting boards, kitchen appliances such as ranges and stoves, sinks, etc. In this specification, these are collectively referred to as "kitchen utensils." EXAMPLES

[0081] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0082] (Raw materials used) <Component (A)> a-1: Alkyl ether sulfate (AES), polyoxyethylene (1) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) sulfate sodium salt, Lion Corporation's "BRES (1)"; R in formula (a1) 11 A compound in which is a linear alkyl group having 12 to 14 carbon atoms, n=1, and M=Na. a-2: Sodium secondary alkane sulfonate (SAS) having 14 to 17 carbon atoms, "HOSTAPUR (registered trademark) SAS30A" manufactured by Clariant Japan. a-3: Sodium α-olefin sulfonate (AOS) with 14 carbon atoms, "Liporan LB-440" manufactured by Lion Specialty Chemicals.

[0083] <Component (A')> a'-1: Linear alkylbenzene sulfonate (LAS), "Lion LH-200" manufactured by Lion Specialty Chemicals.

[0084] <(B) component> b-1: Alkylamine oxide (AAO) having a linear alkyl group with 12 carbon atoms, "Cadenax DM12D-W(C)" manufactured by Lion Specialty Chemicals. b-2: Amidopropyldimethylamine oxide (APDMAO), “GENAMINOX AP” manufactured by Clariant Japan.

[0085] <(C) component> c-1: Guerbet-type alcohol ethoxylate (AE(EO10)) having an alkyl group with 10 carbon atoms and an average repeat number of oxyethylene groups of 10, "Lutensol XP-100" manufactured by BASF. c-2: Alcohol ethoxylate (AE(EO5)) having a branched alkyl group with 10 carbon atoms and an average repeat number of oxyethylene groups of 5, "Lutensol TO-5" manufactured by BASF. c-3: Alcohol ethoxylate (AE(EO9)) having a secondary alkyl group with 12 to 14 carbon atoms and an average number of repeating oxyethylene groups of 9, "Leocol SC-90" manufactured by Lion Specialty Chemicals. c-4: Alcohol ethoxylate (AE(EO6)) having a linear alkyl group with 12 to 14 carbon atoms and an average repeating number of oxyethylene groups of 6, "BRE(6)" manufactured by Lion Corporation. c-5: Alkyl polyglycoside (APG) having a linear alkyl group with 12 to 14 carbon atoms, BASF's "Glucopon 600CS UP".

[0086] <(D) component> d-1: A mixture of amylase and protease (amylase / protease), "MedleyCore 210L" manufactured by Novozymes. d-2: Amylase, Novozymes' "Achieve Alpha 100L". d-3: Protease, Novozymes' "Blaze Pro 100L". d-4: Lipase, Novozymes' "Lipex Evity 200L". d-5: Mannanase, Novozymes' "Mannaway 200L". d-6: Cellulase, Novozymes' "Carezyme Premium 4500L".

[0087] <(E) component> e-1: Isothiazolinone, 1,2-benzisothiazol-3-one (BIT), "NIPACIDE 20" manufactured by Clariant Japan. e-2: Phenylboronic acid, 4-formylphenylboronic acid (4FPBA). e-3: Isothiazolinone, 2-methyl-4-isothiazolin-3-one (MIT), "ACTICIDE M20" manufactured by Thor Japan.

[0088] <(F) Component> f-1: Sodium lactate (Na lactate), "Fermented Sodium Lactate" manufactured by Corbion Japan. f-2: Sodium malate (Na malate), "DL-Sodium Malate" manufactured by Fuso Chemical Co., Ltd.

[0089] <Optional ingredients> Catalase: Novozymes "Terminox Ultra 50L". ethanol. Citric acid. Paratoluenesulfonic acid (pTS). Sodium benzoate (Na benzoate). Zinc oxide. Sulfamic acid. Fragrance. Sodium hydroxide (NaOH). Water: Ion-exchanged water.

[0090] (Measurement method) <Amylase activity> Amylase activity was measured by the following method. Phadebas tablets (Magle, Phadebas Amylase Test for measuring amylase activity), which are cross-linked starch polymers containing insoluble blue pigment, were hydrolyzed with alpha amylase, and the absorbance (620 nm) of the water-soluble blue pigment was measured to determine alpha amylase activity. 20.0g of sodium sulfite (Junsei Chemical Co., Ltd., special grade, etc.), 6.15g of potassium dihydrogen phosphate (Hayashi Pure Chemical Co., Ltd., special grade, etc.), 10.86g of disodium hydrogen phosphate dodecahydrate (Kanto Chemical Co., Ltd., special grade, etc.), 0.015g of calcium chloride dihydrate (Kanto Chemical Co., Ltd., deer grade 1, etc.), and 0.75mL of Brij35 (MERCK, 30% aqueous solution) were precisely weighed, dissolved in ion-exchanged water, and the volume was adjusted to 1L to obtain a buffer solution. 0.5g of the liquid detergent composition of each example was precisely weighed, dissolved in the above buffer solution, and the volume was adjusted to 100mL to obtain a sample solution. 1mL of the sample solution was placed in a test tube (18mm x 180mm). 5.0mL of the buffer solution previously adjusted to 37°C was placed in the sample test tube, followed by one Padebath tablet, which was stirred with a flash mixer for 10 seconds, and then the test tube was placed in a water bath at 37°C. This procedure was repeated for each sample at 30 second intervals. After exactly 15 minutes, 1.0 mL of 1 mol / L NaOH solution was added to the test tube, stirred for 10 seconds with a flash mixer, left at room temperature for 15 minutes, and then immediately filtered through filter paper. If there was any turbidity, it was then filtered with a filtration kit. The absorbance of the sample and blank (enzyme-free composition) filtrate obtained by the above procedure was measured at a measurement wavelength of λ = 620 nm (1 cm quartz cell, slit width 0.5 mm). The enzyme activity of amylase was calculated using the following formula. Enzyme activity (U) = (sample absorbance) - (blank absorbance)

[0091] <Protease activity> Protease activity was measured by the following method. The enzyme was allowed to act on milk casein, and undecomposed proteins were precipitated by adding trichloroacetic acid (TCA), followed by filtration. The absorbance (λ=275 nm) of the filtrate was measured to determine the amount of eluted amino acids having a phenyl group (e.g., tyrosine), and the protease activity was calculated. 1.2 g of milk casein (manufactured by 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 cause swelling. Next, 160 mL of 0.05 mol / L boric acid solution was added, stirred with a stirrer to disperse, and adjusted to pH 10.5 with 1 mol / L-NaOH, and then the volume was adjusted to 200 mL. 1 g of the liquid detergent composition of each example was precisely weighed, dissolved in ion-exchanged water, and the volume was adjusted to 100 mL to prepare a sample solution. 1 mL of the sample solution was placed in a test tube (18 mm x 180 mm). 5.0 mL of casein solution preheated to 37°C was placed in the sample test tube, stirred with a flash mixer for 10 seconds, and then placed in a water bath at 37°C. This procedure was repeated for each sample at 30-second intervals. Exactly 30 minutes later, 5.0 mL of 0.44 mol / L-TCA solution was added to the test tube, stirred with a flash mixer for 10 seconds, and left in a water bath for 30 minutes, then immediately filtered through filter paper. The sample was then filtered through a filter (Tomsic, NP-44525-ACF). The absorbance of the sample and blank (enzyme-free composition) filtrate obtained by the above procedure was measured at a wavelength λ of 275 nm (1 cm quartz cell, slit width 0.5 mm). The enzyme activity of amylase was calculated using the following formula. Enzyme activity (U) = (sample absorbance) - (blank absorbance)

[0092] <Lipase activity> Lipase activity was measured by the following method. Substrate (BALB), SDS, and esterase inhibitor (PMSF) were added to the sample, and esterases other than lipase in the sample were inactivated by PMSF and SDS, while lipase in the sample was activated by SDS. The activated lipase hydrolyzed BALB to generate dimercaprol (BAL). The generated BAL reacted quantitatively with DTNB to generate yellow 5-thio-2-nitrobenzoic acid (TNB) anion. The reaction of lipase was stopped by adding the reaction stop solution. The lipase activity was calculated by measuring the absorbance (λ = 412 nm). 2.4 mL of buffer was added to the container containing the color developer to completely dissolve the color development solution, and 22 mL of purified water was added to prepare the color development stock solution. The reaction stop stock solution solidified when stored in a cool place, so it was melted by heating (30 °C, 5 to 10 minutes). Next, the entire volume was poured into a 500mL graduated cylinder while washing with purified water, and the final volume was adjusted to 500mL with purified water, and then transferred to an Erlenmeyer flask. Two glass test tubes were prepared for each sample, one for the specimen (A) and the other for the blank (B). 1mL of color-developing solution and 50μL of sample were added to both test tubes A and B, and mixed, and then 20μL of esterase inhibitor solution was added. After mixing, each test tube was placed in a thermostatic bath and heated at 30±1℃ for 5 minutes. After 5 minutes, 100μL of substrate solution was added only to test tube A while still in the thermostatic bath, and immediately after mixing, it was incubated exactly at 30±1℃. After the incubation, the reaction stop solution was immediately added to test tube A while still in the thermostatic bath. Next, 2mL of reaction stop solution was added to test tube B. Each test tube was removed from the thermostatic bath and mixed, and then 100μL of substrate solution was added only to test tube B, and mixed again. Using purified water as a control, the absorbance of the sample (A) and blank (B) was measured at a wavelength of 412 nm. Enzyme activity (U) = (sample absorbance) - (blank absorbance)

[0093] <Mannanase activity> Mannanase activity was measured by the following method. The enzyme (mannanase) in liquid detergent was allowed to act on polysaccharide (galactomannan), and the reducing end of galactomanan was also colored with a p-hydroxybenzhydrazide (PAHBAH) coloring reagent.The degree of decomposition of galactomannan was detected by measuring the absorbance (λ = 275 nm), and the mannanase activity was calculated. 0.15 g of galactomannan (Megazyme) was added to 100 mL with ion-exchanged water and stirred in a 50 ° C water bath until it became transparent and uniform. After stirring, it was left to stand in a 50 ° C water bath. 46.85 g of disodium hydrogen phosphate anhydrous (special grade reagent, Kanto Chemical Co., Ltd.) and 9.4 g of sodium dihydrogen phosphate dihydrate (special grade reagent, Kanto Chemical Co., Ltd.) were prepared to 1000 mL with ion-exchanged water. In addition, the PAHBAH coloring reagent was prepared by dissolving 0.552 g of Bismuth (3) acetate, 99% (Alfa Aesar, etc.), 2 g of p-hydroxybenzhydrazide (Wako Pure Chemical Co., Ltd., etc.), and 5 g of (+)-sodium potassium tartrate tetrahydrate (special grade reagent, Junsei Chemical Co., Ltd., etc.) in 0.5 mol / L NaOH to a total of 100 mL. The whole was covered with aluminum foil and stirred while blocking light until the reagent was dissolved. 0.07 g of each liquid detergent composition was weighed out, dissolved in phosphate buffer, and adjusted to a volume of 100 mL. 2 mL of the sample solution was placed in a test tube (18 mm x 180 mm). 5 mL of the galactomannan substrate solution was placed in the sample test tube, stirred with a flash mixer for 10 seconds, and placed in a water bath at 50 ° C. This operation was repeated for each sample at 30 second intervals. Exactly 30 minutes later (using a stopwatch), 4 mL of PAHBAH color reagent was added, stirred with a flash mixer for 10 seconds, and left on ice for 10 minutes. At this time, 4 mL of PAHBAH color reagent was also added to the blank, stirred with a flash mixer for 10 seconds, and the enzyme was inactivated. Then, 5 mL of the galactomannan substrate solution was added, stirred with a flash mixer for 10 seconds again, and left on ice for 10 minutes. Next, the color development operation was performed. Each test tube containing the PAHBAH reagent was placed in a 70°C water bath at 10 second intervals, and then removed exactly 10 minutes later and placed in an ice bath. Immediately after that, the tube was filtered through filter paper, and the OD value of the filtrate was measured at a wavelength of λ=405 nm using an absorbance meter (subject: phosphate buffer). Enzyme activity (U) = (sample absorbance) - (blank absorbance)

[0094] <Enzyme quantification method (protein equivalent)> Using a DC protein assay kit manufactured by Bio-Rad, ovalbumin (a protein that forms egg white) was used as the standard protein. The buffer was 0.1N NaOH. 20 μL of S reagent (surfactant solution) was added to 1 mL of reagent A (alkaline copper tartaric acid) to prepare A' solution. 200 μL of the liquid detergent composition of each example was weighed into a 2.0 mL microtube. 100 μL of A' solution and 800 μL of reagent B (Folin's reagent dilution solution) were weighed therein and thoroughly stirred. After that, after leaving it at room temperature, the absorbance was measured at a measurement wavelength of 750 nm within 1 hour (1 cm quartz cell, slit width 0.5 mm). The same treatment was performed on ovalbumin solutions with known concentrations to create a calibration curve. The protein amount was calculated from the calibration curve using the absorbance of the measurement sample, and this was used as the protein equivalent value of the enzyme.

[0095] (Evaluation method) <Carbonara cleaning power> The weight (α1) of the evaluation board SUS304 (7.5cm x 2.5cm) was measured. Milky carbonara (Nissin Seifunsha's "Welna") was heated at 600W for 2 minutes, and the carbonara sauce without the toppings was stirred with a medicine spoon, 0.5g of this was applied to the evaluation board, baked at 130°C for 5 minutes, left to cool, and the weight (β1) was measured. The liquid detergent composition of each example was stored at 40°C for 1 month, and this was diluted with tap water to 0.5% by mass to make a cleaning solution. The evaluation board was immersed in this cleaning solution for 10 minutes. After that, it was lightly washed with tap water collected in a beaker, dried, and the weight (γ1) was measured. The carbonara cleaning power (rounded off to the nearest whole number) was calculated using the following formula, and the results were evaluated according to the following evaluation criteria.

[0096] Carbonara cleaning power = (1-((γ1-α1) / (β1-α1))) x 100

[0097] Evaluation Criteria ◎: Carbonara cleaning power is 76% or more. ○: Carbonara cleaning power is 51% or more and 75% or less. △: Carbonara cleaning power is between 26% and 50%. ×: Carbonara cleaning power is less than 25%.

[0098] <Curry cleaning power> The weight (α2) of the evaluation board SUS304 (7.5 cm x 2.5 cm) was measured. Bon Curry Gold (Otsuka Foods) was heated at 600 W for 2 minutes, the curry without the ingredients was stirred with a medicine spoon, 0.5 g of this was applied to the evaluation board, baked at 130 ° C for 5 minutes, left to cool, and the weight (β2) was measured. The liquid detergent composition of each example was stored at 40 ° C for 1 month, and this was diluted with tap water to 0.5 mass % to make a cleaning solution. The evaluation board was immersed in this cleaning solution for 10 minutes. After that, it was lightly washed with tap water collected in a beaker, dried, and the weight (γ2) was measured. The curry cleaning power (rounded off to the nearest whole number) was calculated using the following formula, and the results were evaluated according to the following evaluation criteria.

[0099] Curry cleaning power = (1-((γ2-α2) / (β2-α2))) x 100

[0100] Evaluation Criteria ◎: Curry cleaning power is 76% or more. ○: Curry cleaning power is 51% or more and 75% or less. △: Curry cleaning power is between 26% and 50%. ×: Curry cleaning power is less than 25%.

[0101] <Slippery feeling when rinsing> A 21 cm diameter earthenware dish with no dirt was prepared. 49.5 g of tap water and 0.5 g of each liquid detergent composition were added to a 100 mL beaker and thoroughly stirred to prepare a diluted solution. 40 g of the diluted solution was dropped onto the earthenware dish. The degree of sliminess when the earthenware dish was rubbed with a finger 10 times was compared with the degree of sliminess of a earthenware dish to which 40 g of tap water was dropped, and the evaluation was performed according to the following evaluation criteria.

[0102] Evaluation Criteria ◎: No slime. ○: Slightly slimy. △: Quite slimy. ×: Very slimy.

[0103] (Examples 1 to 46, Comparative Examples 1 to 11) According to the compositions shown in Tables 1 to 9, components (A) to (F) and optional components were added to water and mixed to prepare the liquid detergents of each example. The amounts in the table are calculated as pure amounts (component (D) is the formulation content). The "appropriate amount" in the amount is the amount required to adjust the pH of the liquid detergent composition to the value in the table, and the "balance" is the remainder required to make the liquid detergent composition 100% by mass. In addition, a "-" in the amount in the table indicates that the component is not included. The liquid detergent composition of each example was evaluated for its carbonara cleaning power, curry cleaning power, and slippery feeling during rinsing, and the results are shown in the table.

[0104] [Table 1]

[0105] [Table 2]

[0106] [Table 3]

[0107] [Table 4]

[0108] [Table 5]

[0109] [Table 6]

[0110] [Table 7]

[0111] [Table 8]

[0112] As shown in Tables 1 to 9, in Examples 1 to 46, the evaluations of carbonara cleaning power, curry cleaning power, and sliminess during rinsing were all "△", "◯", or "◎". Example 1 lacking the component (A), Comparative Example 5 lacking the component (D), Comparative Example 6 in which the content of the component (D) was 695 ppm by mass, and Comparative Example 10 in which the D / E ratio was 0.3 were all rated as “x” for the carbonara cleaning power and curry cleaning power. Comparative Example 3 lacking the (B) component, Comparative Example 4 lacking the (C) component, Comparative Example 7 having a (D) component content of 3117 ppm by mass, Comparative Example 8 lacking the (E) component, Comparative Example 9 lacking the (F) component, and Comparative Example 11 having a D / E ratio of 15.6 were all rated as "x" for slipperiness during rinsing. From the above results, it was confirmed that application of the present invention can provide excellent cleaning power and reduce sliminess during rinsing.

Claims

1. Component (A): one or more selected from alkyl ether sulfate salts, alkanesulfonates, and olefinsulfonates; Component (B): a semi-polar surfactant; (C) component: a nonionic surfactant, (D) component: an enzyme (excluding catalase); Component (E): at least one selected from the group consisting of isothiazolinones and derivatives thereof represented by the following formula (e1) or (e2), and phenylboronic acid and derivatives thereof represented by the following formula (e3), 【Chemistry 1】 [(e1) in formula, R １ is H or an alkyl group having 1 to 8 carbon atoms, R ２ is H, CH ３ , Cl, Br or NH ２ , R ３ is H, CH ３ , Cl or CH ２ N.H. ２ It is.] 【Chemistry 2】 【Chemistry 3】 [(e3) in formula, R ４ , R ５ and R ６ each independently represents H, a hydrocarbon group having 1 to 3 carbon atoms, Cl, Cl, F, OH, or SCH ３ , N.H. ２ Or COH. (F) component: one or more selected from the group consisting of lactic acid, malic acid, and salts thereof; Including, The content of the component (D) is 720 to 3,000 ppm by mass in terms of protein, The mass ratio of the component (D) to the component (E) is 4 to 130. A liquid dishwashing detergent composition.

2. 2. The dishwashing liquid detergent composition according to claim 1, wherein the composition is represented by component (D) / component (F), and the mass ratio of component (D) to component (F) is 0.04 to 3.

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