JP2011162730A - Liquid detergent composition for automatic tableware washing washer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for an automatic tableware washing washer, the sustainability of the oxygen activity of which is high, and the sustainability of the washing performance of which is high. <P>SOLUTION: The liquid detergent composition for an automatic tableware washing washer comprises at least one compound (A) selected from the group consisting of compounds represented by formula (1) and salts thereof, an enzyme (a), a surfactant (b), and water. In the formula, X denotes an imino group, an oxygen atom or a sulfur atom. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition for an automatic dishwasher.

Automatic dishwashers have become rapidly popular in recent years. Also, from the viewpoint of ecology (for example, energy saving and resource saving), a washing machine that can reduce the amount of washing water to be used is popular. However, when washing is performed using such a washing machine in a state in which tableware is packed with a powder detergent, there is often a problem that the detergent remains undissolved, and there is a strong demand for a solution to this problem.
As a countermeasure, it is known to use a liquid detergent with high solubility, and a technique using a nonionic surfactant, enzyme and amino alcohol (Patent Document 1), boron compound, polyhydroxy compound, calcium ion, water In addition, a technique using an enzyme (Patent Document 2) is disclosed.

  Patent Document 1 discloses a detergent composition for an automatic dishwasher that is excellent in egg soil washing performance by blending amylase as an enzyme and alkanolamine. However, in order to further improve the detergency against protein stains such as egg stains, there is a problem in storage stability when a protease is added. In addition, when amylase and protease are stored for a long period of time, the enzyme activity is remarkably reduced, so that there is a big problem that the detergency does not continue.

  Patent Document 2 discloses a technique for maintaining the storage stability of both enzymes in a detergent composition in which amylase and protease coexist using boron, a polyhydroxy compound, and calcium ions. However, it is still difficult to ensure the storage stability of both enzymes.

Japanese Patent Laid-Open No. 3-126798 International Publication No. WO93 / 21299 Pamphlet

It is an object of the present invention to provide a liquid detergent composition for an automatic dishwasher having high enzyme activity and high cleaning performance.
In the present invention, “enzyme activity has good persistence” means that the difference between the enzyme activity measured after storage for a certain period of time and the enzyme activity measured immediately before storage is small and shows a certain enzyme activity. Means.

［式中、Ｘはイミノ基、酸素原子又は硫黄原子を表す。］ The inventor of the present invention has arrived at the present invention as a result of studies to achieve the above object.
That is, the present invention contains at least one compound (A) selected from the group consisting of a compound represented by the following general formula (1) and a salt thereof, an enzyme (a), a surfactant (b) and water. The gist of the invention is that it is a liquid detergent composition for an automatic dishwasher.

[Wherein, X represents an imino group, an oxygen atom or a sulfur atom. ]

  The liquid detergent composition for an automatic dishwasher of the present invention has high enzyme activity and high cleaning performance.

  The liquid detergent composition for an automatic dishwasher of the present invention comprises at least one compound (A) selected from the group consisting of a compound represented by the following general formula (1) and a salt thereof, an enzyme (a), and a surface activity. It is a liquid detergent composition for automatic dishwashers containing agent (b) and water.

[In Formula (1), X represents an imino group, an oxygen atom, or a sulfur atom. ]

  When the enzyme (a) is stored in a liquid detergent, there is a problem that the anti-fading performance is remarkably lowered due to aggregation, hydrolysis, etc. In the present invention, the above compound (A) having a specific chemical structure is used. It can be solved by including it in a liquid detergent composition.

  Specific examples of the compound represented by the general formula (1) include guanidine, urea and thiourea.

Examples of the salt of the compound represented by the general formula (1) include a guanidine salt.
Examples of the salt include hydrochloride, carbonate, borate, sulfate and phosphate.

  The compound (A) is preferably a guanidine salt and urea, more preferably a guanidine salt, and still more preferably a guanidine hydrochloride, from the viewpoint of durability of washing performance.

The content (% by weight) of the compound (A) contained in the liquid detergent composition for an automatic dishwasher of the present invention is based on the weight of the liquid detergent composition for an automatic dishwasher from the viewpoint of durability of washing performance. 0.01-30 is preferable, More preferably, it is 0.02-10, Next, More preferably, it is 0.03-5, Most preferably, it is 0.05-3.
The content of the compound (A) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 1 to 1000% by weight with respect to the weight of the enzyme (a) from the viewpoint of durability of the cleaning performance. More preferably, it is 5 to 500% by weight, and further preferably 10 to 300% by weight.

  The liquid detergent composition for automatic dishwashers of the present invention can further contain a compound (B) represented by the following general formula (2). From the viewpoint of durability of the cleaning performance, it is preferable to contain (B).

  In general formula (2), Q represents an alkyl group, and a part of hydrogen atoms in the alkyl group may be substituted with groups other than hydrogen atoms.

Examples of the alkyl group of Q include an alkyl group having 1 to 22 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. , A cetyl group, a stearyl group, a behenyl group, and the like. Some of the hydrogen atoms in these alkyl groups may be substituted with groups other than hydrogen atoms.
Examples of substituents other than hydrogen atoms include amino groups, carboxyl groups, amide groups, ester groups, imino groups, and hydroxyl groups. The number of substituents is preferably 1 to 3, more preferably 2 to 3. For example, when two hydrogen atoms at the butyl group end are substituted with one amino group and one carboxyl group, (B) represents arginine.

  Examples of the compound (B) include arginine or a salt thereof (B-1), an arginine derivative or a salt thereof (B-2), and a guanidine derivative or a salt thereof (B-3).

  As (B-1), arginine, arginine inorganic acid salt (hydrochloride, borate, phosphate, pyrophosphate, sulfate, silicate, etc.) and arginine organic acid salt (formate, acetate) Oxalate, lactate, citrate, trimellitic acid salt and pyromellitic acid salt).

In (B-2), the arginine derivative is a derivative in which the α-amino group or α-carboxyl group of arginine represented by the following general formula (3) or both of these groups are substituted.
The substitution of the α-amino group is substitution to an N-alkylcarbonyl-amide group represented by the following general formula (4) or an imino group represented by the general formula (5), and substitution of the α-carboxyl group is Substitution to an ester group represented by the following general formula (6) or an N-alkylamide group represented by the following general formula (7).

  In general formula (3), Y represents an amino group, an N-alkylcarbonyl-amide group (Y-1) represented by the following general formula (4), or an imino group represented by general formula (5) (Y-2). ). Z represents a carboxyl group, an ester group (Z-1) represented by the following general formula (6) or an N-alkylamide group (Z-2) represented by the general formula (7).

  In (B-2), at least one of an α-amino group and an α-carboxyl group is substituted. That is, when Y is an amino group, Z is (Z-1) or (Z-2), and when Z is a carboxyl group, Y is (Y-1) or (Y-2).

In the general formula (4), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 36 carbon atoms, and this hydrocarbon group has a part of the hydrogen atom as a functional group other than a hydrogen atom. May be substituted.

The hydrocarbon group for R ¹ in (Y-1) is a monovalent hydrocarbon group having 1 to 36 carbon atoms, a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic group. Hydrocarbon groups are included.
Linear aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, lauryl, palmityl, stearyl, oleyl and Examples include a behenyl group.
Examples of the branched aliphatic hydrocarbon group include an isopropyl group and a t-butyl group.
Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a methylcyclohexyl group, and a cyclohexylmethyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a methylphenyl group, a benzyl group, a phenylethyl group, and a methylbenzyl group.
Of these hydrocarbon groups, a linear aliphatic hydrocarbon group is preferable from the viewpoint of sustaining enzyme activity, more preferably a methyl group and an ethyl group, and most preferably a methyl group.
Examples of substituents other than hydrogen atoms include amino groups, carboxyl groups, amide groups, ester groups, imino groups, and hydroxyl groups.

  Specific examples of (Y-1) include formamide group, acetylamide group, propionic acid amide group, butyric acid amide group, hexylic acid amide group, cyclohexylic acid amide group, octylic acid amide group and benzoylamide group. .

In the general formula (5), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms, and these hydrocarbon groups have a part of their hydrogen atoms other than hydrogen atoms. The functional group may be substituted.

In (Y-2), R ² and R ³ include the same hydrocarbon group as R ^1, and these hydrocarbon groups are partially substituted with other functional groups as in R ^1. May be.

  Examples of (Y-2) include a methylimino group.

In general formula (6), R ⁴ represents a hydrocarbon group having 1 to 36 carbon atoms, or a residue obtained by removing one hydroxyl group from a polyhydric alcohol or sugar.
In this hydrocarbon group, part of the hydrogen atoms may be substituted with another functional group, for example, a functional group selected from the group consisting of a hydroxyl group, a methoxyl group, an ethoxyl group, a nitro group, and a hydroxyphenyl group.

When R ⁴ is a hydrocarbon group having 1 to 36 carbon atoms, the hydrocarbon group includes the same hydrocarbon group as R ¹ .
In the case where R ⁴ is a hydrocarbon group having 1 to 36 carbon atoms, among these hydrocarbon groups, a linear aliphatic hydrocarbon group is preferable from the viewpoint of sustaining enzyme activity, and more preferably a methyl group and an ethyl group. Group, most preferably an ethyl group.

Examples of the polyhydric alcohol include divalent to trivalent alcohols, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, and glycerin.
Examples of the sugar include glucose, sucrose, sorbitol, mannitol and trehalose.

In General Formula (7), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms, and in this hydrocarbon group, a part of the hydrogen atom is substituted with another functional group other than a hydrogen atom. May be.

In (Z-2), when R ⁵ is a hydrocarbon group having 1 to 36 carbon atoms, the hydrocarbon group includes the same hydrocarbon group as R ^1, and these hydrocarbon groups are R ¹ Similarly to the above, a part thereof may be substituted with another functional group.
In the case where R ⁵ is a hydrocarbon group having 1 to 36 carbon atoms, among these hydrocarbon groups, a linear aliphatic hydrocarbon group is preferable from the viewpoint of sustaining enzyme activity, and more preferably a methyl group and an ethyl group. Group, most preferably a methyl group.

  When (B-2) is a salt of an arginine derivative, an inorganic acid salt (hydrochloride, borate, phosphate, pyrophosphate, sulfate, silicate, etc.) and an organic acid salt (formate, acetate) Oxalate, lactate, citrate, trimellitic acid salt and pyromellitic acid salt).

  Specific examples of the compound (B-2) include N-acetylarginine ethyl ester hydrochloride.

The content (% by weight) of the compound (B) contained in the liquid detergent composition for an automatic dishwasher of the present invention is the weight of the liquid detergent composition for an automatic dishwasher from the viewpoint of durability of the washing performance. On the other hand, it is preferably from 0.01 to 30, more preferably from 0.03 to 10, and further preferably from 0.05 to 5.
The content of the compound (B) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably from 1 to 1000% by weight, more preferably from the weight of the enzyme, from the viewpoint of durability of the washing performance. Is from 5 to 500% by weight, more preferably from 10 to 300% by weight.

  The liquid detergent composition for an automatic dishwasher of the present invention may contain only the compound (A), but it is preferable to contain the compound (A) and the compound (B) from the viewpoint of durability of washing performance.

  In the case of containing (A) and (B), the weight ratio of (A) to (B) (weight of (A) / weight of (B)) is from 0.1 to 0.1 from the viewpoint of durability of cleaning performance. 9 is preferable, more preferably 0.2 to 8, and particularly preferably 0.5 to 5.

  As the enzyme (a) which is an essential component in the present invention, protease (a-1), cellulase (a-2), amylase (a-3), lipase (a-4) and oxidoreductase (a-5) are included. included.

  The protease (a-1) includes those of animal, plant or microbial origin, and those of microbial origin are preferred from the viewpoint of availability. Chemically or genetically modified variants are also included. Among proteases, serine proteases are preferable from the viewpoint of detergency, and alkaline microbial proteases and trypsin-like proteases are more preferable.

Alkaline microbial proteases include subtilisins, particularly those derived from Bacillus, such as subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168.
Trypsin-like proteases include trypsin (eg, of porcine or bovine origin) and Fusarium protease.

Commercially available protease, Novozymes Inc. ^{Alcalase TM, Savinase TM, Primase TM} , etc. Durazym ^TM and Esperase ^TM and Genencor Purafect ^TM and Purafect OXP ^TM and the like.

Cellulases (a-2) include those of bacterial or fungal origin. Chemically or genetically modified variants are also included. Cellulases include those disclosed in US Pat. No. 4,435,307 as fungal cellulases produced from Humicola insolens. Also particularly suitable cellulases are cellulases useful for color care, including cellulases described in European Patent Application No. 0 495 257.
Commercial cellulases include Novozymes Celluzyme ^™ and Kao KAC-500 (B) ^™ produced by strains of Humicola insolens.

Amylase (a-3) includes those of bacterial or fungal origin. Chemically or genetically modified variants are also included. Examples of the amylase include B.I. described in detail in British Patent No. 1,296,839. Examples include α-amylase obtained from a special strain of B. licheniformis.
Commercially available amylases, Novozymes of Duramyl ^TM, Termamyl ^TM, include Fungamyl ^TM and BAN ^TM and Gist-Brocades Inc., Rapidase ^TM and Maxamyl P ^TM.

  Lipases (a-4) include those of bacterial or fungal origin. Chemically or genetically modified variants are also included. Examples of lipases include Humicola langinosa lipase (EP 258 068 and EP 305 216), Rhizomucor miehei lipase and Candida (Candida) Patent No. 238 023), C.I. Antactica lipase A and B, Pseudomonas lipase (European Patent No. 214 761), P. P. pseudoalcaligenes and P. p. P. alcaligenes lipase (EP 218 272), P. a. P. cepacia lipase (European Patent No. 331 376); P. stutzeri lipase, P. p. P. fluorescens lipase and Bacillus lipase (UK Patent No. 1,372,034); B. subtilis lipase (Dartois et al. (1993), Biochemica et Biophysica Acta 1131, 253-260), B. stearothermophilus lipase (Japanese Patent Publication No. 64-744992) and B. stearothermophilus lipase. And B. pumilus lipase (WO 91/16422).

Commercially available lipases, Genencor M1 Lipase ^TM, Luma fast ^TM and Lipomax ^TM, include Novozymes of Lipolase ^TM and Lipolase Ultra ^TM and Amano Enzyme Inc. of Lipase P "Amano" ^TM.

Oxidoreductase (a-5) includes peroxidase and oxidase (for example, laccase).
Peroxidases include those of plant, bacterial or fungal origin. Chemically or genetically modified variants are also included. Peroxidases include Coprinus (e.g., derived from C. cinereus or C. macrolithus strains), Bacillus (from B. pumilus strains). And the peroxidase described in WO 91/05858 are preferable, and the peroxidase described in WO 91/05858 is particularly preferable.
Laccases include those of bacterial or fungal origin. Laccases include Trametes (eg, derived from strains of T. villosa or T. versicolol), Coprinus (eg, strains of C. cinereus). Derived from] and Myceliophthora [for example, derived from a strain of M. thermophila].

  Among the above enzymes, protease (a-1), cellulase (a-2), amylase (a-3), and lipase (a-) from the viewpoint of detergency against protein stains, fat stains, dietary fiber stains and carbohydrate stains. 4) is preferred, and protease (a-1) and amylase (a-3) are more preferred.

  In the present invention, the enzyme (a) contained in the liquid detergent composition for an automatic dishwasher can contain two or more kinds from the viewpoint of detergency. Examples of combinations of two or more include protease and amylase, protease and lipase, and protease, amylase and lipase.

  The content of the enzyme (a) contained in the liquid detergent composition for an automatic dishwasher of the present invention is 0.01 to 5% by weight based on the weight of the liquid detergent composition for an automatic dishwasher from the viewpoint of detergency. Is more preferable, and 0.05 to 3% by weight and 0.1 to 2% by weight are more preferable.

  The surfactant (b), which is an essential component of the present invention, is a nonionic surfactant (b-1), an anionic surfactant (b-2), a cationic surfactant (b-3), and an amphoteric surfactant. An agent (b-4) is mentioned.

  As nonionic surfactant (b-1), aliphatic alcohol (carbon number 8-24) alkylene oxide (carbon number 2-8) adduct (degree of polymerization = 1-100) [oleyl alcohol ethylene oxide propylene oxide addition Products], (poly) oxyalkylene (carbon number 2-8, polymerization degree = 1-100) glycol higher fatty acid (carbon number 8-24) ester [polyethylene glycol monostearate (polymerization degree = 20) and polyethylene distearate Glycol (degree of polymerization = 30), etc., polyvalent (divalent to 10-valent or higher) alcohol fatty acid (carbon number 8-24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan monolaurate, etc.], Multivalent (divalent to 10-valent or higher) alcohol higher fatty acid (8 carbon atoms) 24) Ester (poly) alkylene oxide adduct (alkylene group having 2 to 8 carbon atoms, degree of polymerization = 1 to 100) [sorbitan monolaurate ethylene oxide (degree of polymerization = 10) adduct and methyl glucose dioleate ethylene oxide (Degree of polymerization = 50) adducts, etc.], fatty acid N-hydroxyalkylamide [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, etc.], alkyl (C1-22) (poly) Oxyalkylene (carbon number 2-8, polymerization degree = 1-100) phenyl ether, alkyl (carbon number 8-24) (poly) oxyalkylene (carbon number 2-8, polymerization degree = 1-100) -aminoalkyl ( C8-24) -ether and alkyl (C8-24) dialkyl (C1-6) amineoxy Include [lauryl dimethylamine oxide, etc.] or the like.

  Examples of the anionic surfactant (b-2) include an alkyl ether carboxylic acid having 8 to 24 carbon atoms or a salt thereof and an alkyl (poly) oxyethylene ether carboxylic acid having 8 to 24 carbon atoms or a salt thereof [(poly) oxy Ethylene (degree of polymerization = 1 to 100) sodium lauryl ether acetate and (poly) oxyethylene (degree of polymerization = 1 to 100) disodium lauryl sulfosuccinate, etc.], alkyl sulfate salts having 8 to 24 carbon atoms and carbon numbers 8 to 8 24 alkyl (poly) oxyethylene sulfate esters [sodium lauryl sulfate, lauryl (poly) oxyethylene (degree of polymerization = 1-100) sodium sulfate and lauryl (poly) oxyethylene (degree of polymerization = 1-100) sulfate-tri Ethanolamine salts, etc.], palm oil fatty acid monoethanolamide sulfate sulfonate Lithium, alkyl phenyl sulfonates having 8 to 24 carbon atoms [sodium dodecylbenzene sulfonate, etc.], alkyl phosphate salts having 8 to 24 carbon atoms and alkyl (poly) oxyethylene phosphate salts having 8 to 24 carbon atoms [Sodium lauryl phosphate and (poly) oxyethylene (degree of polymerization = 1-100) sodium lauryl ether phosphate, etc.], fatty acid salt [sodium laurate, triethanolamine laurate, etc.], acylated amino acid salt [coconut oil fatty acid Methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium and lauroylmethyl-β -Alanine Sodium etc.].

  As the cationic surfactant (b-3), quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.] and amine salts Type [diethylaminoethylamide stearate lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.] and the like.

  As the amphoteric surfactant (b-4), a betaine-type amphoteric surfactant [coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazoli Nium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate, etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate, etc.].

  As (b), 1 type (s) or 2 or more types can be used. When two or more types are used, combinations thereof include, for example, a nonionic surfactant and an anionic surfactant, a nonionic surfactant and a cationic surfactant, and a nonionic surfactant and an amphoteric surfactant. A combination etc. are mentioned.

  (B) is preferably a nonionic surfactant from the viewpoint of cleaning performance, and more preferably an aliphatic alcohol (carbon number 8-24) alkylene oxide (carbon number 2-8) adduct (degree of polymerization = 1-100). ), Polyvalent (divalent to 10-valent or higher) alcohol higher fatty acid (carbon number 8 to 24) ester (poly) alkylene oxide adduct (carbon number of alkylene group 2 to 8, degree of polymerization = 1 to 100) and It is an alkyl (C8-24) dialkyl (C1-6) amine oxide.

  The content of the surfactant (b) contained in the liquid detergent composition for an automatic dishwasher of the present invention is 0.1% relative to the weight of the liquid detergent composition for an automatic dishwasher from the viewpoint of washing performance and foaming. -20% by weight is preferable, more preferably 0.5-10% by weight, and particularly preferably 1-5% by weight.

  Water that is an essential component of the present invention is not particularly limited, and examples thereof include tap water, ion exchange water, distilled water, and reverse osmosis water.

  The content of water contained in the liquid detergent composition for an automatic dishwasher of the present invention is 5 to 98% by weight with respect to the weight of the liquid detergent composition for an automatic dishwasher from the viewpoint of durability of washing performance. More preferably, it is 10 to 97% by weight, and particularly preferably 45 to 95% by weight.

  The liquid detergent composition for an automatic dishwasher of the present invention includes, in addition to the compounds (A) and (B), the enzyme (a), the surfactant (b), and water, in order to improve the cleaning properties. Water-miscible organic solvent (c), inorganic salt (d), sugar (e), amino acid (f) other than arginine, builder (g), alkali agent (h) and chelating agent (i) can be contained. .

  The water-miscible organic solvent (c) is not particularly limited as long as it is a solvent miscible with water, and examples thereof include ethanol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, and sorbitol.

  Examples of the inorganic salt (d) include sodium chloride, sodium borate, calcium chloride, magnesium chloride, sodium formate, magnesium sulfate, and ammonium sulfate.

  Examples of the sugar (e) include trehalose, sucrose, dextrin, cyclodextrin, maltose, fructose, hyaluronic acid and chondroitin sulfate.

  Examples of amino acids (f) other than arginine include glycine, alanine, aspartic acid, asparagine, phenylalanine, tryptophan, tyrosine, leucine, lysine, histidine, and salts thereof.

  Builders (g) include poly (meth) acrylates and polycarboxylic acids {eg oxalic acid, citric acid, succinic acid and malic acid}.

  Examples of the alkaline agent (h) include caustic soda, soda ash, ammonia, triethanolamine, diethanolamine, monoethanolamine, and sodium tripolyphosphate.

  As a chelating agent (i), the well-known thing used for a liquid detergent can be used. For example, aminopolyacetic acid or salts thereof such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid and diencoric acid, diglycol Acids, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid and carboxymethyl tartaric acid and their salts and aminotri (methylene Phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or their alkali metals or lower Min salts.

The content of the water-miscible organic solvent (c) contained in the liquid detergent composition for an automatic dishwasher of the present invention is the weight of the liquid detergent composition for an automatic dishwasher from the viewpoint of durability of the washing performance. The inorganic salt (d) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 5 to 50% by weight, more preferably 7 to 30% by weight, particularly preferably 9 to 20% by weight. The content (% by weight) is preferably from 0.01 to 10, more preferably from 0.05 to 5, and even more preferably from 0.1 to 3 based on the weight of the liquid detergent composition from the viewpoint of detergency. is there.
The content (% by weight) of sugar (e) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 0 to 5, more preferably from the weight of the liquid detergent composition from the viewpoint of detergency. Is 0-3, more preferably 0-1.
The content (% by weight) of the amino acid (f) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 0 to 10, more preferably from the weight of the liquid detergent composition from the viewpoint of detergency. Is 0-5, more preferably 0-3.
The content (% by weight) of the builder (g) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 0 to 5, more preferably from the weight of the liquid detergent composition from the viewpoint of detergency. Is 0-3, then more preferably 0-2.
The content (% by weight) of the alkaline agent (h) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 1 to 30 based on the weight of the liquid detergent composition from the viewpoint of detergency. Preferably it is 1-10, then more preferably 2-7.
The content (% by weight) of the chelating agent (i) contained in the liquid detergent composition for an automatic dishwasher of the present invention is preferably 0 to 5 based on the weight of the liquid detergent composition from the viewpoint of detergency. Preferably 0-3, then more preferably 0-2.

  From the viewpoint of detergency, the pH of the liquid detergent composition for an automatic dishwasher of the present invention is preferably 7 to 12 and more preferably 8 to 11 with a 1% (w / w) aqueous solution.

The liquid detergent composition for an automatic dishwasher of the present invention is obtained by mixing each component, and the production method is not particularly limited. An example is shown below.
(1) Add surfactant, compound (A) and, if necessary, compound (B) to water and stir at 25 ° C. until uniform.
(2) A predetermined amount of components other than enzyme (a) is added and dissolved uniformly.
(3) Finally, the enzyme (a) is added and dissolved to produce a liquid detergent composition.

The method of using the liquid detergent composition for an automatic dishwasher of the present invention may be the same as the method of using the conventional liquid detergent composition for an automatic dishwasher, and is not particularly limited. An example is shown below.
(1) Put the liquid detergent composition for an automatic dishwasher into the detergent inlet of an automatic dishwasher containing dishes, close the lid, and tap water.
(2) Wash the dishes in the washing course of the washing machine.
At this time, the tap water is heated and the liquid detergent composition diluted with the tap water is sprayed onto the tableware.
(3) Rinse with tap water.
(4) Dry.

  The following examples further illustrate the invention, but the invention is not limited thereto.

<Production Example 1>
N-α-acetylarginine {Arginine acetamide, MP Bio Japan Co., Ltd.} 12.6 parts (0.05 mole part), 1 part of methanesulfonic acid and 92 parts (2 mole parts) of ethanol were mixed uniformly at 80 ° C. The mixture was heated and stirred for 5 hours, concentrated with an evaporator, and then neutralized by adding 5.2 parts (0.05 mol) of hydrochloric acid. Thereafter, it was recrystallized from water and dried under reduced pressure {60 ° C., 20 Pa} to obtain {N-α-acetylarginine ethyl ester hydrochloride}.

<Examples 1 to 12>
The liquid detergent composition for automatic dishwashers of the present invention was prepared by blending at a rate of Table 1 at 25 ° C.

<Comparative Examples 1-3>
A liquid detergent composition for comparison was prepared by blending at a rate of Table 1 at 25 ° C.

<Detergency test>
<Cleanability against protein stains (immediately after preparation)>
In the automatic dishwasher [Matsushita Electric Industrial Co., Ltd., Model NP-60SS6], the following contaminated dishes are placed, and the detergent compositions of Examples 1-12 and Comparative Examples 1-3 immediately after preparation are placed in a dedicated detergent container. I drove on a standard course. This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). (Warm) and then dried.
Contaminated dishes: 4 (prepared by the following method)
Water used: tap water detergent composition addition amount: 6 g
The mass of the dish before contamination (P1), the mass of the dish (P2), and the mass of the dish after washing (P3) were measured, and the washing rate was calculated by the following equation.

Cleaning rate (%) = 100 × (P2-P3) / (P2-P1)

Detergency was evaluated according to the following scale. The evaluation results are shown in Table 1.
○: Cleaning rate of 80% or more Δ: Cleaning rate of 50% or more and less than 80% ×: Cleaning rate of less than 50%

<Preparation of contaminated dishes>
2 g of egg yolk was applied as uniformly as possible to a magnetic dish having a diameter of 23 cm and denatured at 90 ° C. for 1 hour, and used for the detergency test.

<Cleanability against protein stains (after storage at 25 ° C for 3 months)>
In place of the cleaning compositions of Examples 1-12 and Comparative Examples 1-3 immediately after production, the cleaning compositions of Examples 1-12 and Comparative Examples 1-3 stored at 25 ° C. for 3 months are used. In the same manner as described above, a detergency test was performed, and a cleaning rate was calculated and evaluated in the same manner as described above. The evaluation results are shown in Table 1.

<Durability of cleaning against protein stains>
In the evaluation of detergency against protein stains, the continuity (%) of detergency representing how much the detergency after storage for 3 months at 25 ° C. with respect to the detergency immediately after production was calculated by the following formula.

Persistence of detergency (%) = 100 × (cleaning rate after storage at 25 ° C. for 3 months / cleaning rate immediately after preparation)

Detergency was evaluated according to the following scale. The evaluation results are shown in Table 1.
5: Persistence of detergency 95% or more 4: Persistence of detergency 80% or more and less than 95% 3: Persistence of detergency 62.5% or more and less than 80% 2: Persistence of detergency 50% or more 62. Less than 5% 1: Persistence of detergency less than 50%

<Detergency against starch stains (immediately after compounding)>
In the preparation of the staining dish used in the cleaning test for protein stains, a cleaning test was performed in the same manner as described above except that 2 g of starch was used instead of 2 g of egg yolk, and the cleaning rate was calculated and evaluated in the same manner as described above. . The evaluation results are shown in Table 1.

<Detergency against starch stains (after storage at 25 ° C. for 3 months)>
In place of the cleaning compositions of Examples 1-12 and Comparative Examples 1-3 immediately after production, the cleaning compositions of Examples 1-12 and Comparative Examples 1-3 stored at 25 ° C. for 3 months are used. In the same manner as described above, a detergency test was performed, and a cleaning rate was calculated and evaluated in the same manner as described above. The evaluation results are shown in Table 1.

<Durability of detergency against starch stains>
In the evaluation of detergency against starch stains, the detergency (%) of detergency representing how much the detergency after storage for 3 months at 25 ° C. with respect to the detergency immediately after production was calculated by the following formula.

Persistence of detergency (%) = 100 × (cleaning rate after storage at 25 ° C. for 3 months / cleaning rate immediately after preparation)

Detergency was evaluated according to the following scale. The evaluation results are shown in Table 1.
5: Persistence of detergency 95% or more 4: Persistence of detergency 80% or more and less than 95% 3: Persistence of detergency 62.5% or more and less than 80% 2: Persistence of detergency 50% or more 62. Less than 5% 1: Persistence of detergency less than 50%

The following were used for the enzyme (a), the compound (A) and the compound (B) in Table 1.
Protease: Wako Pure Chemical Industries, Ltd. Amylase: Wako Pure Chemical Industries, Ltd. Lipase: Wako Pure Chemical Industries, Ltd. Guanidine Hydrochloride: Wako Pure Chemical Industries, Ltd. Urea: Wako Pure Chemical Industries, Ltd. ) Arginine hydrochloride manufactured by Wako Pure Chemical Industries, Ltd. In Table 1, the ratio of each component is shown in parts by weight.

From Table 1, it can be seen that the liquid detergent composition of Comparative Example 1 to which no substance that preserves storage stability is added has a marked decrease in detergency after storage at 25 ° C. for 3 months. Moreover, although the comparative examples 2 and 3 containing a boric acid can suppress the fall of the washing | cleaning rate after 3 months storage at 25 degreeC some, it turns out that it is not a level which is fully satisfactory.
On the other hand, it turns out that the liquid detergent composition for automatic dishwashers of Examples 1 to 12 containing the compound (A) has high cleaning performance even after storage at 25 ° C. for 3 months. Furthermore, it turns out that Examples 1-11 also have high detergency.

  The detergent composition for an automatic dishwasher of the present invention can be used not only for home use but also for commercial dishwashers.

Claims (5)

For an automatic dishwasher containing at least one compound (A) selected from the group consisting of a compound represented by the following general formula (1) and a salt thereof, an enzyme (a), a surfactant (b) and water Liquid detergent composition.

[Wherein, X represents an imino group, an oxygen atom or a sulfur atom. ] The liquid detergent composition for an automatic dishwasher according to claim 1, wherein the enzyme (a) is one or more selected from the group consisting of protease, amylase and lipase. The liquid detergent composition for an automatic dishwasher according to claim 1 or 2, wherein the compound (A) is guanidine hydrochloride. Furthermore, the liquid detergent composition for automatic dishwashers in any one of Claims 1-3 containing the compound (B) represented by following General formula (2).

[Wherein, Q represents an alkyl group, and a part of hydrogen atoms in the alkyl group may be substituted with a group other than a hydrogen atom. ] The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 4, wherein the content of the compound (A) is 0.01 to 30% by weight based on the weight of the liquid detergent composition for an automatic dishwasher. object.