JP2011094122A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition having a good lasting property of the enzymatic activity of an enzyme, and capable of maintaining cleaning property for a long period of time. <P>SOLUTION: This liquid detergent composition contains (A) an organic compound satisfying the following (1) to (3) conditions, (a) an enzyme, (b) a surfactant and water. (1) In the case of attaching a proton to the molecule of the organic compound (A), in at least one atom (Z) at the inside of molecule, the π-bonding formed by the π-electrons of the atom (Z) and an atom (Y) bonding with the atom (Z) takes a resonance structure, and in the electrons that the atom (Z) and atom (Y) have, the number of the π-electrons associating with the π-bonding of the resonance structure are ≥4. (2) The ionic strength of its 0.1 mol/dm<SP>3</SP>solution is ≥0.1. (3) The molecular weight is <300. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

  Dirt varies depending on the type of clothing. Among soils, complex soils such as sebum soils, protein soils and particle soils are considered difficult to clean. Conventionally, it has been known that a detergent containing an enzyme such as a surfactant excellent in sebum dirt removal and particle dirt dispersion and a protease excellent in protein dirt degradation is effective against such dirt. .

  As is well known, enzymes are now indispensable for detergents due to their high degradability. On the other hand, detergents are changing from conventional solid detergents to liquid detergents in terms of ease of use. However, the enzyme has a problem that its enzyme activity is poor in an aqueous solution and the enzyme activity is remarkably lowered during storage. Therefore, it has become a big problem to provide a liquid detergent that has high enzyme activity and can maintain its detergency.

For example, the persistence of enzyme activity has been improved by adding protease inhibitors. Non-patent document 1 describes that boronic acid inhibits serine protease and subtilisin. Patent Document 1 describes that 4-substituted phenylboronic acid inhibits protease and sabinase.
In addition, Patent Document 2 also describes the addition of a polyol (for example, 1,2-propanediol, sorbitol, glycerol) in order to stabilize the enzyme.
However, although liquid detergents containing these compositions have certain effects, they cannot sufficiently suppress the decrease in enzyme activity during storage, and it is impossible to obtain detergency sufficient to meet consumer needs.
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.

Japanese National Patent Publication No. 11-507680 JP 2009-507085 A

Molecular & Cellular Biochemistry, 51, 1983, p5-32.

  It is an object of the present invention to provide a liquid detergent composition having good enzyme activity sustainability and high detergency, particularly to provide a liquid detergent composition capable of realizing high washing performance for clothing. .

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 liquid detergent composition of the present invention is a liquid detergent composition containing an organic compound (A), an enzyme (a), a surfactant (b) and water that satisfy the following conditions (1) to (3);
(1) When a proton is added to the molecule of the organic compound (A), at least one atom (Z) in the molecule has an atom (Z) and an atom (Y) bonded to the atom (Z). The π bond with π electricity c has a resonance structure,
There are four or more π electrons that are atoms (Z) and atoms (Y) involved in the π bond of this resonance structure. (2) The ionic strength of the 0.1 mol / dm ³ solution is It is 0.1 or more. (3) The molecular weight is less than 300.

  The liquid detergent composition of the present invention can maintain cleanability for a long time.

Hereinafter, the organic compound (A) is also simply referred to as the compound (A).
The liquid detergent composition of the present invention is a liquid detergent composition containing an organic compound (A), an enzyme (a), a surfactant (b), and water that satisfy the following conditions (1) to (3).
(1) When a proton is added to the molecule of the organic compound (A), at least one atom (Z) in the molecule has an atom (Z) and an atom (Y) bonded to the atom (Z). The π bond formed by π electrons has a resonance structure,
There are four or more π electrons that are atoms (Z) and atoms (Y) involved in the π bond of this resonance structure. (2) The ionic strength of the 0.1 mol / dm ³ solution is 0.1 or more (3) Molecular weight is less than 300

  When the enzyme is stored in a liquid detergent, there is a problem in that the enzyme causes aggregation and hydrolysis and the enzyme activity (titer) is remarkably reduced. In the present invention, the compound (A) having a specific chemical structure is used. Can be solved by including in a liquid detergent composition.

The condition (1) will be described.
For example, when the organic compound (A) is a guanidine molecule represented by the following general formula (1), the carbon atom (I) is bonded to nitrogen atoms (II), (III), and (IV). When a proton is added to the guanidine molecule, the carbon atom (I) becomes a cation and has a vacant orbit, and (II) to (IV) each have a lone electron pair in the sp3 hybrid orbital. These three lone electron pairs can form a π bond with the carbon atom (I) and have a resonance structure.
That is, when the carbon atom (I) in the guanidine molecule is the atom (Z), the atom (Y) bonded to the atom (Z) is a nitrogen atom (II) to (IV), This atom (Z) {carbon atom (I)} and atom (Y) have six electrons, which are involved in the π bond of this resonance structure.
When protons are added to the guanidine molecule, nitrogen atoms (II) to (IV) are bonded to carbon atom (I) and two hydrogen atoms, respectively, and each lone pair forms a π bond. Therefore, when the nitrogen atoms (II) to (IV) are the atoms (Z), they each have two π electrons involved in the π bond.
Therefore, guanidine satisfies the condition (1) because the carbon atom (I) satisfies the condition of the atom (Z).

  Examples of the compound satisfying the condition (1) include guanidinium salts, guanazine, guanamine, formamidine, heterocyclic compounds (pyrrole, imidazole, pyridine, pyrimidine, indole, quinoline, isoquinoline, purine, etc.), organic phosphoric acid ( For example, phosphoric acid esters of alcohols having 1 to 30 carbon atoms).

In the condition (2) above, the ionic strength I is obtained by adding the product of the squares of the molar concentration m of each ion and the charge z for the ionic species i in the solution, and halving it. And is represented by the following equation.
I = 1 / 2Σm _i z _i ²
That is, the ionic strength of the 0.1 mol / dm ³ solution being 0.1 or more indicates that the value of I calculated by the above equation is 0.1 or more.

Examples of the organic compound (A) satisfying the above conditions (1) to (3) of the present invention include a heterocyclic compound (A-1), an organic phosphoric acid (A-2), nitrogen having 1 to 20 carbon atoms, oxygen And a compound (A-3) having two or more sulfur atoms and a salt thereof (A-4).
Examples of the heterocyclic compound (A-1) include nitrogen-containing heterocyclic compounds, oxygen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, and phosphorus-containing heterocyclic compounds, such as pyrrole, imidazole, pyridine, pyrimidine, indole, Examples include quinoline, isoquinoline, purine, indole, quinoline, isoquinoline, furan, thiophene, oxazole, thiazole, isoxazole, and isothiazole.
Examples of the organic phosphoric acid (A-2) include organic phosphoric acids having 1 to 20 carbon atoms, such as methyl phosphoric acid, ethyl phosphoric acid, isopropyl phosphoric acid, butyl phosphoric acid, dimethyl phosphoric acid, diethyl phosphoric acid, dipropyl phosphoric acid, dibutyl phosphorous. Examples of the compound (A-3) having 2 or more of nitrogen, oxygen and sulfur atoms having 1 to 20 carbon atoms include compounds represented by the following general formula (2): acid, methyl pyrophosphate, ethyl pyrophosphate, etc. (A2), an amidino group-containing compound, an amide group-containing compound and the like can be mentioned, and examples thereof include guanidine, urea, thiourea, formamidine, methylamidine, biguanide and the like.
Examples of these salts (A-4) include salts of the compound (a) represented by the following general formula (2), such as inorganic acid salts such as hydrochloride, phosphate, sulfate, and carbonic acid. Examples thereof include organic acid salts such as salts, citrates and acetates.

The content (% by weight) of the organic compound (A) contained in the liquid detergent composition of the present invention is preferably 0.01 to 30 with respect to the weight of the liquid detergent composition from the viewpoint of durability of detergency. Preferably it is 0.02 to 10, then more preferably 0.03 to 5, particularly preferably 0.05 to 3.
The content (% by weight) of the compound (A) contained in the liquid detergent composition of the present invention is 1 to 1,000% by weight with respect to the weight of the enzyme from the viewpoint of durability of detergency. It is preferably contained, more preferably 5 to 500% by weight, and further preferably 10 to 300% by weight.

  In the liquid detergent composition of the present invention, as the organic compound (A), the salt of the compound (A2) and the compound (A2) represented by the following general formula (2) is preferable from the viewpoint of durability of detergency.

  In the general formula (2), X represents an imino group, an oxygen atom or a sulfur atom.

  Specific examples of the compound (A2) represented by the general formula (2) include guanidine, urea and thiourea.

Examples of the salt of the compound (A2) represented by the general formula (2) include a guanidine salt.
Examples of the salt include hydrochloride, carbonate, borate, sulfate and phosphate.

  The salt of the compound (A2) and the compound (A2) 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 detergency.

  The liquid detergent composition of the present invention can further contain a compound (B) represented by the following general formula (3). It is preferable to contain (B) from a viewpoint of durability of detergency.

  In general formula (3), Q represents an alkyl group, and a part of the hydrogen atoms in the alkyl group may be substituted with a group other than a hydrogen atom.

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) and an arginine derivative or a salt thereof (B-2).

  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 (4) 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 (5) or an imino group represented by the general formula (6), and substitution of the α-carboxyl group is Substitution to an ester group represented by the following general formula (7) or an N-alkylamide group represented by the following general formula (8).

  In general formula (4), Y is an amino group, an N-alkylcarbonyl-amide group (Y-1) represented by the following general formula (5) or an imino group (Y-2 represented by general formula (6)). ). Z represents a carboxyl group, an ester group (Z-1) represented by the following general formula (7) or an N-alkylamide group (Z-2) represented by the general formula (8).

  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 (5), 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, from the standpoint of detergency and durability, a linear aliphatic hydrocarbon group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is most preferable.
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 (6), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms, and in these hydrocarbon groups, a part of the hydrogen atom is other than the original hydrogen atom. 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 the general formula (7), R ⁴ represents a residue obtained by removing one hydroxyl group from a hydrocarbon group or a polyhydric alcohol or sugar having 1 to 36 carbon atoms.
In this hydrocarbon group, part of the hydrogen atoms may be substituted with another functional group such as a hydroxyl group, a methoxyl group, an ethoxyl group, a nitro group, or 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 durability of detergency, 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 (8), 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 durability of detergency, 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.

  As the compound (B) contained in the liquid detergent composition of the present invention, (B-2) is preferable from the viewpoint of durability of detergency, and more preferably α-amino group and α-carboxyl group of arginine. It is a derivative in which both groups are substituted, and N-α-acetylarginine ethyl ester hydrochloride is particularly preferred.

The content (% by weight) of the compound (B) contained in the liquid detergent composition of the present invention is preferably from 0.01 to 30, more preferably from the weight of the liquid detergent composition from the viewpoint of durability of detergency. Is 0.03 to 10, and more preferably 0.05 to 5.
The content of the compound (B) contained in the liquid detergent composition of the present invention may be contained so as to be 1 to 1,000% by weight with respect to the weight of the enzyme, from the viewpoint of durability of detergency. Preferably, it is contained so as to be 5 to 500% by weight, and further preferably contained so as to be 10 to 300% by weight.

  Although the liquid detergent composition of this invention should contain only an organic compound (A), it is preferable to contain an organic compound (A) and a compound (B) from a durable viewpoint of detergency.

  When (A) and (B) are contained, the weight ratio of (A) and (B) (weight of (A) / weight of (B)) is preferably 0.1 to 9, more preferably 0.8. It is 2-8, Most preferably, it is 0.5-5.

  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. Can be mentioned.

  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-4) from the viewpoint of detergency against protein soil, fat soil, particle soil and carbohydrate soil. ) Is preferred, and protease (a-1) is more preferred.

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

  The content of the enzyme (a) contained in the liquid detergent composition of the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to the weight of the liquid detergent composition from the viewpoint of detergency. 2% by weight, 0.1 to 1% by weight.

  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 (polymerization degree = 1-100) [oleyl alcohol ethylene oxide 11 mol 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 to 24 carbon atoms) (Poly) alkylene oxide adduct (alkylene group having 2 to 8 carbon atoms, polymerization degree = 1 to 100) [sorbitan monolaurate ethylene oxide (polymerization degree = 10) adduct and methyl glucose dioleate ethylene oxide (polymerization) Degree = 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 (C2-8, degree of polymerization = 1-100) phenyl ether, alkyl (C8-8) (poly) oxyalkylene (C2-8, degree of polymerization = 1-100) -aminoalkyl (carbon number) 8-24) -ethers and alkyls (8-24 carbon atoms) dialkyl (1-6 carbon atoms) amine oxides [lauryl Methylamine oxide, and the like] and 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-
Sodium glutamate, sodium lauroylmethyl-β-alanine, 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 kinds are used, the combination includes, for example, a combination of a nonionic surfactant and an anionic surfactant, a nonionic surfactant and a cationic surfactant, and a nonionic surfactant and an amphoteric surfactant. Etc.

As (b), from the viewpoint of detergency, it is preferable to use a nonionic surfactant alone or a combination of a nonionic surfactant and an anionic surfactant.
The nonionic surfactant is preferably an aliphatic alcohol (8 to 24 carbon atoms) ethylene oxide adduct (degree of polymerization = 1 to 100), more preferably an aliphatic alcohol (12 to 12 carbon atoms) from the viewpoint of detergency. 18) Ethylene oxide adduct (degree of polymerization 4-20), then more preferably aliphatic alcohol (carbon number 12-15) ethylene oxide adduct (degree of polymerization = 8-12), particularly preferably oleyl alcohol ethylene oxide 11 Mole adduct.
As an anionic surfactant, from a viewpoint of detergency, an alkylphenyl sulfonate having 8 to 24 carbon atoms, a fatty acid salt, an alkyl sulfate ester having 8 to 24 carbon atoms, and an alkyl (poly) having 8 to 24 carbon atoms. Preferred are oxyethylene sulfate salts, more preferably alkyl phenyl sulfonates having 12 to 16 carbon atoms and fatty acid salts having 8 to 16 carbon atoms, and more preferably dodecylbenzenesulfonic acid monoethanolamine salts and lauric acid. Sodium.

  The content of the surfactant (b) contained in the liquid detergent composition of the present invention is preferably 5 to 80% by weight, more preferably 10 to 50% by weight based on the weight of the liquid detergent composition from the viewpoint of detergency. %, Particularly preferably 20 to 40% 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 of the present invention is preferably from 5 to 90% by weight, more preferably from 13 to 80% by weight, particularly preferably from the weight of the liquid detergent composition, from the viewpoint of detergency. Is 29 to 70% by weight.

In addition to the compounds (A) and (B), the enzyme (a), the surfactant (b) and water, the liquid detergent composition of the present invention includes an inorganic salt (F), a polyhydric alcohol (G), Sugar (H), amino acids (I) other than arginine, builder (J), alkali agent (K) and chelating agent (L) can be contained.

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

  Examples of the polyhydric alcohol (G) include ethylene glycol, propylene glycol, and glycerin.

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

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

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

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

  As a chelating agent (L), 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 (% by weight) of the inorganic salt (F) contained in the liquid detergent composition of the present invention is preferably 0.01 to 10 with respect to the weight of the liquid detergent composition from the viewpoint of detergency, and more preferably 0. .05 to 5, and more preferably 0.1 to 3.
The content (% by weight) of the polyhydric alcohol (G) contained in the liquid detergent composition of the present invention is preferably 0 to 20 with respect to the weight of the liquid detergent composition from the viewpoint of the uniformity of the liquid detergent composition, More preferably, it is 0-10, and further preferably 0-5.
The content (% by weight) of sugar (H) contained in the liquid detergent composition of the present invention is preferably 0 to 5, more preferably 0 to 3, with respect to the weight of the liquid detergent composition from the viewpoint of detergency. Next, it is more preferably 0-1.
The content (% by weight) of amino acid (I) contained in the liquid detergent composition of the present invention is preferably 0 to 10, more preferably 0 to 5, with respect to the weight of the liquid detergent composition from the viewpoint of detergency. Next, it is more preferably 0-3.
The content (% by weight) of the builder (J) contained in the liquid detergent composition of the present invention is preferably 0 to 5, more preferably 0 to 3, with respect to the weight of the liquid detergent composition from the viewpoint of detergency. Next, it is more preferably 0-1.
The content (% by weight) of the alkaline agent (K) contained in the liquid detergent composition of the present invention is preferably from 0 to 5, more preferably from 0.1 to the weight of the liquid detergent composition from the viewpoint of detergency. ~ 4, then more preferably 0.5-3.
The content (% by weight) of the chelating agent (L) contained in the liquid detergent composition of the present invention is preferably 0 to 5, more preferably 0 to 3 with respect to the weight of the liquid detergent composition from the viewpoint of detergency. Then, more preferably, it is 0-2.

  From the viewpoint of detergency, the pH of the liquid detergent composition of the present invention is preferably 7 to 11 and more preferably 7 to 10 with a 1% (w / w) aqueous solution.

The liquid detergent composition of this invention is obtained by mixing each component, and a manufacturing method is not specifically 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 of the present invention may be the same as the method of using the conventional liquid detergent composition, and is not particularly limited. An example is shown below.
(1) Tap water in a washing machine containing laundry, add the liquid detergent composition at 25 ° C., and gently stir to dissolve.
(2) Wash the laundry with a washing machine.
(3) Drain the liquid from the washing machine and rinse with tap water once or twice.
(4) Appropriate dehydration.

  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 by weight (0.05 mole part), 1 part of methanesulfonic acid and 92 parts by weight of ethanol (2 mole part) were mixed uniformly. The mixture was heated and stirred at 5 ° C. for 5 hours, concentrated by an evaporator, and then neutralized by adding 5.2 parts by weight (0.05 mol) of hydrochloric acid (concentration: 35% by weight). Then, it recrystallized from water, dried under reduced pressure {60 degreeC, 20Pa}, and obtained N- (alpha) -acetylarginine ethyl ester hydrochloride which is a compound (B).

<Examples 1 to 20>
Organic compound (A), compound (B), enzyme (a), surfactant (b), alkaline agent (K) and water in the proportions of Table 1 (in Table 1, the unit of each component represents% by weight) At 25 ° C. to obtain the liquid detergent composition of the present invention.

<Comparative Examples 1-5>
Conventional enzyme stabilizer, enzyme (a), surfactant (b), alkali agent (K) and water in the proportions of Table 2 (in Table 2, the unit of each component represents weight%) at 25 ° C. The liquid detergent composition of the comparative example was obtained, respectively.

In Tables 1 and 2, the following reagents were used as the compound (A), the compound (B), the enzyme (a), and the surfactant (b).
Guanidine hydrochloride: Wako Pure Chemical Industries, Ltd. Urea: Wako Pure Chemical Industries, Ltd. Pyridine: Wako Pure Chemical Industries, Ltd. Arginine hydrochloride: Wako Pure Chemical Industries, Ltd. Arginine ethyl ester: Wako Pure Acetylarginine hydrochloride manufactured by Yakuhin Co., Ltd .: Protease manufactured by Wako Pure Chemical Industries, Ltd .: Cellulase manufactured by Wako Pure Chemical Industries, Ltd .: Lipase manufactured by Wako Pure Chemical Industries, Ltd .: Amylase manufactured by Wako Pure Chemical Industries, Ltd. : Wako Pure Chemical Industries, Ltd. oleyl alcohol EO11 mol adduct: Sanyo Chemical Industries, Ltd. “Emarumin NL-110”
Dodecylbenzenesulfonic acid monoethanolamine salt: “ADEKA HOPE SAN-40PD” manufactured by ADEKA CORPORATION
Sodium laurate: Wako Pure Chemical Industries, Ltd.

なお、表２において、従来の酵素安定化剤は下記の試薬を使用した。
ホウ酸：和光純薬工業（株）製
プロピレングリコール：和光純薬工業（株）製
グリセリン：和光純薬工業（株）製

In Table 2, the following reagents were used as conventional enzyme stabilizers.
Boric acid: Wako Pure Chemical Industries, Ltd. Propylene glycol: Wako Pure Chemical Industries, Ltd. Glycerin: Wako Pure Chemical Industries, Ltd.

  Using the liquid detergent compositions of Examples 1 to 20 and Comparative Examples 1 to 5, the following detergency test was performed.

<Detergency test>
<Washing removal rate immediately after blending>
For each of the liquid detergent compositions obtained in Examples 1 to 20 and Comparative Examples 1 to 5, 0.8 g of the liquid detergent composition was dissolved in 999.2 g of water immediately after the liquid detergent composition was prepared to obtain a solution. Into this solution, 5 wet artificially contaminated cloths (4 cm × 4 cm) were put, and washed and rinsed under the following conditions using a targotometer (manufactured by Daiei Chemical Seiki Seisakusho, model “TM-4”). Thereafter, the cloth was taken out and dried at 70 ° C. for 60 minutes using a gear oven (manufactured by Tabai, GPS-222) to obtain a test cloth.
Then, using a multi-light source spectrocolorimeter (model “MSC-2”, manufactured by Suga Test Instruments Co., Ltd.), the reflectance of 540 nm of this test cloth is a total of four places, two on each side of the test cloth. (A total of 20 locations with 5 test cloths) were measured, the average value was obtained, and the cleaning removal rate (%) was calculated by the following formula. The results are shown in Tables 1 and 2.
(Cleaning conditions)
Time: 10 minutes, temperature: 25 ° C., rotation speed: 120 rpm
(Rinsing conditions)
Time: 1 minute, temperature: 25 ° C., rotation speed: 120 rpm
(Washing removal rate)
Cleaning removal rate (%) = {(R _W −R _S ) / (R _I −R _S )} × 100
Incidentally, R _I is the reflectivity of the clean cloth, R _W is the reflectance of the washed cloth, R _S represents the reflectance of the stained cloth.
Moreover, the used wet artificial contamination cloth is a wet artificial contamination cloth (reflectance at 540 nm of 40 ± 5%) manufactured by the Japan Laundry Science Association having the dirt composition shown in Table 3.

<Washing removal rate after storage at 25 ° C for 3 months>
For each of the liquid detergent compositions obtained in Examples 1 to 20 and Comparative Examples 1 to 5, in the above <Washing and removal rate immediately after compounding>, instead of the liquid detergent composition immediately after preparation, preparation of the liquid detergent composition Thereafter, a washability test was conducted in the same manner except that the liquid detergent composition stored at 25 ° C. for 3 months was used, and the washing removal rate was calculated. The results are shown in Tables 1 and 2.

<Washing removal rate ratio>
The ratio between the washing removal rate immediately after blending and the washing removal rate after storage at 25 ° C. for 3 months was calculated by the following formula. The results are shown in Tables 1 and 2.
Wash removal rate ratio = (wash removal rate after storage at 25 ° C. for 3 months) / (wash removal rate immediately after preparation)

From the results in Table 2, it can be seen that the conventional liquid detergent composition shown in Comparative Example 5 has a low detergency immediately after preparation, and the detergency is greatly reduced after storage at 25 ° C. for 3 months. Further, in Comparative Examples 6 to 8 to which conventional stabilizers were added, the detergency was slightly improved, but it was found that the detergency was lowered after storage at 25 ° C. for 3 months and is not suitable for long-term storage. Moreover, it turns out from the result of the comparative example 9 which used 2 types of enzymes, even if it increases the kind of enzyme simply, detergency is not improved.
On the other hand, from the results shown in Table 1, the liquid detergent compositions of Examples 1 to 4 containing the compound (A) are largely suppressed from deteriorating in washability after being stored at 25 ° C. for 3 months. It can be seen that it can be maintained. Further, in Examples 5 to 16 including (B), it can be seen that the cleaning performance is hardly deteriorated and the cleaning performance can be maintained for a long time even after storage at 25 ° C. for 3 months.
Moreover, in Examples 17-20 which used multiple types of enzyme together, it turns out that not only washing | cleaning property falls, but washing | cleaning property improves further compared with the case where an enzyme is used independently.

  The liquid detergent composition of the present invention has good persistence of enzyme activity and can maintain cleanability for a long period of time, and can be used particularly for liquid detergent compositions for clothing.

Claims (7)

A liquid detergent composition containing an organic compound (A), an enzyme (a), a surfactant (b) and water that satisfy the following conditions (1) to (3);
(1) When a proton is added to the molecule of the organic compound (A), at least one atom (Z) in the molecule has an atom (Z) and an atom (Y) bonded to the atom (Z). The π bond formed by π electrons has a resonance structure,
An atom (Z) and an atom (Y) have,
There are 4 or more π electrons participating in the π bond of this resonance structure (2) The ionic strength of the 0.1 mol / dm ³ solution is 0.1 or more (3) The molecular weight is less than 300 thing. The liquid detergent composition according to claim 1, wherein the organic compound (A) is a salt of the compound (A2) represented by the general formula (2).

[Wherein, X represents an imino group, an oxygen atom or a sulfur atom. ] The liquid detergent composition according to claim 1 or 2, wherein the organic compound (A) is guanidine hydrochloride. The liquid detergent composition according to claim 1, wherein the organic compound (A) is a compound (A2) represented by the following general formula (2).

[Wherein, X represents an imino group, an oxygen atom or a sulfur atom. ] Furthermore, the liquid detergent composition in any one of Claims 1-4 containing the compound (B) represented by following General formula (3).

[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 according to any one of claims 1 to 5, wherein the enzyme (a) is at least one enzyme selected from the group consisting of protease, cellulase, amylase and lipase. The liquid detergent composition according to any one of claims 1 to 6, wherein the content of the compound (A) is 0.01 to 30% by weight based on the weight of the liquid detergent composition.