KR20140052972A - Liquid cleaning agent composition - Google Patents

Abstract

At least one component selected from the group consisting of (A) at least 40% by mass of a nonionic surfactant, (B) at least one component selected from the group consisting of an amino carboxylic acid or a salt thereof and a phosphonic acid or a salt thereof, and (C) A monocarboxylic acid or a salt thereof, and (D) an enzyme.

Description

[0001] LIQUID CLEANING AGENT COMPOSITION [0002]

The present invention relates to a liquid detergent composition.

The present application claims priority under U.S. Patent Application No. 2011-096005, filed on April 22, 2011, the contents of which are incorporated herein by reference.

The detergent used for washing such as medical care (clothes) has a powder type and a liquid type. The liquid detergent has a low usage rate due to the fact that there is less concern about the residue of the liquid and the liquid can be directly applied to medical treatment.

In the cleaning agent, a surfactant acts as a main cleaning component, and various components such as enzymes are mixed. In particular, enzymes play an important role as a component exhibiting various performances in small amounts.

However, the liquid detergent containing the enzyme has a problem that the stability of the enzyme is lower than that of the powder detergent, and the enzyme performance tends to deteriorate over time. Particularly, when a chelating agent (hereinafter also referred to as a metal ion sequestering agent) is coexisted, the calcium ions stabilizing the enzyme are lost, so that the enzyme performance tends to deteriorate.

In order to solve such a problem, various studies have been made to improve the stability of the enzyme in the liquid detergent. For example, Patent Document 1 discloses that at least one compound selected from the group consisting of a surfactant and a protein hydrolyzing enzyme, a sequestering agent, and an alkanolamine and / or a pyrrolidonecarboxylate, , And a calcium salt which gives 0.1 to 15 millimoles of free calcium ions per liter. Patent Document 2 discloses a liquid detergent composition comprising a surfactant as a main component, at least one short chain carboxylate selected from a formate salt and a lactate, an endogenous protein hydrolyzing enzyme, and a sequestering agent Discloses a liquid detergent composition that is substantially free of free calcium ions in the composition.

Patent Document 1: JP-A-5-179291 Patent Document 2: JP-A-5-179292

In recent years, a so-called " compact type " detergent containing a surfactant at a high concentration and having a small amount of use once has become mainstream in consideration of environment and convenience at the time of purchase.

The compact type liquid detergent has a water content as low as that containing a high concentration of a surfactant. Therefore, when an enzyme is added to a liquid cleaning agent of a compact type, precipitation or denaturation of the enzyme tends to occur, and stability is further lowered. In particular, when a protease is used as an enzyme, the performance of the enzyme tends to be deteriorated by self-digestion (self-digestion).

The methods described in Patent Documents 1 and 2 are effective to some extent when the surfactant concentration is low. However, when the surfactant is contained at a high concentration of 40% or more, it can not be said that the stabilization effect is sufficient. When the preservation test is conducted, the enzyme performance may be lowered to a level at which the performance can not be sufficiently exhibited. The deterioration of the enzyme performance leads to the deterioration of the detergency, and therefore improvement is required.

Although many studies have been carried out to increase the performance of the enzyme itself by changing the intramolecular structure of the enzyme itself, it takes labor and cost and can not be said to be practical.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid detergent composition which contains a surfactant at a high concentration and which also has excellent performance and stability of an enzyme.

The present invention for solving the above problems has the following aspects.

That is, a first aspect of the present invention is a composition comprising: (A) 40% by mass or more of a nonionic surfactant; (B) at least one component selected from an amino carboxylic acid or a salt thereof, and a phosphonic acid or a salt thereof, (C) an? -Hydroxy-monocarboxylic acid or a salt thereof, (D) ≪ / RTI >

A second aspect of the present invention is the liquid detergent composition according to the first aspect, wherein the component (C) is at least one component selected from the group consisting of lactic acid (lactic acid) and sodium lactate .

A third aspect of the present invention is the liquid detergent composition according to the first or second aspect, wherein the component (D) comprises at least a protease.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid detergent composition containing a surfactant at a high concentration and having both excellent performance and stability of an enzyme.

The liquid detergent composition of the present invention contains the following components (A) to (D) as essential components.

[Component (A)] [

The component (A) is a nonionic surfactant. The component (A) is a surfactant used for imparting cleaning power to the liquid detergent composition.

Examples of the component (A) include, but are not limited to, polyoxyalkylene type nonionic surfactants, alkyl phenol, alkylene oxide adducts such as fatty acids having 8 to 22 carbon atoms and amines having 8 to 22 carbon atoms,

Polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, hydrogenated castor oil alkyl A fatty acid ester, a N-alkyl polyhydroxy fatty acid amide, an alkyl glycoside, and the like. Any one of them may be used alone, or two or more kinds may be used in combination.

Among the above components, as the component (A), a polyoxyalkylene type nonionic surfactant is preferable from the viewpoints of viscosity and appearance stability. Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (I) (hereinafter referred to as compound (I)).

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is a divalent linking group; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO and is an integer of 0 to 6]

In the formula (I), the number of carbon atoms of the hydrocarbon group of R ¹ is from 8 to 22, preferably from 10 to 18, and more preferably from 12 to 18. The hydrocarbon group may be straight chain or branched chain. Further, it may or may not have an unsaturated bond.

Examples of the divalent linking group of -X- include -O-, -COO-, -CONH-, and the like.

The alkyl group in R ² has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

The carbon number of the alkenyl group in R ² is 2 to 6, preferably 2 to 3. The compound (I) wherein -X- is -O-, -COO- or -CONH- is a primary or secondary alcohol having 8 to 22 carbon atoms (R ¹ -OH or (R ¹ ) ₂ -C-OH ), A fatty acid having 8 to 22 carbon atoms (R ¹ -COOH) or a fatty acid amide having 8 to 22 carbon atoms (R ¹ -CONH) as raw materials.

s is an integer of 3 to 20, preferably an integer of 5 to 18. When the average addition mole number s of EO exceeds 20, the HLB value becomes too high and deteriorates sebum (sebum) deterioration, so that the cleaning function tends to be deteriorated. On the other hand, if the average addition mole number (s) of EO is less than 3, the effect of preventing the odor from deteriorating is lowered.

t is an integer of 0 to 6, preferably an integer of 0 to 3; If the average addition mole number t of PO exceeds 6, the storage stability of the liquid detergent composition at high temperatures tends to be lowered.

When t is 1 or more, that is, when the compound (I) is an adduct in which both EO and PO are added, the addition method of EO and PO is not particularly limited and may be, for example, a random addition or a block addition . As the block addition method, for example, a method of adding PO after adding EO; Adding PO and then adding EO; A method in which PO is added after addition of EO, and EO is added.

Here, the "average addition mole number" means the number of moles of ethylene oxide to be reacted with respect to 1 mole of the alcohol used.

The addition mole number distribution of EO or PO is not particularly limited.

The addition mole number distribution is liable to fluctuate depending on the reaction method when the nonionic surfactant is produced. For example, when ethylene oxide or propylene oxide is added to a hydrophobic raw material by using an ordinary alkali catalyst such as sodium hydroxide or potassium hydroxide, the added mole number distribution of EO or PO tends to have a relatively wide distribution. In addition, Al ^{+ 3} as described in Unexamined Japanese Patent Publication Hei 6-15038 Ho, Ga ^{+ 3,} In ^{+ 3,} Tl ^{+ 3,} Co ^{+ 3,} Sc ^{+ 3,} La ^{+ 3,} the addition of metal ions such as Mn ^{+ 2} When ethylene oxide or propylene oxide is added to a hydrophobic raw material by using a specific alkoxysilylation catalyst such as magnesium oxide or the like, the distribution of addition mole number of EO or PO tends to become a relatively narrow distribution.

As the compound (I), in particular, a compound wherein -X- is -O- (alcohol ethoxylate); Or a compound in which -X- is -COO- and R ² is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (fatty acid alkyl or alkenyl ester).

When -X- in formula (I) is -O-, the number of carbon atoms of R ¹ is preferably from 10 to 22, more preferably from 10 to 20, and particularly preferably from 10 to 18. R ² is preferably a hydrogen atom.

When -X- in the formula (I) is -COO-, the carbon number of R ¹ is preferably 9 to 21, and more preferably 11 to 21. R ² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

As specific examples of the compound wherein -X- is -O- or -COO-,

12 mol equivalent of alcohol such as Diol (C13, C represents the number of carbon atoms, hereinafter the same) manufactured by Mitsubishi Chemical Corporation, Neodol (C12 / C13) Or a nonionic surfactant to which ethylene oxide equivalent to 15 moles is added;

A nonionic surfactant obtained by adding ethylene oxide equivalent to 12 moles or 15 moles to a natural alcohol such as CO-1214 or CO-1270, manufactured by P &

A nonionic surfactant (trade name: LutensolTO7 manufactured by BASF) to which 7 mol equivalent of ethylene oxide was added to the C13 alcohol obtained by providing C12 alkene obtained by trimerizing butene to the oxo method;

A nonionic surfactant (trade name: Lutensol XL70 manufactured by BASF) to which 7 mol equivalent of ethylene oxide is added to the C10 alcohol obtained by providing pentanol to the Gerber reaction;

A nonionic surfactant (trade name: Lutensol XA60, manufactured by BASF) to which ethylene oxide equivalent to 6 moles is added to the C10 alcohol obtained by providing pentanol to the Gerber reaction;

A nonionic surfactant (trade name: Sofutanol 0 or Sofutanol 50, manufactured by Nippon Catalysts Co., Ltd.) to which ethylene oxide equivalent to 9 moles or 15 moles was added to the secondary alcohol having 12 to 14 carbon atoms;

(Polyoxyethylene coconut fatty acid methyl ester EO 15 mol (product name)) obtained by adding 15 mol of ethylene oxide to the methyl palm fatty acid (lauric acid / myristic acid = 8/2) using an alkoxysilylation catalyst );

 And the like.

As the compound (I), a compound in which -X- is -COO-, R ² is an alkyl group having 1 to 6 carbon atoms and t is 0, that is, a polyoxyethylene fatty acid alkyl ester is preferable, and R ² is a methyl group (Hereinafter may be sometimes referred to as " MEE ") is particularly preferable as the polyoxyethylene fatty acid methyl ester.

By containing the polyoxyethylene fatty acid alkyl ester, the liquid detergent composition of the present invention is excellent in solubility in water and easy to obtain a high washing power. In addition, even when a surfactant at a high concentration is contained, the concentration of the liquid detergent composition is not so much increased (gelation), and the liquid detergent composition can have a good flowability.

Polyoxyethylene fatty acid alkyl esters, particularly MEE, are nonionic surfactants having weak orientation of molecules in an aqueous solution system and unstable micelles, so gelation or the like does not occur at a high concentration, It is assumed that it can be done. It is also presumed that the solubility in water is improved. It is also believed that it contributes to good fluidity in high concentration. Therefore, when the polyoxyethylene fatty acid alkyl ester is put into the water in the washing machine, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid becomes uniform quickly, and since the cleaning agent can contact the substrate at a predetermined concentration from the beginning of cleaning, I think it can be obtained.

The polyoxyethylene fatty acid alkyl ester is preferably used in an amount of 30% by mass or more, more preferably 30% by mass or less, more preferably 30% by mass or less, Or more of ethylene oxide.

The elongation percentage is preferably 55% by mass or more, and more preferably 65% by mass or more. The higher the elongation percentage is, the better, but the upper limit value is substantially 80 mass% or less.

That is, the elongation percentage is 30 mass% or more and 80 mass% or less; Preferably 55 mass% or more and 80 mass% or less; More preferably, it is 65 mass% or more and 80 mass% or less. When the elongation percentage is 30% by mass or more, preferably 55% by mass or more, the cleaning power, the rinsing property, and the liquid stability of the liquid detergent composition are improved. In addition, it becomes easy to obtain a liquid detergent composition having a low odor of the raw material of the surfactant. Further, as the desired component (ethylene oxide adduct having the desired number of moles of added ethylene oxide) increases, the cleaning power also improves. This is presumably because, after the production of the polyoxyethylene fatty acid alkyl ester, the number of the fatty acid ester (the compound in which s is 0) as the raw material and the ethylene oxide adduct in which s is 1 or 2 in the general formula (I) do.

Among the compounds contained as an impurity in the polyoxyethylene fatty acid alkyl ester, the ratio of the total of the fatty acid ester in which the addition mole number (s) of ethylene oxide is 0 and the ethylene oxide adduct in which s is 1 or 2 (Hereinafter referred to as " Y0-2 ") is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, based on the total amount of the polyoxyethylene fatty acid alkyl ester. If Y0-2 is 0.5% by mass or less, a liquid detergent composition having less raw material for surfactant can be obtained.

The narrowing ratio of polyoxyalkylene type nonionic surfactant such as polyoxyethylene fatty acid alkyl ester is a value obtained by the following formula (S).

In the formula (S), S _max represents the number of added moles (the value of s + t) of the alkylene oxide in the alkylene oxide adduct which is the most abundant in the polyoxyalkylene-type nonionic surfactant.

i represents an addition mole number of the alkylene oxide.

Yi represents the ratio (mass%) of the alkylene oxide adduct having an addition mole number of the alkylene oxide present in the polyoxyalkylene nonionic surfactant to the total amount of the polyoxyalkylene nonionic surfactant.

[Equation 1]

The above-mentioned elongation percentage can be controlled by, for example, a production method of a polyoxyethylene fatty acid alkyl ester.

The method for producing the polyoxyethylene fatty acid alkyl ester is not particularly limited, and for example, a method of addition polymerization of ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (Japanese Patent Application Laid-Open No. 2000-144179 ). ≪ / RTI >

Examples suitable of such surface-modified mixed metal oxide catalysts, specifically, the surface-modified by a metal hydroxide, metal ions ^{(Al 3 +, Ga 3 +} , In 3 +, Tl 3 +, Co 3 +, Sc 3 ⁺ , La ³⁺ , Mn ^{2 +,} etc.); Hydrotalcite fired catalysts that have been surface-modified with at least one compound selected from the group consisting of metal hydroxides, metal alkoxides, and the like.

In the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and at least one compound selected from the group consisting of metal hydroxides and metal alkoxides is preferably in the range of from 1 to 100 parts by mass, The proportion of at least one compound selected from the group consisting of metal alkoxide is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass.

As the component (A), a single kind of nonionic surfactant may be used alone, or plural kinds of nonionic surfactants may be used in combination.

The detergent container which can be washed in a small amount of usage can be made compact by high mixing (high mixing) of the surfactant. However, in such a case, the gelation area is small even at a high concentration, From the viewpoint of ease, it is preferable to use a secondary alcohol ethoxylate (for example, Soputanolate manufactured by Nippon Kogyo Co., Ltd.) in which ethylene oxide is added to the secondary alcohol and MEE to which ethylene oxide is added to the fatty acid methyl. Since these gelation regions are small even at a high concentration, gelation is unlikely to occur at a high mixing ratio.

These may be used in combination with a primary alcohol ethoxylate to which ethylene oxide is added to the primary alcohol.

Particularly, in the component (A), the ratio of the secondary alcohol ethoxylate or MEE to the alcohol ethoxylate of the first class (mass ratio: secondary alcohol ethoxylate or MEE / primary alcohol Is preferably 3/7 to 10/0, more preferably 5/5 to 10/0, and even more preferably 7/3 to 10/0.

The blending amount of the component (A) is 40% by mass or more, preferably 40% by mass to 70% by mass, more preferably 40% by mass to 65% by mass, and still more preferably 45% by mass to 55% by mass with respect to the total mass of the liquid detergent composition . The effect of the present invention is easily obtained by the blending amount of the component (A) being 40 mass% or more with respect to the total mass of the liquid detergent composition. And can be easily used as a liquid detergent composition of a concentrated type. On the other hand, increase in the viscosity of the liquid detergent composition at low temperature is suppressed by the amount of the component (A) being 70 mass% or less, preferably 65 mass% or less, with respect to the total mass of the liquid detergent composition.

[Component (B)] [

(B) is at least one component selected from an amino carboxylic acid (salt) and a phosphonic acid (salt).

The aminocarboxylic acid (salt) represents an aminocarboxylic acid or a salt thereof.

The phosphonic acid (salt) represents a phosphonic acid or a salt thereof.

By mixing the component (B), the performance of the component (D) can be improved without compromising the stability of the component (D). This improves the cleaning performance (for example, cleaning performance against protein contamination in the case of protease) contributed by the component (D). As the aminocarboxylic acid, a polycarboxylic acid containing a plurality of carboxyl groups is preferable. The number of carboxyl groups in one molecule is preferably 2 to 5, more preferably 2 or 3.

Examples of salts of aminocarboxylic acids include alkanolamine salts such as sodium salt, potassium salt, ammonium salt and ethanolamine.

As the aminocarboxylic acid (salt), a compound represented by the following general formula (b1) is particularly preferable.

[Chemical Formula 1]

Wherein R ³ is - (CH ₂ ) _n -A; A is H, OH or COOM; M is H, Na, K, and NH ₄ or an alkanol amine; and n is an integer of 0 to 5]

Specific examples of the aminocarboxylic acid (salt) include methylglycine diacetic acid (salt) such as methylglycine diacetate trisodium (MGDA), ethylglycine diacetic acid (salt) such as ethylglycine diacetate trisodium, nitrile triacetic acid (Salt), iminodiposaccharic acid (salt), tetrasodium aspartate-N, N-2 acetic acid, trisodium acetic acid diacetate, and tetrasodium glutamate diacetate. Among them, methylglycine diacetic acid (salt) and ethylglycine diacetic acid (salt) are preferable, and methylglycine diacetate (MGDA) is particularly preferable.

Examples of the phosphonic acid include hydroxyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, CH ₃ C (OH) [PO (OH) ₂ ] ₂ (abbreviation: HEDP), aminotri _{acid) «N [CH 2 PO (OH} ) 2] 3 »( abbreviation: ATMP), ethylene diamine tetra (methylenephosphonic _{acid) «N 2 (CH 2) 2} [CH 2 PO (OH) 2] 4», D triamine penta (methylene phosphonic _{acid) «N 3 (CH 2) 2} [CH 2 PO (OH) 2] 5 », 2- phosphono-1,2,4-butane tricarboxylic acid «PO (OH) ₂ CH ₂ CCH ₂ CH ₂ (COOH) ₃ (abbreviation: PBTC).

Examples of the salt of phosphonic acid include alkanolamine salts such as the sodium salt, potassium salt, ammonium salt and ethanolamine of the above phosphonic acid.

As the phosphonic acid (salt), among them, hydroxyphosphonic acid is preferable, and HEDP is particularly preferable.

Any one of the components (B) may be used alone, or two or more of them may be used in combination.

The blending amount of the component (B) is preferably from 0.1 to 5 mass%, more preferably from 0.15 to 2 mass%, and still more preferably from 0.2 to 1.5 mass% with respect to the total mass of the liquid detergent composition. When the blending amount of the component (B) is in the range of 0.1 to 5 mass% with respect to the total mass of the liquid detergent composition, the activity of the enzyme can be sufficiently increased. In addition, the stability (sedimentation, etc.) of the preparation over time can be increased. The reason why the activity of the enzyme is improved is thought to be that it acts on the active center of the enzyme during washing and improves the catalytic action, though the details are not clear.

On the other hand, if the content of the component (B) is less than 0.1% by mass with respect to the total mass of the liquid detergent composition, the effect of improving the performance of the enzyme may become insufficient. On the other hand, if it is more than 5% by mass, precipitation may occur during formulation.

[Component (C)] [

The component (C) is? -Hydroxy-monocarboxylic acid (salt).

The? -hydroxy-monocarboxylic acid (salt) represents? -hydroxy-monocarboxylic acid or its salt.

The component (C) is blended for the purpose of enhancing the stability of the component (D) in the preparation. It is considered that the component (D) is adsorbed on the surface of the component (D) and plays a role of maintaining the structure (that is, preventing the attack from the outside). In general, the chelating agent deteriorates the stability of the enzyme by depriving the Ca of the enzyme. However, in the present invention, by blending the specific component (component (B)) as the chelating agent and the component (C) The stability of the component (D) can be maintained.

The? -hydroxy-monocarboxylic acid is preferably represented by the following general formula (c1).

R-C (OH) (R ') - COOH ... (c1)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group having 2 to 6 carbon atoms, An ether group, an amino group which may have a substituent, or an amine derivative group; R 'represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group of 2 to 6 carbon atoms, an ether group of 2 to 6 carbon atoms , Or an amino group which may have a substituent, or an amine derivative group].

Examples of the substituent which the alkyl group or the aryl group in R and R 'may have in the formula (c1) include an aryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a nitro group, a nitro derivative group, An ester group of 6 to 6 carbon atoms, an ether group of 2 to 6 carbon atoms, an amino group which may have a substituent, an amine derivative group, an amide group, an amide derivative group and a halogen atom.

Examples of the substituent which the amino group may have include an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a benzyl group, a phenyl group and a pyridyl group.

Examples of the salt of? -hydroxy-monocarboxylic acid include alkali metal salts such as sodium salt and potassium salt; Alkaline earth metal salts such as calcium salts and magnesium salts; And alkanolamine salts such as ammonium salts and ethanol amines.

(C) is preferably at least one component selected from the group consisting of glycolic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, mandelic acid, optical isomers thereof and salts thereof; More preferably at least one component selected from mandelic acid, lactic acid and salts thereof; Particularly preferred are at least one component selected from lactic acid and salts thereof. As the lactate, sodium lactate is preferable.

As the component (C), any one of them may be used alone, or two or more of them may be used in combination.

The blending amount of the component (C) is preferably from 0.1 to 5 mass%, more preferably from 0.15 to 2 mass%, and still more preferably from 0.2 to 1.5 mass% with respect to the total mass of the liquid detergent composition. (C) is sufficiently adsorbed on the surface of the component (D) when the compounding amount of the component (C) is within the range of 0.1 to 5 mass% with respect to the total mass of the liquid refining composition. Stability can be enhanced.

On the other hand, if the content of the component (C) is less than 0.1% by mass based on the total mass of the liquid detergent composition, the effect of stabilizing the component (D) may become insufficient. If it exceeds 5% by mass, precipitation may occur at the time of formulation.

[Component (D)] [

Component (D) is an enzyme.

The term " enzyme " in the present specification and claims refers to an enzyme preparation.

As the component (D), an enzyme conventionally used for a medical cleaning agent can be used. For example, protease, amylase, lipase, cellulase, mannanase and the like can be mentioned as general enzymes.

The protease in the present invention is preferably a protease having serine, histidine, and aspartic acid in its molecule, such as serine protease.

Examples of the protease include Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, and Purafect L, Purafect OX, and Properase L, available from Genencor.

As the amylase, 300 l of Termamyl, 300 l of Termamyl, 300 l of Duramyl, 12 l of Stainzyme, 12 l of Stainzyme Plus, trade name Maxamyl available from Zeneco, available from Novozymes, Inc. as a preparation for amylase, PURANAZEAMANO, DB-250 available from Seikagaku Kogyo Co., Ltd., and the like.

As the lipase, 100 l of Lipex and 100 l of Lipolase available from Novozymes, Inc. as a lipase preparation can be mentioned.

Examples of the cellulase include 5000 liters of Endolase, 0.4 l of Cellu yme, and 4500 l of CaRyme available from Novozymes, Inc. as a cellulase preparation.

Mannaway 4L, which is available from Novozymes < (R) >

In the present invention, it is particularly preferable that the component (D) contains at least a protease.

As the protease, Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L, Everlase Ultra 16L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, and Coronase 48L are preferable among the above. Everlase 16L, Savinase 16L, and Coronase 48L are particularly preferred.

As the component (D), any one species may be used alone, or two or more species may be used in combination.

The blending amount of the component (D) is not particularly limited in terms of stability, but is preferably 0.01% by mass or more, more preferably 0.03% by mass or more based on the total mass of the liquid detergent composition from the viewpoint of improvement in cleaning performance. It is preferably 2% by mass or less, more preferably 1% by mass or less, and most preferably 0.8% by mass or less based on the total mass of the liquid detergent composition in terms of enzyme precipitation and performance saturation in a composition having a low water content .

That is, the blending amount of the component (D) is preferably 0.01% by mass or more and 2% by mass or less with respect to the total mass of the liquid detergent composition; More preferably 0.01 mass% or more and 1 mass% or less; More preferably 0.03 mass% or more and 1 mass% or less; More preferably 0.03 mass% or more and 0.8 mass% or less.

(B) / (C)) of the blending amount of the component (B) to the blending amount of the component (C) in the liquid detergent composition is preferably in the range of 0.05 to 40, more preferably 0.08 to 20 , And most preferably within the range of 0.1 to 15.

(B) / (C) is in the range of 0.05 to 40, it is possible to suppress the decrease of the enzyme activity by the preservation, and the effect of improving the cleaning power by the component (B) can be expected.

When the ratio (B) / (C) is less than 0.05, the cleaning performance improving effect by the component (B) can not be exerted advantageously. When the ratio (B) / (C) exceeds 40, the stability of the enzyme deteriorates. After storage, sufficient performance can not be exhibited, and precipitation occurs, resulting in problems in the appearance of the liquid.

(B) / (D)) of the blending amount of the component (B) to the blending amount of the component (D) in the liquid detergent composition is preferably in the range of 0.05 to 500, more preferably in the range of 0.1 to 20 Is more preferable. (B) / (D) is in the range of 0.05 to 500, the component (B) can activate the component (D) at the time of cleaning to improve the cleaning performance.

(C) / (D)) of the amount of the component (C) to the amount of the component (D) in the liquid detergent composition is preferably 0.05 to 500, more preferably 0.1 to 20 . (C) / (D) is in the range of 0.05 to 500, the stability of the component (D) is not impaired, the cleaning effect is not deteriorated during cleaning, and the activation effect by the component (B) .

[Other ingredients]

The liquid detergent composition of the present invention may contain other components than the above components (A), (B), (C) and (D) within the range that does not impair the effect of the present invention It is also good. As the other component, components commonly used in a liquid detergent can be blended, and examples thereof include the following components.

Examples of the water-miscible organic solvent include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol; Glycols such as propylene glycol, butylene glycol and hexylene glycol; Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, and dipropylene glycol; And alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether.

The blending amount of the water-miscible organic solvent is preferably 0.1 to 15 mass% with respect to the total mass of the liquid detergent composition.

As the anionic surfactant, a known anionic surfactant can be used and can be easily obtained on the market.

Examples of the anionic surfactant include straight chain alkylbenzenesulfonic acid or a salt thereof; -olefin sulfonic acid salts; Straight-chain or branched-chain alkylsulfuric ester salts; Alkyl ether sulfuric acid ester salts or alkenyl ether sulfuric acid ester salts; An alkane sulfonate having an alkyl group; alpha -sulfo fatty acid ester salts, and the like.

Examples of salts thereof include alkali metal salts such as sodium and potassium; Alkaline earth metal salts such as magnesium; And alkanolamine salts such as monoethanolamine and diethanolamine.

The straight-chain alkylbenzenesulfonic acid or a salt thereof is preferably a straight-chain alkylbenzene sulfonic acid or a salt thereof having 8 to 16 carbon atoms in the straight-chain alkyl group, and particularly preferably a straight-chain alkylbenzenesulfonic acid or a salt thereof having 10 to 14 carbon atoms.

As the? -olefin sulfonic acid salt, an? -olefin sulfonic acid salt having 10 to 20 carbon atoms is preferable.

As alkylsulfuric ester salts, alkylsulfuric ester salts having 10 to 20 carbon atoms are preferred.

Examples of the alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt include an alkyl ether sulfuric acid ester salt having an average of from 1 to 10 moles of ethylene oxide having an alkyl group or alkenyl group having 10 to 20 carbon atoms, Ether sulfuric acid ester salts (i.e., polyoxyethylene alkyl ether sulfuric acid ester salts or polyoxyethylene alkenyl ether sulfuric acid ester salts) are preferable.

As the alkane sulfonate, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is particularly preferable.

As the? -sulfo fatty acid ester salt, an? -sulfo fatty acid ester salt having 10 to 20 carbon atoms is preferable.

Of these, straight-chain alkylbenzenesulfonic acid or its salt, alkanesulfonic acid salt, polyoxyethylene alkyl ether sulfate, and? -Olefin sulfonic acid salt are particularly preferable.

Examples of other anionic surfactants include fatty acid salts having 8 to 22 carbon atoms, alkyl ether carboxylates having 8 to 22 carbon atoms, polyoxyalkylene ether carboxylates having 8 to 22 carbon atoms, alkyl having 8 to 22 carbon atoms (Or alkenyl) amide ether carboxylate, acylaminocarboxylate having 8 to 22 carbon atoms, and the like; A polyoxyalkylene alkyl phosphate ester salt having 8 to 22 carbon atoms, a polyoxyalkylene alkylphenyl phosphate ester salt having 8 to 22 carbon atoms, a glycerin fatty acid ester monophosphate ester having 8 to 22 carbon atoms Phosphate-type negative-ionic surfactants such as salts thereof, and the like.

Examples of salts thereof include alkali metal salts such as sodium and potassium; Alkaline earth metal salts such as magnesium; And alkanolamine salts such as monoethanolamine and diethanolamine.

As the anionic surfactant, a single kind of anionic surfactant may be used alone, or plural kinds of anionic surfactants may be used in combination.

The blending amount of the anionic surfactant is preferably 0 to 20% by mass with respect to the total mass of the liquid detergent composition.

Examples of the cationic surfactant include alkyltrimethylammonium salts of 4 to 22 carbon atoms, dialkyldimethylammonium salts of 4 to 22 carbon atoms, alkylbenzyldimethylammonium salts of 10 to 22 carbon atoms, and cationic surfactants of alkylpyridinium salts of 6 to 22 carbon atoms And an activator.

Examples of salts thereof include alkali metal salts such as sodium and potassium; Alkaline earth metal salts such as magnesium; And alkanolamine salts such as monoethanolamine and diethanolamine.

Examples of the amphoteric surfactant include alkyl betaine type having 4 to 22 carbon atoms, alkyl amide betaine type having 4 to 22 carbon atoms, imidazoline type, alkylaminosulfone type having 4 to 22 carbon atoms, An alkyl aminocarboxylic acid type, an alkyl amide carboxylic acid type having 4 to 22 carbon atoms, an amide amino acid type, and a phosphoric acid type amphoteric surfactant.

Examples of the reducing agent and the solubilizing agent include aromatic sulfonic acids or salts thereof such as toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, toluenesulfonic acid salt, xylenesulfonic acid salt, Naphthalenesulfonic acid salts.

Examples of the salt of an aromatic sulfonic acid include a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an ammonium salt, and an alkanolamine salt.

These acids or salts thereof may be used alone or in combination of two or more.

The blending amount of the reducing agent and the solubilizing agent is preferably 0.01 to 15% by mass relative to the total mass of the liquid detergent composition. Within this range, the effect of inhibiting the formation of a film formed by gelation of the liquid detergent composition on the liquid surface of the liquid detergent composition is improved.

Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine and the like. The alkaline agent may be used alone or in combination of two or more.

The blending amount of the alkaline agent is preferably 0.5 to 5% by mass with respect to the total mass of the liquid detergent composition.

(Chelating agent) other than the component (B) include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid.

The blending amount of the metal ion capturing agent other than the component (B) is preferably 0.01 to 20% by mass relative to the total mass of the liquid detergent composition.

The antioxidant is not particularly limited, but is preferably a phenol antioxidant because of its good washing power and liquid stability, and is preferably a monophenol antioxidant of dibutylhydroxytoluene or butylhydroxyanisole, a 2,2 ' -Methylenebis (a bisphenol-based antioxidant such as 4-methyl-6-t-butylphenol and a macromolecular phenol-based antioxidant such as dl-? -Tocopherol are more preferable; a monophenol antioxidant, More preferable.

Among the monophenol-based antioxidants, dibutylhydroxytoluene is particularly preferable. Among the polymer type phenol antioxidants, dl -? - tocopherol is particularly preferable.

The antioxidant may be used alone or in combination of two or more.

The blending amount of the antioxidant is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent composition.

As the preservative, for example, 0.001 to 1% by mass, based on the total mass of the liquid detergent composition, may be contained, for example, the product name Codex CG or the like manufactured by Rohm and Haas Company.

For the purpose of improving the storage stability, benzoic acid or a salt thereof (also having an effect as an antiseptic) may be contained. Examples of salts include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, and alkanolamine salts. The amount of the benzoic acid or its salt to be blended is preferably from 0.1 to 5 mass%, more preferably from 0.15 to 2.0 mass%, based on the total mass of the liquid detergent composition.

Boric acid, borax, formic acid or a salt thereof for the purpose of stabilizing the enzyme; Calcium salts such as calcium chloride and calcium sulfate may be contained in an amount of 0 to 2 mass% with respect to the total mass of the liquid detergent composition.

Silicon such as dimethyl silicone, polyether-denatured silicone, and amino-modified silicone may be contained in an amount of 0 to 5 mass% with respect to the total mass of the liquid detergent composition for the purpose of improving touch.

A fluorescent whitening agent such as a distyryl rubiphenyl type may be contained in an amount of 0 to 1 mass% based on the total mass of the liquid detergent composition for the purpose of improving the whiteness of the white garment.

For the purpose of preventing migration and preventing contamination, a re-contamination preventing agent such as polyvinyl pyrrolidone or carboxymethyl cellulose may be contained in an amount of 0 to 2 mass% with respect to the total mass of the liquid detergent composition.

Poultice, soil release agent, and the like.

For the purpose of improving the added value of the product, a flavoring agent, an extracting agent such as a coloring agent, an emulsifying agent, or a natural product may be contained.

As the representative examples of the flavor, the flavor compositions A, B, C, and D described in Tables 11 to 18 of Japanese Patent Application Laid-Open No. 2002-146399 can be used. The blending amount of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent composition.

Examples of the colorant include general-purpose pigments and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3 and Tacos P- . The blending amount of the colorant is preferably about 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent composition.

Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and emulsions with a solid content of 30 to 50 mass% are suitably used. As a specific example, a polystyrene emulsion (Saibinol PX-196 PE-3 made by Saiden Chemical Industry Co., Ltd., solid content: 40 mass%) and the like can be mentioned. The blending amount of the emulsifying agent is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent composition.

Examples of the extracts of natural products include, but are not limited to, elk trees, Uba urushii, Echinaceae, golden, yellow, white, chrysanthemum, allspice, oregano, painting trees, camomile, , Vinegar, peony, ginger, canadian seaweed, western broadleaf tree, sage, mistletoe, creation, time, pollen, sperm, wenzhou citrus, tea tree, bayberry, Echinacea, Lavender, Rose, Rosemary, Leaf, Cedar, Giladard Balsam Trees, Ringworm, Chrysanthemum, Pineapple, Chrysanthemum , Alfalfa, alfalfa, licorice, spinach, and the like.

The blending amount of extract such as natural product is preferably about 0 to 0.5% by mass relative to the total mass of the liquid detergent composition.

The liquid detergent composition of the present invention preferably has a pH of 4 to 9 at 25 ° C, and more preferably a pH of 6 to 9. When the pH is in this range, the storage stability of the liquid detergent composition can be satisfactorily maintained.

The pH of the liquid detergent composition can be adjusted by adding a pH adjusting agent, if necessary. As the pH adjuster, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable in view of the stability of the component (D), as long as the effect of the present invention is not impaired.

The liquid detergent composition of the present invention is prepared by mixing the above components (A) to (D) and, if necessary, other components with water.

The mixing conditions are not particularly limited, but the pH (25 ° C) when the component (D) is added is preferably around 7. The temperature for adding the component (D) is preferably 40 占 폚 or lower. Further, when the component (D) is blended with a solution containing a predetermined amount of the component (A), there is a fear that the solution becomes coagulated and turbidity due to low water content. Therefore, it is preferable that the component (D) is previously mixed with an aqueous solution to which water (water) or sodium benzoate is added, and then mixed with other components.

Examples of the water include purified water, distilled water, ion-exchanged water, pure water, and highly pure water.

The water is not particularly limited, but is preferably 30 to 45% by mass, and more preferably 25 to 55% by mass based on the total mass of the liquid detergent composition, so long as the total amount of the liquid cleaning composition is 100% by mass.

The method of using the liquid detergent composition of the present invention is the same as the method of using the ordinary liquid detergent composition. That is, the liquid detergent composition of the present invention (hereinafter, may be referred to as the present invention) may be added to water together with the laundry at the time of washing, the method of directly applying the present invention to muddy or sebum A method in which the present invention is dissolved in water in advance to immerse the clothes, and the like. It is also preferable to apply the product of the present invention to a laundry, leave it properly, and then perform normal washing through a normal (normal) washing liquid. At that time, the amount of use of the present invention can be made substantially smaller than the amount of the conventional liquid detergent composition used.

As an embodiment of the liquid detergent of the present invention,

(A) at least one component selected from the group consisting of a nonionic surfactant, (B) an aminocarboxylic acid or a salt thereof, and a phosphonic acid or a salt thereof and (C) an? -Hydroxy-monocarboxylic acid or (D) an enzyme, and water, wherein the total amount of the liquid detergent,

The content of the component (A) is 40 to 70% by mass,

(B) is 0.1 to 5% by mass,

(C) is 0.1 to 5% by mass,

(D) is contained in an amount of 0.01 to 2% by mass, and

The water content is 30 to 45 mass%, and

And a liquid detergent in which the total amount of each of the above components does not exceed 100% by mass.

As another aspect of the liquid detergent of the present invention,

(A) at least one component selected from the group consisting of a nonionic surfactant, (B) an aminocarboxylic acid or a salt thereof, and a phosphonic acid or a salt thereof and (C) an? -Hydroxy-monocarboxylic acid or A salt thereof, (D) an enzyme, water, and other components, wherein, for the total mass of the liquid detergent,

The content of the component (A) is 40 to 70% by mass,

(B) is 0.1 to 5% by mass,

(C) is 0.1 to 5% by mass,

(D) is contained in an amount of 0.01 to 2% by mass, and

The water content is 30 to 45% by mass,

It is also possible to include other components as desired,

And a liquid detergent in which the total amount of each of the above components does not exceed 100% by mass.

As another aspect of the liquid detergent of the present invention,

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) at least one component selected from the group consisting of an amino carboxylic acid represented by the following formula (b1) or a salt thereof, and a phosphonic acid or a salt thereof;

(C) an? -Hydroxy-monocarboxylic acid represented by the following formula (c1) or a salt thereof;

(D) a liquid detergent containing at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and manzase.

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is a divalent linking group; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO, and is an integer of 0 to 6;

Wherein R ³ is - (CH ₂ ) _n -A; A is H, OH or COOM; M is H, Na, K, and NH ₄ or an alkanol amine; n is an integer from 0 to 5;

R-C (OH) (R ') - COOH ... (c1)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group having 2 to 6 carbon atoms, An ether group, an amino group which may have a substituent, or an amine derivative group; R 'represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group of 2 to 6 carbon atoms, an ether group of 2 to 6 carbon atoms , Or an amino group which may have a substituent, or an amine derivative group].

As another aspect of the liquid detergent of the present invention,

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) at least one component selected from the group consisting of an amino carboxylic acid represented by the following formula (b1) or a salt thereof, and a phosphonic acid or a salt thereof;

(C) an? -Hydroxy-monocarboxylic acid represented by the following formula (c1) or a salt thereof;

(D) at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and mannanase;

Liquid cleansing agents which contain other ingredients if desired:

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is a divalent linking group; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO, and is an integer of 0 to 6;

Wherein R ³ is - (CH ₂ ) _n -A; A is H, OH or COOM; M is H, Na, K, and NH ₄ or an alkanol amine; n is an integer from 0 to 5;

R-C (OH) (R ') - COOH ... (c1)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group having 2 to 6 carbon atoms, An ether group, an amino group which may have a substituent, or an amine derivative group; R 'represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group of 2 to 6 carbon atoms, an ether group of 2 to 6 carbon atoms , Or an amino group which may have a substituent, or an amine derivative group].

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) methylglycine diacetic acid or a salt thereof, ethylglycine diacetic acid or a salt thereof, nitriloacetic acid or a salt thereof, iminodipacic acid or a salt thereof, tetrasodium acid N, N-2 acetic acid, (Methylenephosphonic acid) or a salt thereof, ethylenediamine tetra (methylenephosphonic acid) or a salt thereof, diethylenetriamine penta (methylenephosphonic acid) or a salt thereof, A salt, and at least one component selected from the group consisting of 2-phosphono-1,2,4-butanetricarboxylic acid or a salt thereof;

(C) at least one component selected from the group consisting of glycolic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, mandelic acid, optical isomers thereof, and salts thereof;

(D) a liquid detergent containing at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and manzase.

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is -O-, -COO-, or -CONH-; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO and is an integer of 0 to 6]

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) methylglycine diacetic acid or a salt thereof, ethylglycine diacetic acid or a salt thereof, nitriloacetic acid or a salt thereof, iminodipacic acid or a salt thereof, tetrasodium acid N, N-2 acetic acid, (Methylenephosphonic acid) or a salt thereof, ethylenediamine tetra (methylenephosphonic acid) or a salt thereof, diethylenetriamine penta (methylenephosphonic acid) or a salt thereof, A salt, and at least one component selected from the group consisting of 2-phosphono-1,2,4-butanetricarboxylic acid or a salt thereof;

(C) at least one component selected from the group consisting of glycolic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, mandelic acid, optical isomers thereof, and salts thereof;

(D) at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and mannanase,

Liquid cleansing agents which contain other ingredients if desired:

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is -O-, -COO-, or -CONH-; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO and is an integer of 0 to 6]

As another aspect of the liquid detergent of the present invention,

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) at least one component selected from the group consisting of an amino carboxylic acid represented by the following formula (b1) or a salt thereof, and a phosphonic acid or a salt thereof;

(C) an? -Hydroxy-monocarboxylic acid represented by the following formula (c1) or a salt thereof;

(D) at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and mannanase;

1. A liquid detergent containing water, wherein, for the total mass of the liquid detergent,

The content of the component (A) is 40 to 70% by mass,

(B) is 0.1 to 5% by mass,

(C) is 0.1 to 5% by mass,

(D) is contained in an amount of 0.01 to 2% by mass, and

The water content is 30 to 45 mass%, and

And a total amount of each of the above components does not exceed 100% by mass.

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is a divalent linking group; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO, and is an integer of 0 to 6;

Wherein R ³ is - (CH ₂ ) _n -A; A is H, OH or COOM; M is H, Na, K, and NH ₄ or an alkanol amine; n is an integer from 0 to 5;

R-C (OH) (R ') - COOH ... (c1)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group having 2 to 6 carbon atoms, An ether group, an amino group which may have a substituent, or an amine derivative group; R 'represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group of 2 to 6 carbon atoms, an ether group of 2 to 6 carbon atoms , Or an amino group which may have a substituent, or an amine derivative group].

As another aspect of the liquid detergent of the present invention,

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) at least one component selected from the group consisting of an amino carboxylic acid represented by the following formula (b1) or a salt thereof, and a phosphonic acid or a salt thereof;

(C) an? -Hydroxy-monocarboxylic acid represented by the following formula (c1) or a salt thereof;

(D) at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and mannanase;

Water;

A liquid detergent containing other components as desired, wherein the total amount of the liquid detergent,

The content of the component (A) is 40 to 70% by mass,

(B) is 0.1 to 5% by mass,

(C) is 0.1 to 5% by mass,

(D) is contained in an amount of 0.01 to 2% by mass, and

The water content is 30 to 45 mass%, and

And a total amount of each of the above components does not exceed 100% by mass.

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is a divalent linking group; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO, and is an integer of 0 to 6;

Wherein R ³ is - (CH ₂ ) _n -A; A is H, OH or COOM; M is H, Na, K, and NH ₄ or an alkanol amine; n is an integer from 0 to 5;

R-C (OH) (R ') - COOH ... (c1)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group having 2 to 6 carbon atoms, An ether group, an amino group which may have a substituent, or an amine derivative group; R 'represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 10 carbon atoms which may have a substituent, a nitro group, an ester group of 2 to 6 carbon atoms, an ether group of 2 to 6 carbon atoms , Or an amino group which may have a substituent, or an amine derivative group].

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) methylglycine diacetic acid or a salt thereof, ethylglycine diacetic acid or a salt thereof, nitriloacetic acid or a salt thereof, iminodipacic acid or a salt thereof, tetrasodium acid N, N-2 acetic acid, (Methylenephosphonic acid) or a salt thereof, ethylenediamine tetra (methylenephosphonic acid) or a salt thereof, diethylenetriamine penta (methylenephosphonic acid) or a salt thereof, A salt, and at least one component selected from the group consisting of 2-phosphono-1,2,4-butanetricarboxylic acid or a salt thereof;

(C) at least one component selected from the group consisting of glycolic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, mandelic acid, optical isomers thereof, and salts thereof;

(D) at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and mannanase;

1. A liquid detergent containing water, wherein, for the total mass of the liquid detergent,

The content of the component (A) is 40 to 70% by mass,

(B) is 0.1 to 5% by mass,

(C) is 0.1 to 5% by mass,

(D) is contained in an amount of 0.01 to 2% by mass, and

The water content is 30 to 45 mass%, and

And a total amount of each of the above components does not exceed 100% by mass.

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is -O-, -COO-, or -CONH-; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO and is an integer of 0 to 6]

(A) a polyoxyalkylene type nonionic surfactant comprising a compound represented by the following formula (I);

(B) methylglycine diacetic acid or a salt thereof, ethylglycine diacetic acid or a salt thereof, nitriloacetic acid or a salt thereof, iminodipacic acid or a salt thereof, tetrasodium acid N, N-2 acetic acid, (Methylenephosphonic acid) or a salt thereof, ethylenediamine tetra (methylenephosphonic acid) or a salt thereof, diethylenetriamine penta (methylenephosphonic acid) or a salt thereof, A salt, and at least one component selected from the group consisting of 2-phosphono-1,2,4-butanetricarboxylic acid or a salt thereof;

(C) at least one component selected from the group consisting of glycolic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, mandelic acid, optical isomers thereof, and salts thereof;

(D) at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, and mannanase;

Water;

Liquid cleansing agents which contain other ingredients if desired:

R ¹ -X- (EO) _s (PO) _t -R ² (I)

Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms; -X- is -O-, -COO-, or -CONH-; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO is an ethylene oxide group; s represents an EO average addition mole number, and is an integer of 3 to 20; PO is a propylene oxide group; t represents an average addition mole number of PO and is an integer of 0 to 6]

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

In each of the examples described below, the pH was measured at 25 캜 using a pH meter (product name: HM-30G, manufactured by DOKAI KK).

The raw materials used in each example are shown below.

[Materials used]

As the component (A), the following reagents were used.

(A-1): a mixture of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ and C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) _m OCH _{3 in} a mass ratio of 8/2, m = Yield: 33% by mass.

(A-2): a mixture of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ and C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) _m OCH _{3 in} a mass ratio of 8/2, m = Yield: 65% by mass.

(A-3): C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ , m = average 15, elongation rate 33 mass%

_{(A-4): C 11} H 23 CO (OCH 2 CH 2) m OCH 3 , and _{C 13 H 27 CO (OCH 2} CH 2) m OCH 3 , and _{C 15 H 31 CO (OCH 2} CH 2) m OCH 3 M / z = 15, m / z 33% by mass;

(A-5): a nonionic surfactant having an average of 15 moles of ethylene oxide added to natural alcohol CO-1217 (trade name) manufactured by P & G.

(A-6): a nonionic surfactant having an average of 12 moles of ethylene oxide added to the natural alcohol CO-1217 (trade name) manufactured by P & G.

(A-7): A nonionic surfactant obtained by block addition of natural alcohol (C12 / C14 = 7/3) in the order of 8 moles of ethylene oxide, 2 moles of propylene oxide and 8 moles of ethylene oxide.

(A-8): trade name " Soputanol 0 ", Nippon Catalyst.

The elongation percentage of (A-1) to (A-4) was measured in the following sequence.

The distribution of the ethylene oxide adducts in which the number of added moles of ethylene oxide was different was measured under the following measurement conditions and the elongation percentage (% by mass) was calculated by the above formula (S).

[Conditions for measuring the distribution of ethylene oxide adduct by HPLC]

Apparatus: LC-6A (manufactured by Shimadzu Corporation),

Detector: SPD-10A,

Measured wavelength: 220 nm,

Column: Zorbax C8 (manufactured by Du Pont Co., Ltd.),

Mobile phase: acetonitrile / water = 60/40 (volume ratio),

Flow rate: 1 ml / min,

Temperature: 20 ° C

The above-mentioned (A-1) to (A-7) were synthesized in the following order.

(A-1):

Was synthesized in accordance with Example 1 of the embodiment described in JP-A-2000-144179.

Namely, alumina-magnesium hydroxide (trade name: Kyowaido 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O was calcined at 600 ° C. for 1 hour under a nitrogen atmosphere 2.2 g of a calcined hydrous alumina-magnesium (unmodified) catalyst obtained, 2.9 ml of a 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester were placed in a 4 liter autoclave, The catalyst was reformed. Subsequently, the interior of the autoclave was replaced with nitrogen, the temperature was raised, and 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 캜 and the pressure at 3 atm, and the reaction was carried out with stirring. Further, the reaction solution was cooled to 80 DEG C, and 159 g of water and 5 g of active white clay and diatomaceous earth were added as filtration aids, respectively, and then the catalyst was filtered off to obtain (A-1).

The amount of alkali added to the catalyst was adjusted so that the elongation percentage of (A-1) was 33% by mass.

(A-2):

(A-1) was obtained in the same manner as in the above (A-1) except that 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester were used and 1052 g of ethylene oxide was introduced and the amount of alkali added to the catalyst was adjusted to 65% (A-2) was prepared in the same manner as in the synthesis method.

(A-3):

In place of 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, 350 g of lauric acid methyl ester was used, 1079 g of ethylene oxide was introduced, and the amount of alkali added to the catalyst was adjusted to 33% by mass (A-3) was prepared in the same manner as the synthesis method of (A-1).

(A-4):

252 g of lauric acid methyl ester, 63 g of myristic acid methyl ester and 35 g of parumitic acid methyl ester were used and 1023 g of ethylene oxide was introduced and the amount of alkali added to the catalyst was adjusted to 33% by mass. (A-4) was prepared in the same manner as the synthesis method of (A-1).

(A-5):

224.4 g of a natural alcohol CO-1270 manufactured by P & G, and 2.0 g of a 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, dehydration was performed at a temperature of 100 占 폚 and a pressure of 2.0 kPa or lower for 30 minutes, and then the temperature was raised to 160 占 폚. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous state) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 캜 by using a blowing tube.

After completion of the addition of ethylene oxide, the reaction product was matured at a temperature of 180 DEG C and a pressure of 0.3 MPa or less for 30 minutes, and unreacted ethylene oxide was distilled off at 180 DEG C under a pressure of 6.0 kPa for 10 minutes.

Next, after the temperature was lowered to 100 ° C or lower, 70% p-toluenesulfonic acid was added to neutralize the reaction solution so that the pH of the 1% aqueous solution of the reaction product became about 7 to obtain (A-5).

(A-6):

(A-4) except that 224.4 g of a natural alcohol CO-1270 manufactured by P & G was used instead of the natural alcohol CO-1270 and 610.2 g of ethylene oxide was used.

(A-7):

224.4 g of a natural alcohol CO-1270 manufactured by P & G and 2.0 g of a 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the interior of the vessel was replaced with nitrogen. Next, dehydration was performed at a temperature of 100 占 폚 and a pressure of 2.0 kPa or lower for 30 minutes, and then the temperature was raised to 160 占 폚. While stirring the alcohol, 405 g of ethylene oxide (gaseous state) was slowly added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 캜 by using a blowing tube.

After completion of the addition of the ethylene oxide, the mixture was matured for 30 minutes at a temperature of 180 DEG C and a pressure of 0.3 MPa or lower. Then, 130 g of propylene oxide (gaseous state) was fed into the reactor using a blowing tube to adjust the addition rate While gradually adding thereto. After aging at a temperature of 180 DEG C and a pressure of 0.3 MPa or less for 30 minutes, 405 g of ethylene oxide was further reacted. After the aging, the unreacted ethylene oxide was distilled off. The temperature was then cooled to 100 DEG C or lower, and 70 wt% p-toluenesulfonic acid was added to neutralize the solution so that the pH of the 1 mass% -7).

As the component (B), the following reagents and compounds were used.

Methylglycine triacetate (MGDA): trade name "TRYLON M", manufactured by BASF.

Hydroxyethane diphosphonic acid (HEDP): manufactured by Lion Corporation, trade name " Periyox 115A ".

As the component (C), reagents and compounds shown below were used.

Sodium lactate: manufactured by KANTO CHEMICAL CO., LTD.

As the component (D), the following reagents and compounds were used.

coronase 48L: product name, Novogizer subject.

everlase 16L: product name, Novogizer theme.

As the other components, the following reagents were used.

LAS-H: straight chain alkylbenzenesulfonic acid, trade name, Lyfon LH-200, manufactured by Lion.

Monoethanolamine (MEA): Nippon Catalyst Co., Ltd.

Dibutylhydroxytoluene (BHT): manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER BHT-R".

Ethanol: manufactured by Japan Alcohol Sales Co., Ltd., product name " Specific alcohol 95 degree synthesis ".

Sodium benzoate: Doa synthetic agent, trade name "sodium benzoate".

Green No. 3 (coloring matter): manufactured by Kishi Hiraku Co., Ltd., "Green No. 3".

Calcium chloride: manufactured by KANTO CHEMICAL Co., Ltd., trade name "calcium chloride (limited edition)".

Flavor: The fragrance composition according to Tables 11 to 18 of JP-A-2002-146399.

Sodium hydroxide: manufactured by Tsuruomida Corporation.

Sulfuric acid: manufactured by Toho Zinc Co., Ltd.

≪ Examples 1 to 18, Comparative Examples 1 to 6 >

(Preparation of liquid detergent composition)

(A) of 95% ethanol and 1.0% by mass of monoethanolamine and the components and mass (% by mass) shown in Tables 1 and 2 were fed into a 500 ml beaker, and a magnet steerer Manufactured by MITAMURA KOGYO INC.) To dissolve these components. Thereafter, the component (B) (or the component (B ')) and the component (C) (or the component (C')) were added and purified water was added thereto so that the total amount was 96 mass parts. A proper amount of a pH adjuster (sodium hydroxide or sulfuric acid) was added so that the pH at 25 캜 was 7.0, and the component (D) diluted with twice the amount of water (or 35% aqueous sodium benzoate solution) Was added to 100 parts by mass of water to obtain a liquid detergent composition.

The obtained liquid detergent composition was evaluated as follows. The results are shown in Tables 1 and 2.

(Evaluation of enzyme stability (enzyme activity remaining ratio)) [

90 g of the liquid detergent composition of each example was placed in a transparent glass bottle (model number: PS-NO. 11 of a hole standard bottle), sealed with a plastic stopper, and then kept at 35 캜 and 4 캜 for 4 weeks. Subsequently, using the sample after storage, the enzyme activity was measured as follows.

(1 mol / l sodium hydroxide solution (1N), manufactured by KANTO CHEMICAL CO., LTD.), PH was adjusted to 10.5, and 0.05 M boric acid (boric acid (Manufactured by KANTO CHEMICAL CO., LTD.) To a concentration of 0.6% by mass of milk casein, and was used as a protease substrate.

1 g of the liquid detergent composition preserved at 35 ° C was diluted 25 times with 3 ° DH water (hard water) of calcium chloride (calcium chloride (special grade), Kanto Kagaku). 5 g of the above protease substrate was added to 1 g of the sample solution, stirred for 10 seconds by a vortex mixer, and then allowed to stand at 37 DEG C for 30 minutes to carry out an enzymatic reaction. Thereafter, 5 g of an aqueous solution of 0.44 M of TCA (trichloroacetic acid (special grade), manufactured by KANTO CHEMICAL CO., LTD.) As an enzyme reaction terminator was added, stirred for 10 seconds by a vortex mixer, and allowed to stand at 20 캜 for 30 minutes. The substrate was removed with a 0.45 mu m filter.

The absorbance (A) at a measurement wavelength of 275 nm of the filtrate was measured by using a spectrophotometer UV-160 when the concentration of the enzyme-decomposed substrate (tyrosine) present in the obtained filtrate was measured by a spectrophotometer Respectively.

In order to exclude the effect of absorption other than the target component, the absorbance (B) at 275 nm of the sample solution containing no protease substrate was measured.

As the initial value of the enzyme activity, the liquid detergent composition preserved at 4 캜 was diluted with the same procedure as described above, immediately reacted with the protease substrate, and after filtration, the absorbance (C) at 275 nm was determined. In order to exclude the effect of absorption other than the target component, the absorbance (D) at 275 nm of the sample solution containing no protease substrate was measured.

From the absorbances (A to D), the enzyme activity remaining ratio (%) was obtained by the following formula. The values of absorbance at 275 nm of each of the samples substituted for the following formulas were used except for the absorbance at 600 nm measured at the same time in order to exclude scattered light such as bubbles from the absorbance.

Enzyme activity remaining ratio (%) = {(absorbance A-absorbance B) / (absorbance C-absorbance D)} x 100

(Evaluation of appearance stability)

100 ml of the obtained liquid detergent composition was added to a clear glass bottle (block standard bottle PS-NO. 11), and the lid was closed and sealed. In this state, the sample was kept in a thermostatic chamber at 35 DEG C for one month, and then the appearance of the solution was visually observed and evaluated according to the following criteria.

○: No sediment was observed at the bottom of the bottle.

△: Though deposits were recognized at the bottom of the bottle, the precipitate dissolves (dissolves) due to slight shaking.

X: The sediment was recognized at the bottom of the bottle, and the sediment did not disappear even if lightly shaken.

(Evaluation of cleaning power)

Protein-contaminated cloth (protein-contaminated cloth) EMPA117 (manufactured by EMPA Testmaterial) was cut into 5 × 5 cm, and the result was regarded as "protein contaminated cloth". As the liquid detergent composition, a liquid detergent composition of each example immediately after preparation was used, and a liquid detergent composition (composition (B) component-free composition) having the same composition, except that the component (B) was not blended. Also, for each liquid cleaner composition, the liquid cleaner composition immediately after preparation was used. The wash liquor was prepared by stirring for 30 seconds in a ratio of 10 ml of the liquid detergent composition to 30 l of water.

Subsequently, 10 pieces of the protein-contaminated cloth, the cleansing mellitus cloth, and the washing liquid were put into the cleaning tester using a Terg-O-tometer (manufactured by UNITED STATES TESTING Co., Ltd.) Followed by washing at 120 rpm and 15 캜 for 10 minutes.

Thereafter, the resultant was transferred to a two-piece washing machine (manufactured by Mitsubishi Electric Corp., product number CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 liters of tap water (15 DEG C, 4? DH) for 3 minutes, .

With regard to the fine-definition contaminated cloth and the post-cleaned cloth, the reflectance was measured by a color difference meter (product name: SE200 type) manufactured by Nippon Denko KK and the cleaning rate (%) was calculated by the following formula.

(%) = (K / S of the contaminated cloth before cleaning - K / S of the contaminated cloth after cleaning) / (K / S of the contaminated cloth before washing)

However, K / S is a value obtained by the formula: (1-R / 100) ² / (2R / 100) and R is the reflectance (%) of the myoinfilter, contaminated cloth or cleaning cloth.

In addition, the cleaning rate (%) was calculated with respect to five contaminated cloths, and the average value was used to evaluate the relative detergency based on the following criteria.

Relative cleaning rate (%) = (cleaning rate of liquid detergent composition) / (cleaning rate of blended composition without ingredient (B)) × 100.

[Table 1]

[Table 2]

As shown in the results, the liquid detergent compositions of Examples 1 to 18 had good enzyme stability. From the result of the relative cleaning rate, it was confirmed that the component (B) had an effect of improving the enzyme performance. In addition, appearance stability was also good. The same results were obtained in Example 16 with everlase 16L instead of coronase48L as the enzyme.

On the other hand, the liquid detergent compositions of Comparative Examples 1 and 6, which did not contain the component (B), did not have an effect of improving the enzyme performance and had insufficient cleansing rate against protein contamination.

The liquid detergent composition of Comparative Example 2 did not contain the component (D) and thus had a good appearance stability but a low cleaning rate against protein contamination.

The liquid detergent composition of Comparative Example 3 which did not contain component (C) had poor enzyme stability.

In Comparative Example 4 in which EDTA was added instead of the component (B), the enzyme stability was poor.

In Comparative Example 5 in which sodium acetate was added instead of the component (C), the enzyme stability was poor.

[Industrial Availability]

INDUSTRIAL APPLICABILITY The present invention is extremely useful in industry because it can provide a liquid detergent composition containing a surfactant at a high concentration and having both excellent performance and stability of an enzyme.

Claims (3)

(A) 40% by mass or more of a nonionic surfactant,
(B) at least one component selected from the group consisting of an amino carboxylic acid or a salt thereof, and a phosphonic acid or a salt thereof,
(C) a-hydroxy-monocarboxylic acid or a salt thereof,
(D) an enzyme. The method according to claim 1,
Wherein the component (C) is at least one component selected from the group consisting of lactic acid and sodium lactate. 3. The method according to claim 1 or 2,
Wherein the component (D) comprises at least a protease.