JPWO2014109380A1 - Liquid cleaning agent - Google Patents

Abstract

(A) Component: selected from the group consisting of nonionic surfactant, (B) component: anionic surfactant, (C) component: protease, and (D) component: alkylene terephthalate unit and alkylene isophthalate unit. A water-soluble polymer having at least one unit and at least one unit selected from the group consisting of an oxyalkylene unit and a polyoxyalkylene unit, and component (E): an α-hydroxy-monocarboxylic acid and a salt thereof. At least one component selected from the group, and the total content of all the surfactants is 45% by mass or more based on the total mass of the liquid detergent, and component (B) The liquid cleaning agent has a content of 4% by mass or more based on the total mass of the liquid cleaning agent.

Description

The present invention relates to a liquid cleaning agent.
This application claims priority on January 11, 2013 based on Japanese Patent Application No. 2013-003982 for which it applied to Japan, and uses the content here.

Cleaning agents used for washing clothes and the like include a powder type and a liquid type. In recent years, the usage rate of liquid detergents has increased in that it is less likely to be dissolved and can be directly applied to clothing.
In the cleaning agent, a surfactant functions as a main cleaning component, and various components such as enzymes are blended. Nonionic surfactants are mainly used as surfactants for liquid detergents. On the other hand, the enzyme plays an important role as a component that exhibits various performances in a small amount.

However, the liquid detergent containing the enzyme has a problem that the storage stability of the enzyme is lower than that of the powder detergent, and the enzyme performance tends to deteriorate with time.
In recent years, so-called “compact type” cleaning agents containing a surfactant at a high concentration and having a small amount of use at one time have become mainstream in consideration of environmental aspects and convenience at the time of purchase. The compact type liquid cleaning agent has a small amount of water because the surfactant is contained in a high concentration. Therefore, when an enzyme is mix | blended with a compact type liquid detergent, precipitation and modification | denaturation of an enzyme are easy to produce and storage stability becomes still lower. In particular, when a protease is used as the enzyme, the performance of the enzyme tends to decrease due to autolysis.

In view of this, a liquid detergent containing a surfactant at a high concentration and having excellent enzyme storage stability has been proposed.
For example, Patent Document 1 discloses that 40% by mass or more of a nonionic surfactant, at least one component selected from the group consisting of aminocarboxylic acid or a salt thereof, and phosphonic acid or a salt thereof, and α-hydroxy-monocarboxylic acid Alternatively, a liquid detergent composition containing a salt thereof and an enzyme such as a protease is disclosed.

International Publication No. 2012/144601

  By the way, since a compact liquid detergent usually contains a nonionic surfactant in a high concentration, it easily gels. When an anionic surfactant is added, gelation of the liquid detergent is suppressed, but the storage stability of the enzyme is more likely to be reduced. Therefore, further improvement in the storage stability of the enzyme is required in a liquid detergent containing a high concentration of a surfactant containing an anionic surfactant.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent containing a surfactant at a high concentration and having excellent enzyme storage stability.

  As a result of intensive studies, the present inventors have found that the storage stability of the enzyme can be satisfactorily maintained even when the surfactant is contained in a high concentration by adding a soil release polymer, and the present invention has been completed. It was.

That is, this invention has the following aspects.
[1] The following (A) to (E) components are contained, and the total content of all the surfactants is 45% by mass or more with respect to the total mass of the liquid detergent, and the following (B) The liquid detergent whose content of a component is 4 mass% or more with respect to the total mass of a liquid detergent.
(A) component: Nonionic surfactant.
(B) component: Anionic surfactant.
(C) Component: Protease.
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. polymer. (E) Component: At least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof. [2] The liquid cleaning agent according to [1], further comprising the following component (F).
Component (F): at least one component selected from the group consisting of aminocarboxylic acids and salts thereof, and phosphonic acids and salts thereof.

That is, the present invention relates to the following.
[1 ′] component (A): a nonionic surfactant;
(B) component: an anionic surfactant;
(C) component: protease and
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. A polymer,
(E) component: containing at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof,
The total content of all the surfactants is 45% by mass or more based on the total mass of the liquid detergent, and
The liquid detergent whose content of the said (B) component is 4 mass% or more with respect to the total mass of a liquid detergent.
[2 ′] The liquid detergent according to [1], further comprising (F) component: at least one component selected from the group consisting of aminocarboxylic acid and its salt, and phosphonic acid and its salt.

  According to the present invention, it is possible to provide a liquid detergent containing a surfactant at a high concentration and having excellent enzyme storage stability.

Hereinafter, the present invention will be described in detail.
The liquid detergent of the present invention contains the following components (A) to (E). Moreover, it is preferable that the liquid cleaning agent of this invention further contains (F) component.

<(A) component>
The component (A) is a nonionic surfactant. Component (A) is a surfactant used for imparting detergency to the liquid detergent.
Although it does not specifically limit as (A) component, For example, alkylene oxide adducts, such as a polyoxyalkylene type nonionic surfactant, alkylphenol, a C8-C22 fatty acid, or a C8-C22 amine, polyoxyethylene polyoxy Propylene block copolymer, C10-20 fatty acid alkanolamine, C10-20 fatty acid alkanolamide, C10-20 polyhydric alcohol fatty acid ester or its alkylene oxide adduct, C10-20 polyvalent Alcohol fatty acid ether, C10-20 alkyl (or alkenyl) amine oxide, hydrogenated castor oil alkylene oxide adduct, sugar fatty acid ester, C10-20 N-alkyl polyhydroxy fatty acid amide, C8-18 The alkyl Glycosidic and the like. Any one of these components may be used alone, or two or more components may be used in combination.

Among the above, the component (A) is preferably a polyoxyalkylene type nonionic surfactant in terms of improving the viscosity and appearance stability of the liquid detergent.
Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (1) (hereinafter referred to as “compound (1)”).

R ¹ -X- (EO) _s (PO) _t -R ² (1)
[In formula (1), 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 carbon. EO is an ethylene oxide group; s represents an EO average repeat number (that is, an average added mole number of ethylene oxide), an integer of 3 to 20; PO is a propylene oxide group Yes; t represents the average number of repeating POs (that is, the average number of moles of propylene oxide added), and is an integer of 0-6. ]

In the formula (1), the carbon number of the hydrocarbon group ^{R 1} is from 8 to 22, preferably 10 to 18, 12 to 18 is more preferable. The hydrocarbon group may be linear or branched. Moreover, it may have an unsaturated bond and does not need to have it.
Examples of the -X- divalent linking group include -O-, -COO-, -CONH-, and the like.
The number of carbon atoms in the alkyl group in R ² is 1-6, 1-3 are preferred.
The number of carbon atoms of the alkenyl group in R ² is 2-6, preferably 2-3.
The compound (1) in which —X— is —O—, —COO— or —CONH— is a primary or secondary alcohol having 8 to 22 carbon atoms (that is, R ¹ —OH or (R ¹ ) _2. —CH—OH), a fatty acid having 8 to 22 carbon atoms (ie, R ¹ —COOH), or a fatty acid amide having 8 to 22 carbon atoms (ie, R ¹ —CONH) can be obtained as a raw material.

EO is an ethylene oxide group and PO is a propylene oxide group.
s and t represent the average number of repetitions (average number of added moles) of EO and PO, respectively.
s is an integer of 3-20, and an integer of 5-18 is preferable. If the average number of repetitions s of EO exceeds 20, the HLB value becomes too high, which is disadvantageous for sebum cleaning, and the cleaning function tends to be lowered. On the other hand, if the average number of repetitions s of EO is less than 3, the effect of preventing odor deterioration tends to be reduced.
t is an integer of 0 to 6, and an integer of 0 to 3 is preferable. When the average number of repetitions t of PO exceeds 6, the storage stability of the liquid detergent at a high temperature tends to decrease.
When t is 1 or more, that is, when compound (1) is an adduct to which both EO and PO are added, the addition method of EO and PO is not particularly limited, and may be, for example, random addition. A block may be added. As a block addition method, for example, a method of adding PO after adding EO; a method of adding EO after adding PO; a method of adding PO after adding EO, and further adding EO Is mentioned.
Here, the “average number of repetitions” means the number of moles of ethylene oxide or propylene oxide reacted with 1 mole of alcohol used.

The added mole number distribution of EO and PO is not particularly limited.
The added mole number distribution is likely to vary depending on the reaction method in producing the nonionic surfactant. For example, when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of added EO or PO is relatively wide. It tends to be. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the EO or PO addition mole number distribution tends to be a relatively narrow distribution.

As the compound (1), in particular, a compound in which —X— is —O— (alkyl (alkenyl) ether type surfactant); —X— is —COO—, and R ² has 1 to 6 carbon atoms. A compound (fatty acid alkyl (alkenyl) ester type surfactant) which is an alkyl group or an alkenyl group having 2 to 6 carbon atoms is preferred.
When -X- in the formula (1) is -O-, the carbon number of R ¹ is preferably 10-22, more preferably 10-20, and particularly preferably 10-18.
R ² in the case where —X— is —O— is preferably a hydrogen atom.
If the expression (1) in the -X- is -COO-, number of carbon atoms in ^{R 1} is preferably 9 to 21, 11 to 21 is more preferable.
R ² in the case where —X— is —COO— is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

Specific examples of the compound in which —X— is —O— or —COO— include
Made by Mitsubishi Chemical Co., Ltd .: Trade name Diadol (C13, C represents the number of carbons, the same applies hereinafter), manufactured by Shell: Trade name Neodol (C12 / C13), manufactured by Sasol: trade name Safol23 (C12 / C13), etc. Nonionic surfactant obtained by adding 12 mol equivalent or 15 mol equivalent ethylene oxide to the alcohol of
P & G: Nonionic surfactant obtained by adding 12 mol equivalent or 15 mol equivalent ethylene oxide to natural alcohols such as trade names CO-1214 and CO-1270;
Nonionic surfactant in which 7 mol equivalent of ethylene oxide is added to C13 alcohol obtained by subjecting C12 alkene obtained by trimerization of butene to oxo method (BASF, trade name: LutensolTO7);
Nonionic surfactant in which 7 mol equivalent of ethylene oxide is added to C10 alcohol obtained by subjecting pentanol to gerbet reaction (BASF, trade name: Lutensol XL70);
Nonionic surfactant in which 6 mole equivalent of ethylene oxide is added to C10 alcohol obtained by subjecting pentanol to gerbet reaction (BASF: trade name Lutensol XA60);
Nonionic surfactant added with 9 mol equivalent or 15 mol equivalent ethylene oxide to C12-14 secondary alcohol (Nippon Shokubai Co., Ltd .: trade name Softanol 90 or Softanol 150);
Nonionic surfactant obtained by adding 15 mol equivalent of ethylene oxide to coconut fatty acid methyl (lauric acid / myristic acid = 8/2) using an alkoxylation catalyst (polyoxyethylene coconut fatty acid methyl ester EO 15 mol); Etc.

As the compound (1), among the above, -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. Polyoxyethylene fatty acid methyl ester (hereinafter sometimes referred to as “MEE”) in which R ² is a methyl group is preferable.
By containing the polyoxyethylene fatty acid alkyl ester, the liquid detergent of the present invention is excellent in solubility in water and can easily obtain a high detergency. Further, even if a high concentration of surfactant is contained, it is difficult to cause a significant increase in viscosity (gelation), and a concentrated liquid cleaning agent having good fluidity can be obtained.
Polyoxyethylene fatty acid alkyl esters, especially MEE, are nonionic surfactants with poor molecular orientation in aqueous systems and unstable micelles. It is estimated that a large amount can be blended in the liquid detergent. Moreover, it is estimated that the solubility of the liquid detergent in water is improved by blending the polyoxyethylene fatty acid alkyl ester. Furthermore, the polyoxyethylene fatty acid alkyl ester blended at a high concentration is considered to contribute to the good fluidity of the liquid detergent. Therefore, when the polyoxyethylene fatty acid alkyl ester is poured into the water in the washing machine tub, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid becomes uniform quickly and comes into contact with the object to be washed at a predetermined concentration from the beginning of washing. Therefore, it is considered that high detergency can be obtained.

The narrow ratio indicating the proportion of the distribution of ethylene oxide adducts with different numbers of added moles of ethylene oxide is preferably 20% by mass or more based on the total mass of the polyoxyethylene fatty acid alkyl ester, and the upper limit is substantially It is preferable that it is 80 mass% with respect to the total mass of polyoxyethylene fatty-acid alkylester. That is, the narrow rate is preferably 20 to 80% by mass with respect to the total mass of the polyoxyethylene fatty acid alkyl ester. The narrow ratio is more preferably 20 to 50% by mass with respect to the total mass of the polyoxyethylene fatty acid alkyl ester, and the storage stability and solubility are improved, so that the total mass of the polyoxyethylene fatty acid alkyl ester is increased. More preferably, it is 30-45 mass%.
The higher the narrow rate, the better the cleaning power. Further, when the narrow ratio is 20% by mass or more, particularly 30% by mass or more, it becomes easy to obtain a liquid cleaning agent with less raw material odor of the surfactant. Furthermore, the detergency is also improved by increasing the desired components (the ethylene oxide adduct having the desired number of moles of added ethylene oxide). This is because, after the production of the polyoxyethylene fatty acid alkyl ester, the raw material fatty acid ester (compound in which s is 0), or an ethylene oxide adduct in which s in the general formula (1) as a by-product is 1 or 2 This is thought to be due to a decrease in
Of the compounds contained as impurities in the polyoxyethylene fatty acid alkyl ester, the total mass of the polyoxyethylene fatty acid alkyl 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 The ratio of the ester to the total mass (hereinafter, the ratio is expressed as “Y0-2”) is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less. When Y0-2 is 0.5% by mass or less, a liquid detergent with less raw material odor of the surfactant can be obtained.

In addition, the narrow rate of polyoxyalkylene type nonionic surfactants, such as polyoxyethylene fatty-acid alkylester, is a value calculated | required by following numerical formula (S).
In the formula (S), S _max represents the number of added moles of alkylene oxide (value of s + t) in the alkylene oxide adduct most present in the polyoxyalkylene type nonionic surfactant.
i represents the number of added moles of alkylene oxide.
Yi represents the ratio (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the polyoxyalkylene type nonionic surfactant to i based on the total amount of the polyoxyalkylene type nonionic surfactant.

The narrow rate can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester.
The production method of the polyoxyethylene fatty acid alkyl ester is not particularly limited. For example, a method of addition polymerization of ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP, A 2000-144179).
As a suitable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , surface-modified with a metal hydroxide or the like, A composite metal oxide catalyst such as magnesium oxide to which Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc. are added; and at least one compound selected from the group consisting of metal hydroxides and metal alkoxides. Examples thereof include a calcined hydrotalcite catalyst.
In the surface modification of the composite metal oxide catalyst, a mixing ratio of the composite metal oxide and at least one compound selected from the group consisting of a metal hydroxide and a metal alkoxide is used as a composite metal oxide. The proportion of at least one compound selected from the group consisting of a metal hydroxide and a metal alkoxide is preferably 0.5 to 10 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass. More preferred.

As the component (A), a single type of nonionic surfactant may be used alone, or a plurality of types of nonionic surfactants may be used in combination.
By blending the component (A) in a high amount, washing can be done with a small amount of use and the detergent container can be made compact. In such a case, the gelation region is small and high even at high concentrations. In terms of easy compounding, secondary alcohol ethoxylates in which ethylene oxide is added to secondary alcohols (for example, Softanol series manufactured by Nippon Shokubai Co., Ltd.) and MEE in which ethylene oxide is added to fatty acid methyl are preferable. Since these gelation regions are small even at high concentrations, gelation hardly occurs at the time of high blending.
These may be used in combination with a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol.
In particular, in the component (A), the blending ratio of the secondary alcohol ethoxylate or MEE to the primary alcohol ethoxylate (mass ratio; secondary alcohol ethoxylate or MEE / primary alcohol ethoxylate) Is preferably 3/7 to 10/0, more preferably 5/5 to 10/0, and still more preferably 7/3 to 10/0.

  (A) As for content of a component, 20 mass% or more is preferable with respect to the gross mass of a liquid detergent, 30-60 mass% is more preferable, 30-55 mass% is further more preferable, 35-50 mass% is Particularly preferred. If content of (A) component is 20 mass% or more with respect to the gross mass of a liquid detergent, the effect of this invention will become easy to be acquired. On the other hand, when the content of the component (A) is 60% by mass or less, more preferably 55% by mass or less with respect to the total mass of the liquid detergent, an increase in the viscosity of the liquid detergent at a low temperature is suppressed.

<(B) component>
The component (B) is an anionic surfactant. Component (B) is a surfactant used for imparting detergency to the liquid detergent. In particular, by using together with the component (A), gelation can be prevented by disturbing the crystallization of the component (A) even when the liquid detergent is left standing and the water is volatilized.

  The component (B) can be appropriately selected from known anionic surfactants. For example, linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched Alkyl sulfate sulfate salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; alkane sulfonate having an alkyl group; α-sulfo fatty acid ester salt; Examples of salts in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

Among these, as the linear alkylbenzene sulfonic acid or a salt thereof, a linear alkyl benzene sulfonic acid having 8 to 16 carbon atoms in a linear alkyl group or a salt thereof is preferable, and a linear alkyl benzene sulfonic acid having 10 to 14 carbon atoms or a salt thereof. The salt is particularly preferred.
As the α-olefin sulfonate, an α-olefin sulfonate having 10 to 20 carbon atoms is preferable.
As the alkyl sulfate ester salt, an alkyl sulfate ester salt having an alkyl group having 10 to 20 carbon atoms is preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide. The added alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt (that is, polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
As the alkane sulfonate, an alkane sulfonate having 10 to 20 carbon atoms in the alkyl group is preferable, and an alkane sulfonate having 14 to 17 carbon atoms is more preferable. Of these, alkane sulfonates (that is, secondary alkane sulfonates) in which the alkyl group is a secondary alkyl group are particularly preferred.
The α-sulfo fatty acid ester salt is preferably an α-sulfo fatty acid methyl ester salt having 10 to 20 carbon atoms in the fatty acid residue.
Among these, at least one selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate ester salt, α-olefin sulfonate salt, α-sulfo fatty acid methyl ester salt Particularly preferred are seed surfactants.

As the component (B), anionic surfactants other than those described above may be used. Examples of the other anionic surfactants include higher fatty acid salts having 10 to 20 carbon atoms, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylic acids. Carboxylic acid type anionic surfactants such as acid salts; phosphoric acid ester types such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts, glycerin fatty acid ester monophosphoric acid ester salts Anionic surfactants and the like are listed.
These anionic surfactants can be easily obtained on the market.
As the component (B), a single type of anionic surfactant may be used alone, or a plurality of types of anionic surfactants may be used in combination.

  (B) Content of a component is 4 mass% or more with respect to the total mass of a liquid detergent, 4-25 mass% is preferable, 4-20 mass% is more preferable, and 5-10 mass% is further. preferable. If content of (B) component exists in the said range, it will become easy to prevent gelatinization of a liquid detergent. Also, the low temperature stability of the liquid detergent is increased.

Moreover, it is preferable that mass ratio ((A) component / (B) component) of (A) component and (B) component is 0.8-15 in a liquid detergent, More preferably, it is 1.5-15. Especially preferably, it is 3.5-10.
The total content of all the surfactants (hereinafter referred to as “total surfactant amount”) is 45% by mass or more, preferably 50% by mass or more with respect to the total mass of the liquid detergent. It is. When the total amount of the surfactant is 45% by mass or more, high cleaning performance can be imparted to the liquid cleaning agent.
The total amount of the surfactant is preferably 80% by mass or less and 70% by mass or less with respect to the total mass of the liquid detergent in that the liquid detergent is less likely to be gelled and can maintain good stability. More preferably, it is more preferably 60% by mass or less.
That is, the total amount of the surfactant is preferably 45% by mass or more and 80% by mass or less, more preferably 45% by mass or more and 70% by mass or less, with respect to the total mass of the liquid detergent. The content is more preferably 50% by mass or more and 70% by mass or less, and particularly preferably 50% by mass or more and 60% by mass or less.
When the liquid detergent of the present invention contains an optional surfactant described later, the total surfactant amount means the sum of the components (A) and (B) and the optional surfactant. When the liquid detergent of the invention does not contain an optional surfactant, the total amount of the surfactant means the total content of the component (A) and the component (B).

<(C) component>
Component (C) is a protease. Component (C) is an enzyme used as a cleaning aid.
In the present invention, “enzyme” refers to an enzyme preparation.

The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease.
Specifically, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX, Everase Ultra 16L, Esperase 8L, Esperase 8L, Esperase 8L, Esperase 8L, and Esperase 8L, available from Novozymes as protease preparations. 5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; trade names Purefect L, Perfect OX, Properase L, etc. available from Genencor.

Component (C) includes, among others, the trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX, Everase Ultra 16L, Liquidase 2.5L, Liquase 2.5L, Liquat 2.5L, LiquidUl. 48L is preferred, and Everase 16L Type EX, Savinase 16L, and Coronase 48L are particularly preferred.
As the component (C), any one protease may be used alone, or two or more proteases may be used in combination.

The content of the component (C) is not particularly limited in terms of storage stability, but is preferably 0.01% by mass or more based on the total mass of the liquid detergent from the viewpoint of improving the cleaning performance, and 0.03 The mass% or more is more preferable. Further, from the viewpoint of inhibition of enzyme precipitation and performance saturation in a composition having a small amount of water, it is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.8% by mass or less based on the total mass of the liquid detergent. Is more preferable.
That is, the content of the component (C) is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, with respect to the total mass of the liquid detergent. 0.03% by mass or more and 1% by mass or less are more preferable, and 0.03% by mass or more and 0.8% by mass or less are particularly preferable.

<(D) component>
The component (D) is a water solution having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. Polymer.
The component (D) is a recontamination preventive agent (soil release polymer) used for imparting recontamination preventing property to the liquid detergent. The component (D) is a liquid detergent containing a high concentration of surfactant, particularly an anionic surfactant, in combination with the component (E) described later, and 4% by mass or more based on the total mass of the liquid detergent. In the liquid detergent contained in a high concentration of (C), there is an effect of maintaining the stability of the component (C).
In the present invention, “water-soluble” means that 10 g of this polymer is added to 1000 g of water under the condition of a water temperature of 40 ° C., and 12 times with a stirrer (1 L beaker having a thickness of 8 mm, a length of 50 mm, and a diameter of 12 cm). It means complete dissolution when stirred for a period of time (200 rpm).

  Among the at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units constituting the water-soluble polymer of component (D), these are hereinafter collectively referred to as “d1 units”. The terephthalate unit is a unit represented by the following general formula (2).

［Ｒ^３は低級アルキレン基である。］

[R ³ is a lower alkylene group. ]

R ³ has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.

Specific examples of alkylene terephthalate units include ethylene terephthalate units, n-propylene terephthalate units, isopropylene terephthalate units, n-butylene terephthalate units, isobutylene terephthalate units, sec-butylene terephthalate units, tert-butylene terephthalate units, and the like. . Of these, isopropylene terephthalate units are preferred.
Specifically, examples of R ³ include ethylene, n-propylene, isopropylene, n-butylene, isobutylene, and sec-butylene, and isopropylene is preferable.

  As the d1 unit, a single type of alkylene terephthalate unit may be used alone, or a plurality of types of alkylene terephthalate units may be used in combination.

  Among the d1 units constituting the water-soluble polymer, the alkylene isophthalate unit is a unit represented by the following general formula (3).

［Ｒ^４は低級アルキレン基である。］

[R ⁴ is a lower alkylene group. ]

R ⁴ has 1 to ⁴ carbon atoms, preferably 2 to 4 carbon atoms.

Specific examples of the alkylene isophthalate unit include an ethylene isophthalate unit, a propylene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, and a tert-butylene isophthalate unit. Of these, propylene isophthalate units are preferred.
Specifically, examples of R ⁴ include ethylene, propylene, n-butylene, sec-butylene, and tert-butylene, and propylene is preferred.

  As the d1 unit, a single type of alkylene isophthalate unit may be used alone, or a plurality of types of alkylene isophthalate units may be used in combination.

  As the d1 unit, a unit selected from the alkylene terephthalate unit and the alkylene isophthalate unit can be used alone or in combination of two or more kinds. That is, the d1 unit may have only an alkylene terephthalate unit, may have only an alkylene isophthalate unit, or an alkylene terephthalate unit and an alkylene isophthalate unit may be mixed.

  The oxyalkylene unit and polyoxyalkylene unit (hereinafter also referred to as “d2 unit”) constituting the water-soluble polymer of component (D) are units represented by the following general formula (4).

_{^{- (R 5 O) u -}} ··· (4)
^{[R 5} is a lower alkylene group, u represents an average repeating number of ^{R 5} O, is an integer of 1 to 100. ]

R ⁵ has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
In the formula (4), when u is 1, it becomes an oxyalkylene unit, and when u is 2 or more, it becomes a polyoxyalkylene unit. u is an integer of 1 to 100, preferably an integer of 1 to 80, particularly preferably an integer of 1 to 50.

Specific examples of the d2 unit include an oxyethylene unit and a polyoxyethylene unit; an oxypropylene unit and a polyoxypropylene unit; a polyoxyethylene polyoxypropylene unit, among which an oxyethylene unit and a polyoxyethylene unit are included. preferable.
As the d2 unit, a unit selected from the above oxyalkylene units and polyoxyalkylene units can be used alone or in combination of two or more kinds. That is, the d2 unit may have only an oxyalkylene unit, may have only a polyoxyalkylene unit, or may contain a mixture of oxyalkylene units and polyoxyalkylene units.

The component (D) is preferably a polymer compound in which the above-mentioned d1 unit and d2 unit are polymerized randomly or in blocks, and particularly preferably a polymer compound polymerized in blocks.
The component (D) may contain units other than the above-mentioned d1 unit and d2 unit (for example, a unit derived from a polymerization initiator, a polymerization terminator or the like, or other copolymerizable unit). In that case, it is preferable that the sum total of d1 unit and d2 unit is 80 mol% or more of all the units which comprise (D) component, and it is more preferable that it is 90 mol% or more.

  Specific examples suitable for the component (D) include compounds represented by the following general formula (5) or the following general formula (6).

［式中、Ａ^１及びＢ^１はそれぞれ独立して、水素原子又はメチル基であり；Ｒ^６及びＲ^７はそれぞれ独立して、炭素数２〜４のアルキレン基であり；ｘ^１は０〜１０であり、ｙ^１はそれぞれ独立して１〜１００である。］

Wherein, ^{A 1} and ^{B 1} are each independently hydrogen atom or methyl group; ^{R 6} and ^{R 7} each independently, an alkylene group having 2 to 4 carbon atoms; ^{x 1} is 0 And y ¹ is independently 1 to 100. ]

In formula (5), A ¹ and B ¹ are each independently a hydrogen atom or a methyl group, preferably both a methyl group.
R ⁶ and R ⁷ are each independently an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.
x ¹ is 0-10, preferably 0.5 to 5, particularly preferably from 0.5 to 2.5.
y ¹ is 1 to 100 independently, preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, particularly preferably from 20 to 30.

［式中、Ａ^２及びＢ^２はそれぞれ独立して、水素原子又はメチル基であり；Ｒ^８及びＲ^９はそれぞれ独立して、炭素数２〜４のアルキレン基であり；ｘ^２は０〜１０であり；ｙ^２はそれぞれ独立して、１〜１００である。］

Wherein, ^{A 2} and ^{B 2} are each independently a hydrogen atom or a methyl group; ^{R 8} and ^{R 9} are each independently an alkylene group having 2 to 4 carbon atoms; ^{x 2} is 0 And y ² is independently 1 to 100. ]

In formula (6), A ² and B ² are each independently a hydrogen atom or a methyl group, preferably both a methyl group.
R ⁸ and R ⁹ are each independently an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.
x ² is 0 to 10, preferably from 0.5 to 5, particularly preferably from 0.5 to 2.5.
y ² are each independently 1 to 100, preferably from 1 to 80, more preferably from 11 to 50, still more preferably 10 to 50, particularly preferably from 20 to 30.

In the formula (5), the ratio between x ¹ and y ¹ is preferably such that x ¹ : y ¹ is 1: 5 to 1:20, more preferably 1: 8 to 1:18.
Further, in the equation (6), the ratio between ^{x 2} and ^{y 2 is,} x 2: ^{y 2} is 1: 5 to 1: is preferably 20, 1: 8 to 1: and more preferably 18 .
x ¹ and the ratio of y ^1, and if the ratio is above the range of the x ² and y ^2, soil release performance can be sufficiently exhibited, and improved solubility in water.

(D) It is preferable that the mass mean molecular weights of a component are 500-10000. If the mass average molecular weight is within the above range, the water dispersibility is improved, the water absorption improvement effect of hydrophobic fibers (especially polyester) is sufficiently exhibited, and the liquid detergent has a good liquid appearance. Become. The lower limit of the mass average molecular weight is more preferably 800, and particularly preferably 1000. On the other hand, the upper limit of the mass average molecular weight is more preferably 9000, and particularly preferably 8000. Therefore, the mass average molecular weight of the component (D) is more preferably 800 to 9000, and particularly preferably 1000 to 8000.
The weight average molecular weight of the component (D) refers to a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent, using PEG (polyethylene glycol) as a calibration curve.

  The component (D) can be easily obtained on the market. Also, synthesis methods disclosed in literatures: Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948), Journal of Polymer Science, Vol. 8, pages 1 to 22 (1951), JP It can be produced by the method described in JP-A-61-218699.

  Specific examples of the component (D) include trade name: TexCare SRN-100 (manufactured by Clariant Japan, mass average molecular weight: 2000 to 3000), trade name: TexCare SRN-300 (manufactured by Clariant Japan, mass average molecular weight: 7000). ), Trade name: Repel-O-Tex Crystal (Made by Rhodia, mass average molecular weight: undecided), product name: Repel-O-Tex QCL (Made by Rhodia, mass average molecular weight: undecided) Can be mentioned. Among these, TexCare SRN-100 is preferable because of its high solubility in water and little reduction in cleaning performance after storage. Particularly preferred are 70 mass% aqueous solutions of TexCare SRN-100, and commercially available components as trade names: TexCare SRN-170 and TexCare SRN-170C (manufactured by Clariant Japan) can be used.

  The content of the component (D) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, and particularly preferably 0.5 to 1% by mass with respect to the total mass of the liquid detergent. If content of (D) component is 0.1 mass% or more with respect to the total mass of a liquid detergent, the storage stability of an enzyme, especially (C) component will improve more. On the other hand, when the content of the component (D) is 5% by mass or less with respect to the total mass of the liquid detergent, the stability of the appearance of the liquid detergent can be favorably maintained.

<(E) component>
The component (E) is at least one component selected from the group consisting of α-hydroxy-monocarboxylic acids and salts thereof. The component (E) is used for the purpose of enhancing the storage stability of the component (C) when used in combination with the component (D).

  Examples of the α-hydroxy-monocarboxylic acid include compounds represented by the following general formula (7).

R ¹⁰ -C (OH) (R ¹¹ ) -COOH (7)
[Wherein, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 10 carbon atoms. An aryl group, a nitro group, an ester group having 2 to 6 carbon atoms, an ether group having 2 to 6 carbon atoms, an amino group which may have a substituent, or an amine derivative group. ]

Examples of the substituent that the alkyl group or aryl group in R ¹⁰ and R ¹¹ may have 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, and a hydroxyl group. , An ester group having 2 to 6 carbon atoms, an ether group having 2 to 6 carbon atoms, an optionally substituted amino group, an amine derivative group, an amide group, an amide derivative group, a halogen atom, and the like.
Examples of the substituent that the amino group in R ¹⁰ and R ¹¹ 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 α-hydroxy-monocarboxylic acid include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; alkanolamine salts such as ammonium salt and ethanolamine. .

The component (E) 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; mandelic acid, lactic acid And at least one component selected from the group consisting of salts thereof and more preferred; at least one component selected from the group consisting of lactic acid and salts thereof is particularly preferred. As the lactate, sodium lactate is preferred.
As the component (E), any one component may be used alone, or two or more components may be used in combination.

(E) 0.1-5 mass% is preferable with respect to the total mass of a liquid detergent, as for content of a component, 0.15-2 mass% is more preferable, 0.2-1.5 mass% is further preferable. If content of (E) component is in the said range, (E) component will fully adsorb | suck to the surface of (C) component, and the stability of (C) component in a formulation can be improved more.
When the content of the component (E) is less than 0.1% by mass with respect to the total mass of the liquid detergent, the stabilizing effect of the component (C) may be insufficient. On the other hand, when the content of the component (E) exceeds 5% by mass with respect to the total mass of the liquid detergent, there is a possibility of causing precipitation when formulated.

Moreover, as a compounding which can expect the improvement effect of the storage stability of (C) component, mass ratio ((D) component / (E) component) of (D) component and (E) component is 0.02-50. It is preferable that it is 0.16, More preferably, it is 0.16-6, Most preferably, it is 0.5-2.
Furthermore, mass ratio ((C) component / (D) component + (E) component) of (C) component and the sum total of content of (D) component and (E) component is 0.001-10. More preferably, it is 0.006-1.5, Most preferably, it is 0.012-1.1.

<(F) component>
The component (F) is at least one component selected from the group consisting of aminocarboxylic acids and salts thereof, and phosphonic acids and salts thereof.
By blending the component (F), the performance of the component (C) can be improved without impairing the stability of the component (C). Thereby, the cleaning performance (for example, the cleaning performance for protein stains) contributed by the component (C) is also improved.

The aminocarboxylic acid is preferably a polycarboxylic acid containing a plurality of carboxy groups. 2-5 are preferable and, as for the number of the carboxy groups in one molecule, 2 or 3 is more preferable.
Examples of aminocarboxylic acid salts include sodium salts, potassium salts, ammonium salts, and alkanolamine salts such as ethanolamine.

  As the aminocarboxylic acid or a salt thereof, a compound represented by the following general formula (8) is preferable.

［式中、Ｒ^１２は−（ＣＨ_２）_ｎ−Ｚであり；ＺはＨ、ＯＨ又はＣＯＯＭであり；ＭはＨ、Ｎａ、Ｋ、ＮＨ_４又はアルカノールアミンであり；ｎは０〜５の整数である。］

[Wherein R ¹² is — (CH ₂ ) _n —Z; Z is H, OH or COOM; M is H, Na, K, NH ₄ or alkanolamine; n is 0-5. It is an integer. ]

In the formula (8), R ¹² is — (CH ₂ ) _n —Z, Z is H, OH or COOM, M is H, Na, K, NH ₄ or alkanolamine, and n is 0 to 0 It is an integer of 5.

  Specific examples of aminocarboxylic acid or a salt thereof include methylglycine diacetic acid or a salt thereof such as trisodium methylglycine diacetate (MGDA), ethylglycine diacetic acid or a salt thereof such as trisodium ethylglycine diacetate, nitrilotriacetic acid Or a salt thereof, iminodisuccinic acid or a salt thereof, aspartic acid-N, N-tetraacetic acid tetrasodium, serine diacetic acid trisodium, glutamic acid diacetic acid tetrasodium, and the like. Among these, methyl glycine diacetate or a salt thereof, ethyl glycine diacetate or a salt thereof are preferable, and trisodium methyl glycine diacetate (MGDA) is particularly preferable.

Examples of phosphonic acid include hydroxyphosphonic acid such as 1-hydroxyethane-1,1-diphosphonic acid << CH ₃ C (OH) [PO (OH) ₂ ] ₂ >> (abbreviation: HEDP), aminotri (methylenephosphonic acid) << N _{[CH 2} PO _(OH) 2] ₃ "(abbreviation: ATMP), ethylenediaminetetra (methylenephosphonic _{acid)" N 2 (CH 2)} 2 _{[CH 2} PO _(OH) 2] ₄ ", diethylenetriamine 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 phosphonic acid salts include sodium salts, potassium salts, ammonium salts, and alkanolamine salts such as ethanolamine.
As the phosphonic acid or a salt thereof, among the above, hydroxyphosphonic acid is preferable, and HEDP is particularly preferable.

As the component (F), any one component may be used alone, or two or more components may be used in combination.
(F) 0.1-5 mass% is preferable with respect to the total mass of a liquid detergent, as for content of a component, 0.15-2 mass% is more preferable, 0.2-1.5 mass% is further preferable. If content of (F) component exists in the said range, the activity of an enzyme ((C) component or the arbitrary enzyme mentioned later) can fully be raised. In addition, the stability (precipitation, etc.) of the preparation over time can be improved. The reason why the activity of the enzyme is improved is not clear in detail, but it is considered that it acts on the active center of the enzyme during washing and improves its catalytic action.
When the content of the component (F) is less than 0.1% by mass with respect to the total mass of the liquid detergent, the enzyme performance improving effect may be insufficient. On the other hand, if the content of the component (F) exceeds 5% by mass with respect to the total mass of the liquid detergent, precipitation may occur when it is formulated.
Moreover, it is preferable that mass ratio ((D) component / (F) component) of (D) component and (F) component is 0.02-50, More preferably, it is 0.25-20, Especially Preferably it is 0.3-5.

<Water>
The liquid cleaning agent of the present invention is prepared by mixing the above components (A) to (E), and optionally the component (F) and optional components described later in water.
Examples of water include purified water, distilled water, ion exchange water, pure water, and ultrapure water.
Water is not particularly limited as long as the total amount of the liquid cleaning agent is 100% by mass, but is preferably 15 to 55% by mass and more preferably 30 to 45% by mass with respect to the total mass of the liquid cleaning agent. preferable.

<Optional component>
The liquid cleaning agent of the present invention, if necessary, within the range not impairing the effects of the present invention, the above component (A), component (B), component (C), component (D), component (E) and ( You may contain other components other than F) component. As said other component, the component normally used for a liquid detergent can be mix | blended, For example, the component shown below is mentioned.

(Water-miscible organic solvent)
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 and tetraethylene glycol. And 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, polyglycols such as dipropylene glycol, and alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether.
The content of the water-miscible organic solvent is preferably 0.1 to 15% by mass with respect to the total mass of the liquid detergent.

(Optional surfactant)
The optional surfactant may be any surfactant except the component (A) and the component (B), and examples thereof include a cationic surfactant and an amphoteric surfactant.
The content of the optional surfactant is preferably 10% by mass or less with respect to the total mass of the liquid detergent.

Examples of the cationic surfactant include alkyl trimethyl ammonium salts having 4 to 22 carbon atoms, dialkyl dimethyl ammonium salts having 4 to 22 carbon atoms, alkyl benzyl dimethyl ammonium salts having 10 to 22 carbon atoms, and alkyl pyridiniums having 6 to 22 carbon atoms. Salt cationic surfactants and the like.
Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine. Moreover, benzalkonium chloride, didecyldimethylammonium chloride, etc. are mentioned.

  Examples of amphoteric surfactants include alkyl betaine type having 4 to 22 carbon atoms, alkylamido betaine type having 4 to 22 carbon atoms, imidazoline type, alkylaminosulfone type having 4 to 22 carbon atoms, and alkyl having 4 to 22 carbon atoms. Examples thereof include aminocarboxylic acid types, alkyl amide carboxylic acid types having 4 to 22 carbon atoms, amide amino acid types, and phosphoric acid type amphoteric surfactants.

(Thickener and solubilizer)
Examples of the thinning agent and the solubilizer include aromatic sulfonic acid or a salt thereof, specifically, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate. Xylene sulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate.
Examples of the aromatic sulfonic acid salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, and alkanolamine salt.
Any of these aromatic sulfonic acids or salts thereof may be used alone, or two or more components may be used in combination.
The content of the thinning agent and the solubilizer is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent. If content of a viscosity reducing agent and a solubilizer is in the said range, the production | generation suppression effect of the membrane | film | coat formed when a liquid detergent will gelatinize on the liquid surface of a liquid detergent improves.

(Alkaline agent)
Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine and the like. The alkali agent can be used by mixing one or more components.
As content of an alkaline agent, 0.5-5 mass% is preferable with respect to the total mass of a liquid detergent.

(Optional enzyme)
Examples of the enzyme (arbitrary enzyme) other than the component (C) include cellulase, amylase, lipase, mannanase and the like.
The content of the optional enzyme is preferably 0.01 to 1.0% by mass with respect to the total mass of the liquid detergent.

(Metal ion scavenger)
Examples of the metal ion scavenger (chelating agent) other than the component (F) include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
The content of the metal ion scavenger (excluding the component (F)) is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent.

(Antioxidant)
The antioxidant is not particularly limited, but is preferably a phenolic antioxidant because of its good detergency and liquid stability; monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole, 2, 2'-methylenebis (bisphenol-based antioxidants such as 4-methyl-6-t-butylphenol and polymer-type phenolic antioxidants such as dl-α-tocopherol are more preferred; monophenolic antioxidants and polymers More preferred are type phenolic antioxidants.
Of the monophenol antioxidants, dibutylhydroxytoluene is particularly preferred.
Among the polymer type phenolic antioxidants, dl-α-tocopherol is particularly preferable.
As the antioxidant, any one component may be used alone, or two or more components may be used in combination.
As for content of antioxidant, 0.01-2 mass% is preferable with respect to the total mass of a liquid detergent.

(Preservative)
Examples of the preservative include Rohm and Haas: trade name Kaison CG.
The content of the preservative is preferably 0.001 to 1% by mass with respect to the total mass of the liquid detergent.

(Other)
The liquid detergent of the present invention may contain benzoic acid or a salt thereof (also effective as a preservative) for the purpose of improving storage stability. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
0.1-5 mass% is preferable with respect to the total mass of a liquid detergent, and, as for content of benzoic acid or its salt, 0.15-2.0 mass% is more preferable.

In addition, the liquid detergent of the present invention contains boric acid, borax, formic acid or a salt thereof; calcium salts such as calcium chloride and calcium sulfate for the purpose of enzyme stabilization with respect to the total mass of the liquid detergent. You may contain 01-2 mass%.
The liquid detergent of the present invention contains 0.01 to 5% by mass of silicone such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone for the purpose of improving the texture with respect to the total mass of the liquid detergent. May be.
Further, the liquid detergent of the present invention contains 0.01 to 1% by mass of a fluorescent whitening agent such as a distyryl biphenyl type for the purpose of improving the whiteness of white clothing with respect to the total mass of the liquid detergent. May be.
Moreover, the liquid detergent of the present invention is 0.01 to 2 masses of the anti-contamination agent and the anti-contamination agent such as polyvinylpyrrolidone and carboxymethylcellulose for the purpose of preventing the recontamination with respect to the total mass of the liquid detergent. % May be contained.
Moreover, the liquid cleaning agent of this invention may contain a pearl agent etc.

Moreover, the liquid detergent of the present invention may contain a flavoring agent, a coloring agent, an emulsifying agent, an extract such as a natural product, etc. for the purpose of improving the added value of the product.
As a flavoring agent, the fragrance | flavor composition A, B, C, D etc. of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 can be used as a typical example. The content of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent.

  General-purpose dyes 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, Turquoise P-GR (all trade names) Is mentioned. The content of the colorant is preferably about 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent.

  Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (manufactured by Syden Chemical Co., Ltd .: trade name Cybinol RPX-196 PE-3, solid content 40% by mass) and the like. The content of the emulsion is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.

Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamoki Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plant extracts such as St. John's Wort.
The content of extracts such as natural products is preferably about 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.

<Physical properties>
The liquid detergent of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 6 to 9. If pH is in the said range, the storage stability of a liquid detergent can be maintained favorable.
In the present specification, “pH at 25 ° C.” means a pH value in the range defined in the present specification when corrected to a pH value at 25 ° C. even if the pH value is outside the range defined in the present specification. As long as they fall within the scope of the present invention.
The pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired. For example, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine (monoethanolamine, etc.), etc. It is preferable from the aspect.

<Manufacturing method>
The liquid detergent of the present invention is prepared by mixing the above components (A) to (E) and, if necessary, the component (F) and optional components in water.
The mixing conditions are not particularly limited, but the pH (25 ° C.) when adding the component (C) is preferably around 7. Moreover, as for the temperature at the time of adding (C) component, 20 to 40 degreeC is preferable.
Moreover, when (C) component is mix | blended with the solution containing (A) component predetermined amount, since there is little water | moisture content, there exists a possibility that it may aggregate and turbidity may arise. Accordingly, the component (C) is preferably mixed with water, the component (E) or an aqueous solution to which sodium benzoate or the like is added in advance, and then mixed with other components.

<How to use>
The method for using the liquid detergent of the present invention may be the same as the method for using a normal liquid detergent. That is, the liquid detergent of the present invention (hereinafter sometimes referred to as the present product) is poured into water together with the laundry during washing, the method of directly applying the present product to mud soil or sebum soil, The method etc. which dissolve | melt an invention product in water beforehand and immerse clothing are mentioned. Also preferred is a method in which the product of the present invention is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. In that case, the usage-amount of this invention product can be made substantially smaller than the usage-amount of the conventional liquid detergent.

<Effect>
Since the liquid detergent of the present invention described above contains the components (A) to (E), the storage stability of the enzyme is excellent even when the surfactant is contained in a high concentration. Moreover, since the liquid detergent of the present invention uses the nonionic surfactant (A) component and the anionic surfactant (B) component in combination, the gel can be used even if the surfactant concentration is high. It is hard to become.

As other aspects of the liquid detergent of the present invention,
(A) component: nonionic surfactant,
(B) component: an anionic surfactant;
(C) component: protease and
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. A polymer,
(E) component: at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof;
(F) component: at least one component selected from the group consisting of aminocarboxylic acid and its salt, and phosphonic acid and its salt;
Containing water,
The total content of all the surfactants is 45% by mass or more and 60% by mass or less with respect to the total mass of the liquid detergent, and
The liquid detergent whose content of the said (B) component is 4 mass% or more with respect to the total mass of a liquid detergent.

As other aspects of the liquid detergent of the present invention,
(A) component: nonionic surfactant,
(B) component: an anionic surfactant;
(C) component: protease and
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. A polymer,
(E) component: at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof;
(F) component: at least one component selected from the group consisting of aminocarboxylic acid and its salt, and phosphonic acid and its salt;
Optionally with other ingredients,
Containing water,
The total content of all the surfactants is 45% by mass or more and 60% by mass or less with respect to the total mass of the liquid detergent, and
The liquid detergent whose content of the said (B) component is 4 mass% or more with respect to the total mass of a liquid detergent.

(A) component: nonionic surfactant,
(B) component: an anionic surfactant;
(C) component: protease and
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. A polymer,
(E) component: at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof;
A liquid detergent containing water,
For the total mass of the liquid detergent,
The component (A) is 20 to 60% by mass,
The component (B) is 4 to 25% by mass,
The component (C) is 0.01 to 2% by mass,
The component (D) is 0.1 to 5% by mass,
The component (E) is 0.1 to 5% by mass,
The water is 15 to 55% by mass, and the total amount of the respective components does not exceed 100% by mass, and the total content of all the surfactants is based on the total mass of the liquid detergent, Examples thereof include a liquid cleaning agent of 45% by mass or more and 60% by mass or less.

(A) component: nonionic surfactant,
(B) component: an anionic surfactant;
(C) component: protease and
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. A polymer,
(E) component: at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof;
(F) component: at least one component selected from the group consisting of aminocarboxylic acid and its salt, and phosphonic acid and its salt;
Optionally with other ingredients,
A liquid detergent containing water,
For the total mass of the liquid detergent,
The component (A) is 20 to 60% by mass,
The component (B) is 4 to 25% by mass,
The component (C) is 0.01 to 2% by mass,
The component (D) is 0.1 to 5% by mass,
The component (E) is 0.1 to 5% by mass,
The component (F) is 0.1 to 5% by mass,
The water is 15 to 55% by mass, and the total amount of the respective components does not exceed 100% by mass, and the total content of all the surfactants is based on the total mass of the liquid detergent, Examples thereof include a liquid cleaning agent of 45% by mass or more and 60% by mass or less.

［Ｒ^３は低級アルキレン基である。］

［Ｒ^４は低級アルキレン基である。］
−（Ｒ^５Ｏ）_ｕ− ・・・（４）
［Ｒ^５は低級アルキレン基であり、ｕはＲ^５Ｏの平均繰り返し数を表し、１〜１００の整数である。］；
（Ｅ）成分：、下記一般式（７）で表されるα−ヒドロキシ−モノカルボン酸及びその塩からなる群から選択される少なくとも１つの成分と：
Ｒ^１０−Ｃ（ＯＨ）（Ｒ^１１）−ＣＯＯＨ ・・・（７）
［式中、Ｒ^１０及びＲ^１１はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数６〜１０のアリール基、ニトロ基、炭素数２〜６のエステル基、炭素数２〜６のエーテル基、置換基を有していてもよいアミノ基、又はアミン誘導体基である。］；
（Ｆ）成分：下記一般式（８）で表されるアミノカルボン酸及びその塩、ならびにヒドロキシホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、及び２−ホスホノ−１，２，４−ブタントリカルボン酸及びその塩からなる群より選ばれる少なくとも１つの成分と：

［式中、Ｒ^１２は−（ＣＨ_２）_ｎ−Ｚであり；ＺはＨ、ＯＨ又はＣＯＯＭであり；ＭはＨ、Ｎａ、Ｋ、ＮＨ_４又はアルカノールアミンであり；ｎは０〜５の整数である。］；
水と、を含有し、
全ての界面活性剤の含有量の合計が、液体洗浄剤の総質量に対して、４５質量％以上、６０質量％以下であり、かつ、
前記（Ｂ）成分の含有量が、液体洗浄剤の総質量に対して、４質量％以上である、液体洗浄剤。As other aspects of the liquid detergent of the present invention,
Component (A): a nonionic surfactant containing a compound represented by the following general formula (1):
R ¹ -X- (EO) _s (PO) _t -R ² (1)
[In formula (1), 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 carbon. EO is an ethylene oxide group; s represents an EO average repeat number (that is, an average added mole number of ethylene oxide), an integer of 3 to 20; PO is a propylene oxide group Yes; t represents the average number of repeating POs (that is, the average number of moles of propylene oxide added), and is an integer of 0-6. ];
Component (B): at least one anionic surfactant selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate ;
(C) component: a protease having serine, histidine, and aspartic acid in the molecule;
Component (D): at least one unit selected from the group consisting of an alkylene terephthalate unit represented by the following general formula (2) and an alkylene isophthalate unit represented by the following general formula (3), and the following general formula (4) A water-soluble polymer having at least one unit selected from the group consisting of units represented by:

[R ³ is a lower alkylene group. ]

[R ⁴ is a lower alkylene group. ]
_{^{- (R 5 O) u -}} ··· (4)
^{[R 5} is a lower alkylene group, u represents an average repeating number of ^{R 5} O, is an integer of 1 to 100. ];
(E) component: and at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid represented by the following general formula (7) and a salt thereof:
R ¹⁰ -C (OH) (R ¹¹ ) -COOH (7)
[Wherein, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 10 carbon atoms. An aryl group, a nitro group, an ester group having 2 to 6 carbon atoms, an ether group having 2 to 6 carbon atoms, an amino group which may have a substituent, or an amine derivative group. ];
(F) component: aminocarboxylic acid represented by the following general formula (8) and salts thereof, and hydroxyphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), And at least one component selected from the group consisting of 2-phosphono-1,2,4-butanetricarboxylic acid and salts thereof:

[Wherein R ¹² is — (CH ₂ ) _n —Z; Z is H, OH or COOM; M is H, Na, K, NH ₄ or alkanolamine; n is 0-5. It is an integer. ];
Containing water,
The total content of all the surfactants is 45% by mass or more and 60% by mass or less with respect to the total mass of the liquid detergent, and
The liquid detergent whose content of the said (B) component is 4 mass% or more with respect to the total mass of a liquid detergent.

［式中、Ａ^１及びＢ^１はそれぞれ独立して、水素原子又はメチル基であり；Ｒ^６及びＲ^７はそれぞれ独立して、炭素数２〜４のアルキレン基であり；ｘ^１は０〜１０であり、ｙ^１はそれぞれ独立して１〜１００である。］

［式中、Ａ^２及びＢ^２はそれぞれ独立して、水素原子又はメチル基であり；Ｒ^８及びＲ^９はそれぞれ独立して、炭素数２〜４のアルキレン基であり；ｘ^２は０〜１０であり；ｙ^２はそれぞれ独立して、１〜１００である。］;
（Ｅ）成分：グリコール酸、乳酸、ヒドロキシ酪酸、ヒドロキシイソ酪酸、マンデル酸、それらの光学異性体、及びそれらの塩からなる群より選ばれる少なくとも１種の成分と；
（Ｆ）成分：メチルグリシン二酢酸三ナトリウムと；
水と、を含有し、
全ての界面活性剤の含有量の合計が、液体洗浄剤の総質量に対して、４５質量％以上、６０質量％以下であり、かつ、
前記（Ｂ）成分の含有量が、液体洗浄剤の総質量に対して、４質量％以上である、液体洗浄剤。As other aspects of the liquid detergent of the present invention,
Component (A): a nonionic surfactant containing a compound represented by the following general formula (1):
R ¹ -X- (EO) _s (PO) _t -R ² (1)
[In formula (1), 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 carbon. EO is an ethylene oxide group; s represents an EO average repeat number (that is, an average added mole number of ethylene oxide), an integer of 3 to 20; PO is a propylene oxide group Yes; t represents the average number of repeating POs (that is, the average number of moles of propylene oxide added), and is an integer of 0-6. ];
Component (B): at least one anionic surfactant selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate ;
(C) component: a protease having serine, histidine, and aspartic acid in the molecule;
Component (D): a compound represented by the following general formula (5) or the following general formula (6):

Wherein, ^{A 1} and ^{B 1} are each independently hydrogen atom or methyl group; ^{R 6} and ^{R 7} each independently, an alkylene group having 2 to 4 carbon atoms; ^{x 1} is 0 And y ¹ is independently 1 to 100. ]

Wherein, ^{A 2} and ^{B 2} are each independently a hydrogen atom or a methyl group; ^{R 8} and ^{R 9} are each independently an alkylene group having 2 to 4 carbon atoms; ^{x 2} is 0 And y ² is independently 1 to 100. ];
(E) component: 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;
Component (F): trisodium methylglycine diacetate;
Containing water,
The total content of all the surfactants is 45% by mass or more and 60% by mass or less with respect to the total mass of the liquid detergent, and
The liquid detergent whose content of the said (B) component is 4 mass% or more with respect to the total mass of a liquid detergent.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

"Raw material"
As the component (A), the following compounds were used.
A-1: 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 = average 15 Narrow ratio 33% by mass, synthetic product.
_{· A-2: C 11 H} 23 CO (OCH 2 CH 2) m OCH 3, m = average 15, narrow ratio 33 wt%, the composition.
· _A-3: a _{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 Mixture of mass ratio 7.2 / 1.8 / 1.0, m = average 15, narrow rate 33% by mass, synthetic product.
A-4: a nonionic surfactant obtained by adding an average of 15 moles of ethylene oxide to natural alcohol CO-1217 (trade name) manufactured by P & G.
A-5: a nonionic surfactant obtained by adding an average of 12 moles of ethylene oxide to natural alcohol CO-1217 (trade name) manufactured by P & G.
A-6: Nonionic surfactant obtained by block addition of 8 mol of ethylene oxide, 2 mol of propylene oxide, and 8 mol of ethylene oxide in this order to natural alcohol (C12 / C14 = 7/3).
A-7: Trade name “Softanol 90”, manufactured by Nippon Shokubai Co., Ltd.

The narrow rate of said a-1 to a-3 was measured in the following procedure.
Under the following measurement conditions, the distribution of ethylene oxide adducts having different numbers of moles of ethylene oxide added was measured, and the narrow ratio (% by mass) was calculated from the above formula (S).
<Measurement conditions of distribution of ethylene oxide adduct by HPLC>
-Apparatus: LC-6A (manufactured by Shimadzu Corporation),
-Detector: SPD-10A,
Measurement wavelength: 220 nm
Column: Zorbax C8 (manufactured by Du Pont),
Mobile phase: acetonitrile / water = 60/40 (volume ratio)
・ Flow rate: 1 mL / min,
-Temperature: 20 degreeC.

The a-1 to a-6 were synthesized by the following procedure.
Synthesis of a-1:
Synthesis was performed according to Production Example 1 in Examples described in JP-A No. 2000-144179.
That is, alumina hydroxide / magnesium hydroxide having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (trade name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina / magnesium hydroxide (unmodified) catalyst (2.2 g) obtained by calcining, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, Was charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added 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 narrow ratio of a-1 was 33% by mass.

Synthesis of a-2:
Instead 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 so that the narrow ratio was 33% by mass. A-2 was produced in the same manner as in the synthesis method of a-1.

Synthesis of a-3:
Except that 252 g of lauric acid methyl ester, 63 g of myristic acid methyl ester and 35 g of palmitic acid methyl ester were used, 1023 g of ethylene oxide was introduced, and the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 33% by mass. A-3 was produced in the same manner as in the synthesis method of -1.

Synthesis of a-4:
224.4 g of natural alcohol CO-1270 manufactured by P & G and 2.0 g of 30% by mass NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. .
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain a-4.

Synthesis of a-5:
A-5 was produced in the same manner as the synthesis method a-4 except that the amount of ethylene oxide was changed to 610.2 g.

Synthesis of a-6:
224.4 g of natural alcohol CO-1270 manufactured by P & G and 2.0 g of 30% by mass NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 405 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, after aging for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, 130 g of propylene oxide (gaseous) is added using a blowing tube so that the reaction temperature does not exceed 180 ° C. While adjusting the speed, it was gradually added to react. After aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, 405 g of ethylene oxide was further reacted. After aging, unreacted ethylene oxide was distilled off, the temperature was cooled to 100 ° C. or less, and 70% by mass p-toluenesulfonic acid was added so that the pH of the 1% by mass aqueous solution of the reaction product was about 7. To obtain a-6.

As the component (B), the following compounds were used.
B-1: linear alkylbenzenesulfonic acid (manufactured by Lion Corporation, alkyl group having 10 to 14 carbon atoms, average molecular weight 322).
B-2: Secondary alkane sulfonate sodium (manufactured by Clariant Japan).
B-3: Sulfur oxide of an ethylene oxide average 2 mol addition product of a synthetic alcohol having 12 to 13 carbon atoms.
B-4: Sodium salt of α-sulfo fatty acid methyl ester (manufactured by Lion Corporation, C16 / C18 = 8/2)

The b-3 was synthesized by the following procedure.
Synthesis of b-3:
In a 4 L autoclave, 400 g of a trade name “Neodol 23” manufactured by Shell and 0.8 g of a potassium hydroxide catalyst were charged, and the inside of the autoclave was purged with nitrogen and heated while stirring. Thereafter, while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, 181 g of ethylene oxide (gaseous) was introduced to obtain a reaction product having an average ethylene oxide repetition number of 2. Next, 280 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain b-3.

The b-4 was synthesized by the following procedure. Synthesis of b-4:
In a 1 kL reactor equipped with a stirrer, fatty acid methyl ester mixture (methyl palmitate (trade name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (trade name: Pastel M-180, manufactured by Lion Corporation) The mixture was premixed so as to have a mass ratio of 8: 2), and 330 kg of the mixture was added and stirred, and anhydrous sodium sulfate was added as a coloring inhibitor to 5 parts by mass with respect to 100 parts by mass of the fatty acid methyl ester mixture. I put it in. Then, while continuing stirring, 115 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with nitrogen gas at a reaction temperature of 80 ° C. (1.2 times mol with respect to the fatty acid methyl ester mixture) was bubbled. Then, it was blown at a constant speed over 3 hours, and then aging was performed for 30 minutes while maintaining at 80 ° C. Then, 14 kg of methanol was supplied as a lower alcohol, and esterification was performed at a temperature of 80 ° C. and a aging time of 30 minutes.
Subsequently, the esterified product extracted from the reaction apparatus was continuously neutralized by adding an equivalent amount of aqueous sodium hydroxide solution using a line mixer.
Next, this neutralized product was injected into the bleaching agent mixing line, and 35% by volume of hydrogen peroxide water was converted into a pure component, and the anionic surfactant concentration (α-sulfo fatty acid methyl ester sodium salt (MES-Na) and α -1 mass% was supplied to and mixed with sulfofatty acid disodium salt (di-Na salt), and bleaching was carried out while maintaining at 80 ° C. to obtain pasty b-4.

As the component (C), the following compounds were used.
C-1: Coronase 48L (trade name, manufactured by Novozymes).
C-2: Everlase 16L Type EX (trade name, manufactured by Novozymes).

As the component (D), the following compounds were used.
D-1: TexCare SRN-170C (trade name, manufactured by Clariant Japan) (mass average molecular weight: 2000 to 3000, pH (5 mass% aqueous solution at 20 ° C.): 4, viscosity (20 ° C.): 300 mPa · s) . TexCare SRN-170C is a 70% by mass aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan) (mass average molecular weight: 2000 to 3000). TexCare SRN-100 corresponds to the compound represented by the general formula (5).
In addition, d-1 is the condition of the above water-soluble polymer (10 g of polymer is added to 1000 g of water at 40 ° C., and stirred for 12 hours (200 rpm) with a stirrer (thickness 8 mm, length 50 mm, 1 L beaker). And completely dissolved).

As the component (E), the following compounds were used.
E-1: Sodium lactate (manufactured by Kanto Chemical Co., Inc.)

As the component (F), the following compounds were used.
F-1: Trisodium methylglycine diacetate (MGDA) (BASF, trade name “Trilon M”).

The following compounds were used as optional components.
Coconut fatty acid: manufactured by Nippon Oil & Fats.
MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.).
Citric acid 3Na: trisodium citrate dihydrate (manufactured by Fuso Chemical Industries, AI = 100%).
EtOH: Ethanol (made by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”)
Polyethylene glycol (Nippon Yushi Co., Ltd., trade name “PEG # 1000”)
Sodium benzoate: sodium benzoate (Fushimi Pharmaceutical Co., Ltd., trade name “sodium benzoate”).
Sulfuric acid: Toho Zinc Co., Ltd.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.

"Examples 1 to 15 and Comparative Examples 1 to 5"
<Preparation of liquid detergent>
A 500 mL beaker is charged with 6.0% by mass of 95% ethanol, an arbitrary amount of purified water and optional components (excluding purified water and a pH adjuster), and a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Stir well. Next, 1.0% by mass of monoethanolamine, and the component (B) of the types and blending amounts (% by mass) shown in Tables 1 and 2 were added to dissolve these components. Next, after adding the component (F) of the type and blending amount (mass%) shown in Tables 1 and 2, the component (A) is charged, and purified water is added so that the total amount becomes 96 parts by mass. Stir well. After adding an appropriate amount of pH adjuster (sulfuric acid, monoethanolamine, or sodium hydroxide) so that the pH at 25 ° C. is 7.0, dilute with component (D) and component (E) in advance. Oita component (C) was added, and purified water was added so that the total amount was 100 parts by mass to obtain a liquid detergent. The pH was measured at 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).
The obtained liquid cleaning agent was evaluated as follows. The results are shown in Tables 1-2.
In Tables 1 and 2, the “balance” of water is an amount such that the total amount of the liquid cleaning agent is 100 parts by mass.

<Evaluation method>
(Evaluation of enzyme stability (protease activity stability))
Protease activity was measured by the following procedure for the liquid detergents of each example stored at 37 ° C. for 4 weeks (stored at 37 ° C.) and those stored at 4 ° C. for 4 weeks (stored at 4 ° C.).
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) is dissolved in 1N sodium hydroxide aqueous solution (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.), pH Was 10.5. This was diluted with 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Inc.) aqueous solution so that the concentration of milk casein was 0.6% by mass to obtain a protease substrate.
Each sample was prepared by diluting 1 g of a 37 ° C. stored product and 4 ° C. stored product of each example 25 times (mass ratio) with 3 ° DH hard water (the hardness was adjusted with calcium chloride (special grade, manufactured by Kanto Chemical Co., Inc.)). It was set as the solution.
5 g of protease substrate was added to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37 ° C. for 30 minutes. Then, 5 g of 0.44 mol / L aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.) was added, stirred for 10 seconds with a vortex mixer, and then allowed to stand at 20 ° C. for 30 minutes to stop the enzyme reaction. did. Next, the precipitate was removed with a 0.45 μm filter, and the filtrate was recovered.
About the collect | recovered filtrate, the light absorbency (absorbance A) in wavelength 275nm was measured with Shimadzu Corporation ultraviolet visible spectrophotometer UV-160. The greater the absorbance A, the greater the amount of tyrosine (produced by the protease degrading the protease substrate) present in the filtrate.
Separately, 5 g of a 0.44 mol / L aqueous solution of TCA was added to 1 g of each sample solution, and after stirring for 10 seconds with a vortex mixer, 5 g of protease substrate was added and stirred for 10 seconds with a vortex mixer. Next, the precipitate was removed with a 0.45 μm filter, and the filtrate was recovered. About the collect | recovered filtrate, the light absorbency (absorbance B) of wavelength 275nm was measured with the ultraviolet visible spectrophotometer UV-160.
Based on the obtained absorbance, the enzyme (protease) activity remaining rate (%) was determined by the following formula. Note that the absorbance value at 275 nm of each sample assigned to the following equation is a value obtained by dividing the absorbance value at 600 nm measured simultaneously in order to exclude scattered light such as bubbles from the absorbance.
Residual rate of enzyme activity (%) = {(absorbance A of product stored at 37 ° C.) − (Absorbance B of product stored at 37 ° C.)} / {(Absorbance A of product stored at 4 ° C.) − (Absorbance B of product stored at 4 ° C.) } × 100

(Evaluation of appearance stability)
100 mL of the obtained liquid detergent was added to a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, it was placed in a constant temperature bath at 37 ° C. and stored for one month, and then the appearance of the liquid was visually observed and evaluated according to the following criteria. What was more than B was set as the pass.
A: No precipitated substance was observed at the bottom of the bottle.
B: A precipitate was observed at the bottom of the bottle, but the precipitate disappeared (dissolved) by gently shaking.
C: Precipitated material was observed at the bottom of the bottle, and the precipitate did not disappear even when shaken lightly.

As is clear from Tables 1 and 2, the liquid detergent obtained in each example had good enzyme stability. Also, the appearance stability was good.
On the other hand, the liquid detergent of Comparative Examples 1 and 2 not containing the component (D) and (E), the liquid detergent of Comparative Example 3 not containing the component (E), and Comparative Examples 4 to 4 not containing the component (D) Each of the liquid detergents 5 had poor enzyme stability.

  INDUSTRIAL APPLICATION Since this invention can provide the liquid detergent which contains surfactant in high concentration and was excellent in the storage stability of an enzyme, it is very useful industrially.

Claims (2)

(A) component: nonionic surfactant,
(B) component: an anionic surfactant;
(C) component: protease and
Component (D): Water-soluble having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. A polymer,
(E) component: containing at least one component selected from the group consisting of α-hydroxy-monocarboxylic acid and salts thereof,
The total content of all the surfactants is 45% by mass or more based on the total mass of the liquid detergent, and
The liquid detergent whose content of the said (B) component is 4 mass% or more with respect to the total mass of a liquid detergent.   Furthermore, (F) component: The liquid cleaning agent of Claim 1 containing at least 1 component chosen from the group which consists of aminocarboxylic acid and its salt, and phosphonic acid and its salt.