JP6071717B2 - Liquid detergent for textile products - Google Patents

Description

  The present invention relates to a liquid detergent for textile products.

Generally, there are mainly granular detergents and liquid detergents as detergents for textile products such as clothing. Since the liquid cleaning agent can be applied directly to the soiled portion and cleaned (coating and cleaning), there is an advantage in terms of usability.
A liquid detergent composition containing a specific nonionic surfactant, a hydrophobic organic solvent that is liquid at 20 ° C., and water as a liquid detergent having improved detergency in application washing (coating detergency) It has been proposed (for example, Patent Document 1).

In recent years, due to increasing awareness of environmental burdens, there is a demand for cleaning agents that can be rinsed with a small amount of water and have good rinsing properties. In particular, washing machines such as drum-type washing machines, such as drum-type washing machines, are used, and cleaning agents are covered with a single rinse even under conditions of low water usage. There is a need to promote washing.
Conventionally, a foam control agent such as a higher fatty acid or a silicone-based antifoaming agent is blended in the detergent for the purpose of enhancing rinsing properties. Such a cleaning agent contains a foam control agent, thereby suppressing the foaming of the cleaning agent or defoaming the generated foam to improve rinsing properties.

JP 2011-168731 A

By the way, the liquid cleaning agent is usually stored and distributed in a container, but when it is filled into a container at the time of manufacture or when it is transferred from a refilling container to the main container (hereinafter generally referred to as filling). There is a case that bubbles. When an anionic surfactant is blended in order to enhance the detergency of the liquid detergent, the foam film becomes stable and the foam becomes more difficult to disappear. In addition, when the viscosity of the liquid cleaning agent is lowered in order to increase the permeability to the object to be cleaned and improve the coating cleaning power, foaming tends to occur when the container is filled.
Here, in the case of liquid detergents containing higher fatty acids for the purpose of improving rinsing properties, the calcium ions and higher fatty acids in tap water used for washing form a calcium salt, thereby suppressing foam and defoaming properties. To demonstrate. For this reason, it cannot suppress that a liquid detergent foams at the time of filling to a container by mix | blending a higher fatty acid.
In addition, the invention of Patent Document 1 does not take into consideration any suppression of foaming of the liquid cleaning agent when filling the container.
Furthermore, the liquid cleaning agent is required to further improve the cleaning power.
Then, this invention aims at the liquid cleaning agent for textiles which was excellent in the detergency and was suppressed from foaming at the time of filling to a container.

  As a result of intensive studies, the present inventors have been able to remarkably enhance the detergency, particularly the application detergency, by using a specific ester compound, a nonionic surfactant, an anionic surfactant and a protease in combination. It was found that foaming at the time of filling can be suppressed, leading to the present invention.

That is, the liquid detergent for textiles of the present invention comprises (A) component: a compound represented by the following general formula (I), (B) component: a nonionic surfactant excluding the component (A), (C) Component: Anionic surfactant and (D) component: Protease are contained.
R ¹ -COO-Y (I)
[In the formula (I), R ¹ is an alkyl group having 5 to 21 carbon atoms, and Y is an alkyl group having 3 to 16 carbon atoms or — (R ² O) _m —R ³ . R ² is an alkylene group having 2 to 4 carbon atoms, m is a number from 1 to 5, and R ³ is an alkyl group having 1 to 22 carbon atoms, a phenyl group, or a benzyl group. ]

  According to the liquid detergent for textiles of the present invention, it is excellent in detergency and can suppress foaming when filling a container.

(Liquid detergent for textile products)
The liquid detergent for textile products of the present invention (hereinafter sometimes simply referred to as “liquid detergent”) comprises (A) component: a compound represented by the following general formula (I), and (B) component: (A Nonionic surfactant excluding component), (C) component: anionic surfactant, and (D) component: protease.
R ¹ -COO-Y (I)
[In the formula (I), R ¹ is an alkyl group having 5 to 21 carbon atoms, and Y is an alkyl group having 3 to 16 carbon atoms or — (R ² O) _m —R ³ . R ² is an alkylene group having 2 to 4 carbon atoms, m is a number from 1 to 5, and R ³ is an alkyl group having 1 to 22 carbon atoms, a phenyl group, or a benzyl group. ]

Although the viscosity (25 degreeC) of a liquid detergent is not specifically limited, 80 mPa * s or less is preferable. If a viscosity is below the said upper limit, the permeability to the textiles which are to-be-washed objects will increase at the time of application washing.
The viscosity of the liquid detergent is a value (measurement condition: rotor No. 2, rotation speed 30 rpm, viscosity after 10 rotations) measured by a B-type viscometer (manufactured by TOKIMEC).

  4-9 are preferable and, as for pH of a liquid detergent, 6-9 are more preferable. If pH is in the said range, application | coating cleaning power will increase more. pH (25 ° C.) indicates a value measured by a pH meter (HM-30G, manufactured by Toa DKK Corporation) or the like.

<(A) Component: Compound represented by Formula (I)>
The component (A) is a compound represented by the above formula (I), that is, an ester compound. By containing the component (A), the liquid cleaning agent of the present invention suppresses foaming of the liquid cleaning agent when filling the container (foaming suppression property during filling). In addition, component (A) has high affinity with hydrophobic soils (oil stains, sebum soils, etc.) and has high permeability to soils. The coating cleaning power against (oil stain, sebum stain, etc.) can be enhanced. Furthermore, by using together with the component (C) and the component (D), a good coating detergency is exhibited in spilled dirt (meat sauce dirt etc.) in which oil dirt and protein dirt are mixed.

(I) In formula, R < ¹ > is a C5-C21 alkyl group, Preferably it is a C5-C13 alkyl group, More preferably, it is a C7-C11 alkyl group. When the number of carbons is within the above range, the foam-suppressing property at the time of filling is enhanced, and the raw material can be easily obtained.
R ¹ may be linear or branched.
(I) wherein, Y is an alkyl group or ^{- _{(R 2 O) m -R 3}} .
When Y is an alkyl group, Y has 3 to 16 carbon atoms, and more preferably 6 to 10 carbon atoms. If the carbon number is less than the above lower limit, the hydrophobicity is weak, there is a possibility that sufficient coating detergency may not be obtained or sufficient foam suppression properties may not be obtained. May become too strong and liquid stability may be impaired.
When Y is an alkyl group, Y may be a straight chain or a branched chain. Among them, a branched chain is preferable from the viewpoint of improving the foam-suppressing property during filling and the coating detergency.
When Y is a branched chain, the number of side chains is preferably 1 to 4, and more preferably 1. When the number of side chains is within the above range, the foam-suppressing property during filling and the coating cleaning power can be further enhanced.
Preferable Y includes, for example, isotridecyl group, ethylhexyl group, hexyldecyl group, isobutyl group, isopropyl group and the like. Among them, from the viewpoint of improving foam stability during filling, coating detergency, and liquid stability. An ethylhexyl group is more preferable.
When Y is an alkyl group, the alkyl group of R ¹ has 5 to 21 carbon atoms, preferably 5 to 13 carbon atoms, more preferably 7 to 11 and particularly preferably 7 to 9. If the carbon number of R ¹ is within the above range, the balance between hydrophilicity and hydrophobicity will be good, and the coating detergency will be further enhanced.

When Y is — (R ² O) _m —R ³ , R ² is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, more preferably 3 carbon atoms. An alkylene group. When the carbon number is within the above range, the balance between hydrophilicity and hydrophobicity becomes good, and the coating cleaning power can be further enhanced.
m is a number of 1 to 5, 2 to 5 is preferable, and 3 is more preferable. If it is less than the above lower limit, the hydrophobicity becomes strong and the liquid stability may be impaired, and if it exceeds the above upper limit, the hydrophilicity becomes too strong and the coating cleaning power may be reduced.
R ³ is an alkyl group having 1 to 22 carbon atoms, a phenyl group or a benzyl group, and an alkyl group is particularly preferable. When R ³ is an alkyl group, the carbon number of ^{R 3} is preferably 1 to 16, more preferably 1 to 12, more preferably 1 to 6, 1 (i.e., methyl) is especially preferred. If it is in the said range, liquid stability will become favorable.
When Y is — (R ² O) _m —R ³ , the alkyl group of R ¹ has 5 to 21 carbon atoms, preferably 5 to 13 carbon atoms, and more preferably 9 carbon atoms. When the carbon number of R ¹ is within the above range, the balance between hydrophilicity and hydrophobicity becomes better, and the coating cleaning power can be further enhanced.

The component (A) can be produced by a conventionally known method. For example, the method for producing the component (A) in which Y is an alkyl group includes, for example, a method by transesterification between fats and oils and a monohydric alcohol, a method by transesterification between waste cooking oil and monohydric alcohols, and monovalent fatty acids. Examples thereof include a method of esterifying with an alcohol and a method of transesterification between a fatty acid alkyl ester and a monohydric alcohol. (A) Carbon number of the fatty acid residue which comprises a component cuts a carbon fraction by distilling (A) component, for example, or two types of carbon fraction of the fatty acid alkyl ester which has desired carbon number It can adjust by using the raw material mix | blended above.
Although it does not specifically limit as fats and oils used for the manufacturing method of (A) component, Vegetable oil and animal oil are preferable and vegetable oil is more preferable. Examples of vegetable oils include rapeseed oil, sunflower oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, corn oil, coconut oil, palm oil, palm kernel oil, and the like. Absent. Among these, palm kernel oil and coconut oil are preferable because of the high content of fatty acids having 6 to 14 carbon atoms. Examples of animal oils include beef tallow, pork tallow, and fish oil, but are not particularly limited thereto.
Moreover, as alcohol used for the manufacturing method of (A) component, although it does not specifically limit, natural alcohol, such as CO-1214 (brand name) or CO-1270 (brand name) by Procter & Gamble, Diadol (trade name, C13, C represents carbon number) manufactured by Mitsubishi Chemical Corporation, Neodol (trade name, mixture of C12 and C13) manufactured by Shell, Safol 23 (trade name) manufactured by Sasol , A mixture of C12 and C13) and the like.

 Examples of such component (A) include 2-ethylhexyl caprylate, isotridecyl myristate, 2-hexyldecyl dodecanoate, propylene glycol methyl ether caprylate, dipropylene glycol methyl ether caprylate, and tripropylene glycol methyl caprylate. Ether, propylene glycol methyl ether caprate, dipropylene glycol methyl ether caprate, tripropylene glycol methyl ether caprate, propylene glycol methyl ether laurate, dipropylene glycol methyl ether laurate, tripropylene glycol methyl ether laurate, caprylic acid Ethylene glycol methyl ether, caprylic acid diethylene glycol methyl ether, caprylic acid triethyl Glycol methyl ether, capric acid ethylene glycol methyl ether, capric acid diethylene glycol methyl ether, capric acid triethylene glycol methyl ether, lauric acid ethylene glycol methyl ether, lauric acid diethylene glycol methyl ether, lauric acid triethylene glycol methyl ether, propylene caprylate Glycol ethyl ether, caprylic acid dipropylene glycol ethyl ether, caprylic acid tripropylene glycol ethyl ether, capric acid propylene glycol ethyl ether, capric acid dipropylene glycol ethyl ether, capric acid tripropylene glycol ethyl ether, lauric acid propylene glycol ethyl ether, Dipropylene laurate Ethyl ether, lauric acid tripropylene glycol ethyl ether, caprylic acid ethylene glycol ethyl ether, caprylic acid diethylene glycol ethyl ether, caprylic acid triethylene glycol ethyl ether, capric acid ethylene glycol ethyl ether, capric acid diethylene glycol ethyl ether, capric acid tri Examples include ethylene glycol ethyl ether, lauric acid ethylene glycol ethyl ether, lauric acid diethylene glycol ethyl ether, and lauric acid triethylene glycol ethyl ether. Among them, 2-ethylhexyl caprylate and tripropylene glycol methyl ether caprate are preferable, and 2-ethylhexyl caprylate is more preferable. By using such a component (A), it is possible to further enhance the foam-suppressing property during filling and the coating cleaning power. These (A) components may be used individually by 1 type, and may be used in combination of 2 or more type.

 0.1-10 mass% is preferable, as for content of (A) component in a liquid detergent, 0.5-5 mass% is more preferable, and 1-3 mass% is further more preferable. If it is in the above-mentioned range, the foam-suppressing property at the time of filling and the coating cleaning power can be further enhanced.

<(B) component: nonionic surfactant except (A) component>
(B) component is a nonionic surfactant except (A) component. (B) component is a main component which exhibits the detergency of a liquid detergent, and has the effect | action which solubilizes (A) component in water. The component (B) is particularly excellent in the detergency of hydrophobic stains (oil stains, sebum stains, etc.), and when used in combination with the component (A), the coating detergency is further increased.

The component (B) is not particularly limited as long as it excludes the component (A), and examples thereof include the following.
(1) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may be a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

 As the component (B), the above (1) or (3) is preferable, and among them, a polyoxyalkylene-type nonionic surfactant represented by the following general formula (b1) (hereinafter referred to as component (b1)). And a polyoxyalkylene type nonionic surfactant represented by the following general formula (b2) (hereinafter sometimes referred to as component (b2)) is more preferred.

^{_{R 11 -X 1 - [(EO}} ) s / (PO) t] -R 12 ··· (b1)
[In the formula (b1), R ¹¹ represents an alkyl or alkenyl group having 8 to 18 carbon atoms. X ¹ is O, COO or CONH. R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. s represents the average number of repetitions of EO and is a number from 3 to 20. t represents the average number of repetitions of PO and is a number from 0 to 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

In the formula (b1), R ¹¹ is preferably an alkyl group or an alkenyl group having 10 to 18 carbon atoms from the viewpoint of detergency, and may be linear or branched. Examples of R ¹¹ include alkyl groups or alkenyl groups derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.
When R ¹² is an alkyl group, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms. When R ¹² is an alkenyl group, R ¹² is preferably an alkenyl group having 2 to 3 carbon atoms.

X ¹ is preferably O or COO.
When X ¹ is O, the component (b1) is an alkyl ether type nonionic surfactant. When X ¹ is O, the carbon number of R ¹¹ is preferably 10 to 18 from the viewpoint of detergency. R ¹¹ may have an unsaturated bond. When X ¹ is O, R ¹² is preferably a hydrogen atom.
When X ¹ is a COO, (b1) component is a fatty acid ester type nonionic surfactant. When X ¹ is a COO, from the viewpoint of ^detergency, the carbon number of ^{R 11} is preferably 9 to 17, 11 to 17 is more preferable. R ¹¹ may have an unsaturated bond. When X ¹ is COO, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms.

In the formula (b1), s is preferably a number of 5 to 18. When s exceeds 20, the HLB value becomes too high and the cleaning power tends to decrease. On the other hand, when s is less than 3, the raw material odor of the component (b1) itself tends to deteriorate.
t is preferably a number from 0 to 3. If t exceeds 6, the liquid stability of the liquid detergent at high temperature tends to be lowered.
EO and PO in (EO) _s / (PO) _t may be mixed and arranged, or EO and PO may be added randomly or may be added in blocks.
In the component (b1), the distribution of added moles of EO or PO is not particularly limited, and is likely to vary depending on the reaction method when the component (b1) is produced. For example, the addition mole number distribution of EO or PO is obtained by using ethylene oxide or propylene oxide as a hydrophobic group raw material (primary or secondary higher alcohol, higher fatty acid) using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. , Higher fatty acid amides, etc.) tend to have a relatively wide distribution. 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 the hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

As the component (b1), for example, Diadol (trade name, C13) manufactured by Mitsubishi Chemical Corporation, Neodol (trade name, a mixture of C12 and C13) manufactured by Shell, and Safol 23 (trade name, C12 manufactured by Sasol) are used. A mixture of 12 mol or 15 mol of ethylene oxide to an alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by Procter & Gamble Co. 12 mole equivalents or 15 mole equivalents of ethylene oxide added to a natural alcohol such as C12 alkene obtained by trimerizing butene to the C13 alcohol obtained by subjecting the oxo method to 7 mole equivalent Ethylene oxide added (trade name: Lutensol
TO7, manufactured by BASF); 9 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to gerbet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 mol equivalent of ethylene oxide added to the C10 alcohol obtained (commercial name: Lutensol XL70, manufactured by BASF); 6 mol based on the C10 alcohol obtained by subjecting pentanol to the garbed reaction Equivalent ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 9 mol equivalent or 15 mole equivalent ethylene oxide added to secondary alcohol having 12 to 14 carbon atoms (trade name: Softanol 90, Softanol 15 , Manufactured by Nippon Shokubai Co., Ltd.), methyl fatty acid (lauric acid / myristic acid (mass ratio) = 8/2) added with 15 mol equivalent of ethylene oxide using an alkoxylation catalyst (polyoxyethylene) And coconut fatty acid methyl ester (EO 15 mol)).

^{_{R 13 -O - [(EO)}} p / (PO) q] - (EO) r -H ··· (b2)
[In the formula (b2), R ¹³ is an alkyl or alkenyl group having 8 to 18 carbon atoms. p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, p, q, r are p> 1, r> 1, 0 <q ≦ 3, p + r = 10-20. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO in (EO) _p / (PO) _q may be mixed. ]

(B2) In the formula, R ¹³ may be linear or branched.
In the formula (b2), the ratio of EO and PO is preferably 0.1 to 0.5, more preferably 0.1 to 0.3 in terms of q / (p + r). . When it is at least the lower limit, the foam-suppressing property during filling is further enhanced. When it is not more than the above upper limit, an appropriate viscosity is easily obtained, and gelation is easily suppressed.
Only one of EO and PO in (EO) _p / (PO) _q may be present or mixed, and EO and PO may be added randomly. It may be added in the form of a block.

The component (b2) can be produced by a conventionally known method. For example, to an alcohol having R ¹³ derived from natural fats and oils, after addition reaction of ethylene oxide and propylene oxide in this order, or after mixed addition (random addition) of ethylene oxide and propylene oxide, ethylene oxide is added again. Can be manufactured.
When the component (b2) is used, the liquid detergent can easily obtain an appropriate viscosity, and gelation is also suppressed. Moreover, the foam suppression property at the time of filling is further increased, and the biodegradability is also improved.

Among the components (B), the component (b1) is preferable from the viewpoint of detergency, and in the formula (b1), X ¹ is O and corresponds to 9 mol or 15 mol with respect to the secondary alcohol having 12 to 14 carbon atoms. Those having a corresponding addition of ethylene oxide (for example, Softanol 90, Softanol 150 (trade name, manufactured by Nippon Shokubai Co., Ltd.), (b1) wherein X ¹ is COO fatty acid ester type nonionic surfactant is preferred, more preferably It is a fatty acid ester type nonionic surfactant.
These (B) components may be used individually by 1 type, and may be used in combination of 2 or more type.

  10-30 mass% is preferable, as for content of (B) component in a liquid detergent, 15-25 mass% is more preferable, and 20-25 mass% is further more preferable. If it is more than the said lower limit, (A) component can fully be solubilized and sufficient coating detergency can be exhibited. If it is below the said upper limit, the liquid stability under low temperature can be improved.

 In the liquid detergent, the mass ratio represented by component (A) / component (B) (hereinafter sometimes referred to as A / B ratio) is preferably 0.01 to 2.5, and preferably 0.04 to 0.00. 15 is more preferable. If it is more than the said lower limit, foam suppression property at the time of filling will improve more, and if it is below the said upper limit, coating cleaning power will increase more.

<(C) component: anionic surfactant>
Component (C) is an anionic surfactant. By containing the component (C), the liquid detergent can enhance the coating cleaning power, particularly the coating cleaning power against protein stains.
Component (C) is not particularly limited. For example, (1) higher fatty acid salt, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, acylaminocarboxylic acid Carboxylic acid types such as salts; (2) higher alcohol sulfate, polyoxyalkylene higher alcohol sulfate, alkylphenyl ether sulfate, polyoxyalkylene alkylphenyl ether sulfate, glycerin fatty acid ester monosulfate, etc. (3) sulfonic acid types such as alkane sulfonate, α-olefin sulfonate, linear alkylbenzene sulfonate, α-sulfo fatty acid ester salt, dialkyl sulfosuccinate; (4) alkyl phosphoric acid Beauty treatment Phosphate salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkyl phenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester, and other phosphate anionic surfactants; the salt in component (C) is sodium, Alkali metal salts such as potassium, alkanolamine salts such as monoethanolamine and diethanolamine, etc. are mentioned. Among them, alkane sulfonate, linear alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate are preferable, alkane sulfonate. Polyoxyethylene alkyl ether sulfate is more preferable.
The alkane sulfonate is more preferably a secondary alkane sulfonate. Moreover, it is preferable that carbon number of the alkyl group which alkanesulfonate has is 10-20, and it is more preferable that it is 10-14.
In the linear alkylbenzene sulfonate, the alkyl group preferably has 8 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms.
The polyoxyethylene alkyl ether sulfate preferably has 10 to 20 carbon atoms in the alkyl group. In addition, it is preferable that the average added mole number of EO is 0.5 to 8 moles. The above polyoxyethylene alkyl ether sulfates and secondary alkane sulfonates, which exhibit particularly good detergency, tend to foam during filling because they form a stable foam film. Since the property is obtained, the surfactant can be used.
These (C) components may be used alone or in combination of two or more.

 1-10 mass% is preferable, as for content of (C) component in a liquid detergent, 2-8 mass% is more preferable, and 4-6 mass% is further more preferable. If it is in the above range, the low-temperature stability of the liquid cleaning agent is improved, and good coating cleaning power can be obtained.

 In the liquid detergent, the mass ratio represented by component (A) / component (C) (hereinafter sometimes referred to as A / C ratio) is preferably 0.06 to 2.5, preferably 0.16 to 0.00. 75 is more preferred. If it is more than the said lower limit, foam suppression property at the time of filling will improve more, and if it is below the said upper limit, coating cleaning power will increase more.

 In the liquid detergent, the mass ratio represented by the component (B) / component (C) (hereinafter sometimes referred to as B / C ratio) is preferably 3 to 20, and more preferably 6 to 10. If it is more than the said lower limit, low temperature stability will improve, and if it is below the said upper limit, a coating cleaning power will increase more.

<(D) component: protease>
Component (D) is a protease. By using the component (D) in combination with the components (A) to (C), the coating cleaning power against dirt such as spilled dirt that contains oil stains and protein stains is improved, and re-contamination to textile products is also achieved. Can be prevented.
The component (D) is not particularly limited as long as it is used in conventional liquid detergents. For example, pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin BPN ′, papain, promeline, carboxypeptide Examples include Tase A, carboxypeptidase B, aminopeptidase, aspergylopeptidase A, and aspergillopeptidase B.
Further, for example, JP-A-51-8401, JP-A-46-43551, JP-A-46-42956, JP-A-59-59189, JP-A-54-62386, Japanese Laid-Open Patent Publication Nos. 48-2794, 50-16435, 53-18594, 55-46711, 57-42310, 58-16200 JP, JP-A-56-24512, JP-A-47-1832, JP-A-52-35758, JP-A-50-34633, JP-B-46-41596, JP-A 58-134990, JP 55-14086, JP 51-82783, JP 51-125407, JP 55-39794, JP 46-1840 JP-A-46-23989, JP-A-58-15282, JP-A-61-280278, JP-A-4-197182, JP-B-3-79987, JP-A-5-25492. What is described in the gazette etc. can also be used. In addition to these purified fractions, crude enzymes and granulated products thereof can also be used.
Examples of commercially available enzymes (protease preparations) include, for example, savinase, alcalase, evalase, cannase, esperase (trade name; manufactured by Novozymes); API21 (Manufactured by Showa Denko KK); Maxatase, Maxacal, Purefect, Maxapem, Properase (above, trade name; manufactured by GENENCOR (Genencore)); KAP (trade name, Examples include protease K-14 and K-16 (trade names) described in JP-A-5-25492. These may be used alone or in combination of two or more. As the protease preparation, Savinase 16L, Everase 16L (above, trade names: manufactured by Novozymes); Purafect L, Perfect OX, Properase L (above, trade names: manufactured by GENENCOR) are preferable, and Savinase 16L, Everase 16L are particularly preferable.

 The content of the component (D) in the liquid detergent is preferably 0.1 to 3% by mass, and more preferably 0.1 to 1% by mass. If it is more than the said lower limit, the application cleaning power with respect to various stain | pollution | contamination will increase more, and if it is below the said upper limit, it becomes economically advantageous.

 In the liquid detergent, the mass ratio represented by component (A) / component (D) (hereinafter sometimes referred to as A / D ratio) is preferably 0.16 to 50, and more preferably 0.16 to 30. . If it is more than the said lower limit, foam suppression property at the time of filling will improve more, and if it is below the said upper limit, coating cleaning power will increase more.

<Optional component>
In addition to the components (A) to (D), the liquid detergent is a water-miscible organic solvent, a cationic surfactant, an amphoteric surfactant, and a viscosity reducing agent as necessary, as long as the effects of the present invention are not impaired. Or solubilizer, alkali agent, metal ion scavenger, antioxidant, texture improver, fluorescent brightener, recontamination inhibitor, pearl agent, soil release agent, enzyme other than component (D), flavoring agent , Colorants, emulsifying agents, extracts, pH adjusting agents and other optional components may be included.

The water-miscible organic solvent is an organic solvent that dissolves 50 g or more in 1 liter of water at 25 ° C. Examples of the water-miscible organic solvent include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, alkylene glycols having 2 to 6 carbon atoms such as a copolymer of ethylene glycol and propylene glycol; ethanol, methanol, propanol Alcohols such as butanol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol mono Butyl ether, diethylene glycol dibu (Poly) alkylene glycol (mono or di) alkyl such as ether, propylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monobutyl ether, oxyethylene dioxypropylene glycol monobutyl ether Ether; aromatic ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether. Among them, from the point of improvement of solubility and liquid stability during low temperature storage, ethanol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monobutyl ether, oxyethylene dioxypropylene glycol monobutyl ether More preferable
These water-miscible organic solvents may be used singly or in combination of two or more.
The content of the water-miscible organic solvent in the liquid detergent is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and even more preferably 7 to 15%. If it exists in the said range, the further improvement of a solubility and liquid stability can be aimed at.

As the cationic surfactant, conventionally known cationic surfactants can be used. For example, (1) dilong chain alkyldishort chain alkyl type quaternary ammonium salt; (2) mono long chain alkyltrishort chain alkyl type Quaternary ammonium salt; (3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt and the like.
The “long chain alkyl” in (1) to (3) represents an alkyl group having 10 to 26 carbon atoms. The alkyl group preferably has 12 to 18 carbon atoms.
“Short-chain alkyl” refers to an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkyl group preferably has 1 or 2 carbon atoms. Examples of the substituent that the alkyl group may have include a phenyl group, a benzyl group, a hydroxyl group, a hydroxyalkyl group, and a polyoxyalkylene group. 2-4 are preferable and, as for carbon number of a hydroxyalkyl group, 2 or 3 is more preferable. 2-4 are preferable and, as for carbon number of the alkylene group in a polyoxyalkylene group, 2 or 3 is more preferable.
Although content of the cationic surfactant in a liquid detergent is not specifically limited, 0.01-30 mass% is preferable and 0.1-20 mass% is more preferable. If it is in the said range, when washing | cleaning clothes, a favorable softness | flexibility will be given to clothes.

As the amphoteric surfactant, conventionally known amphoteric surfactants can be used. For example, alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type Amide amino acid type, phosphate type amphoteric surfactant and the like.
The content of the amphoteric surfactant in the liquid detergent is preferably 0.1 to 15% by mass, for example.

The thinning agent or solubilizer suppresses the formation of a film on the liquid surface due to gelation of the liquid detergent. Examples of the thickener or solubilizer include aromatic sulfonic acids such as toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and salts thereof. Examples of the aromatic sulfonate include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt and alkanolamine salt.
A thinning agent or a solubilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the thinning agent or solubilizer in the liquid detergent is preferably 0.01 to 15% by mass. If it is in the said range, the film formation in the liquid surface of a liquid detergent can be suppressed favorably.

Examples of the alkali agent include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.
An alkali agent may be used individually by 1 type, and 2 or more types may be used in combination.
As for content of the alkaline agent in a liquid detergent, 0.5-5 mass% is preferable.

Examples of the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
A metal ion scavenger may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the metal ion scavenger in the liquid detergent is preferably 0.1 to 20% by mass.

The antioxidant is not particularly limited, but a phenol-based antioxidant is preferable because it has good detergency and liquid stability. As the phenolic antioxidant, dibutylhydroxytoluene, butylhydroxyanisole, 2,2′-methylenebis (4-methyl-6-t-butylphenol, dl-α-tocopherol is preferable, dibutylhydroxytoluene, dl-α-tocopherol. Is more preferable.
An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the antioxidant in the liquid detergent is preferably from 0.01 to 2% by mass.

Examples of the texture improving agent include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone.
The content of the texture improving agent in the liquid detergent is preferably 0 to 5% by mass.

Examples of fluorescent whitening agents intended to improve whiteness of white clothing include distyryl biphenyl type.
The content of the fluorescent brightener in the liquid detergent is preferably 0 to 1% by mass.

Examples of the dye transfer inhibitor or the recontamination inhibitor include polyvinyl pyrrolidone and carboxymethyl cellulose.
The blending amount of the dye transfer inhibitor or the recontamination inhibitor in the liquid detergent is preferably 0 to 2% by mass.

 Examples of the enzyme other than the component (D) include lipase and cellulase.

It does not specifically limit as a fragrance | flavor, For example, the fragrance | flavor composition AD of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399 etc. are mentioned.
The content of the flavoring agent in the liquid detergent is preferably 0.1 to 1% by mass.

Colorants include 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, and Turquoise P-GR (all trade names) Is mentioned.
The content of the colorant in the liquid detergent is preferably 0.00005 to 0.005% by mass.

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. Examples of such emulsion-type emulsifying agents include polystyrene emulsion (trade name: Cybinol RPX-196 PE-3, solid content 40% by mass, manufactured by Seiden Chemical Co., Ltd.).
The content of the emulsifying agent in the liquid detergent is preferably 0.01 to 0.5% by mass.

Extracts include, for example, Inuenju, Ouurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay, Juice, Japanese burdock, Comfrey, Ginger, Waremokaku, Peonies , Ginger, goldenrod, elderberry, sage, mistletoe, buckwheat, thyme, flowering dragonfly, clove, mandarin orange, tea tree, barberry, dokudami, nanten, nikko, yorusa, shirogaya, boufu, dutch hail, hop, honshitan, gray Murasakitagayasan, pokeweed, 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 in the liquid detergent is preferably 0 to 0.5% by mass.

Examples of the pH adjuster include acidic compounds such as sulfuric acid and hydrochloric acid; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkaline compounds such as sodium hydroxide and potassium hydroxide. From the above aspect, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are more preferable. These pH adjusters may be used alone or in combination of two or more.
However, when a liquid detergent having a desired pH can be obtained with only components excluding the pH adjuster, it is not always necessary to use the pH adjuster.

(Method for producing liquid detergent)
As a manufacturing method of the liquid detergent of this invention, what disperse | distributes (A)-(D) component to dispersion media, such as water, is mentioned, for example, (B) component, (C) component, and as needed A method of dispersing an optional component in a dispersion medium, adjusting the pH to 7 and then dispersing the component (A), dispersing the component (D), and further adjusting to an arbitrary pH is preferable.

(How to use liquid detergent)
The method of using the liquid detergent of the present invention (cleaning method) is the same as the method of using a general liquid detergent. For example, a method in which a liquid cleaning agent is put in water together with an object to be cleaned and washed in a washing machine, a method in which a liquid cleaning agent is directly applied to an object to be cleaned, a cleaning agent dissolved in water to form a cleaning liquid, and the cleaning liquid to be cleaned The method of immersing a thing etc. is mentioned. Moreover, after apply | coating a liquid cleaning agent to a to-be-washed object and leaving it to stand suitably, you may wash | clean using a washing machine.
Examples of the textile product to be cleaned include textile products such as clothing, cloths, sheets, and curtains, among which clothing is preferable.

As described above, according to the liquid cleaning agent of the present invention, since the components (B) to (D) are contained, the cleaning power is excellent. In addition, since it contains the component (A), it is excellent in foam suppression at the time of filling, and the coating cleaning power can be synergistically increased.
The reason why the antifoaming property at the time of filling and the coating cleaning power are increased by containing the component (A) is not clear, but can be estimated as follows.
The component (A) is considered to act on the foam film formed by the component (B) or the component (C) and defoam. In addition, it is considered that the component (A) rapidly penetrates into the hydrophobic soil with the components (B) to (D) and promotes the action of the components (B) to (D) on the hydrophobic soil. .

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
The measurement methods and raw materials used in the following examples are shown below.
<(A) Component: Compound represented by Formula (I)>
A-1: 2-ethylhexyl caprylate, pastel 2H-08 (trade name), manufactured by Lion Corporation.
A-2: 2-ethylhexyl caprate (2H-10, synthesized by the following synthesis method).

<< Synthesis Method of A-2 >>
In a 5 L four-necked flask, 1700 g of capric acid methyl ester (product name; Pastel M10, manufactured by Lion Corporation), 1425 g of 2-ethylhexanol, and 17 g of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Inc.) were used. Preparation and nitrogen substitution were performed. Then, while flowing nitrogen at a flow rate of 1 mL / second, the liquid temperature was raised to 140 ° C. to carry out an esterification reaction, and water produced by the reaction was removed by distillation. After removing water, the temperature was raised to 200 ° C. while gradually reducing the pressure to 0.6 kPa to obtain a crude product. Next, 21.5 g (1.5 parts by mass with respect to 100 parts by mass of the crude product) of Hyflo Supercell (trade name, manufactured by Nacalai Tesque Co., Ltd.) as a filter aid is added to 1500 g of the crude product and stirred for 10 minutes. And then uniformly dispersed at 80 ° C. to obtain 2-ethylhexyl caprate.

  A-3: Isotridecyl laurate (M12-TD, synthesized by the following synthesis method).

<Method of synthesizing A-3>
A 5 L four-necked flask was charged with 2114 g of lauric acid, 1470 g of isotridecanol (manufactured by Kyowa Hakko Chemical Co., Ltd.), and 17 g of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) as a catalyst, and nitrogen replacement went. Then, while flowing nitrogen at a flow rate of 1 mL / second, the liquid temperature was raised to 140 ° C. to carry out an esterification reaction, and water produced by the reaction was removed by distillation. After removing water, the temperature was raised to 200 ° C. while gradually reducing the pressure to 0.6 kPa to obtain a crude product. Next, 21.5 g (1.5 parts by mass with respect to 100 parts by mass of the crude product) of Hyflo Supercell (trade name, manufactured by Nacalai Tesque Co., Ltd.) as a filter aid is added to 1500 g of the crude product and stirred for 10 minutes. And then uniformly dispersed at 80 ° C. to obtain isotridecyl laurate.

  A-4: Capric acid tripropylene glycol methyl ether (M10-3PO, synthesized by the following synthesis method).

<Method for synthesizing A-4>
In a 5 L four-necked flask, 1400 g of capric acid methyl ester (trade name, Pastel M10, manufactured by Lion Corporation), 1860 g of tripropylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.), and p-toluenesulfonic acid (as a catalyst) 17 g) (manufactured by Kanto Chemical Co., Inc.) and nitrogen substitution was performed. Then, while flowing nitrogen at a flow rate of 1 mL / second, the liquid temperature was raised to 140 ° C. to carry out an esterification reaction, and water produced by the reaction was removed by distillation. After removing water, the temperature was raised to 200 ° C. while gradually reducing the pressure to 0.6 kPa to obtain a crude product. Next, 21.5 g (1.5 parts by mass with respect to 100 parts by mass of the crude product) of Hyflo Supercell (trade name, manufactured by Nacalai Tesque Co., Ltd.) as a filter aid is added to 1500 g of the crude product and stirred for 10 minutes. And uniformly dispersed, and then filtered under pressure at 80 ° C. to obtain caprylic acid tripropylene glycol monomethyl ether.

<(B) component: nonionic surfactant except (A) component>
B-1: synthesized by the following synthesis method. A natural alcohol (trade name: CO-1214, manufactured by Procter & Gamble Co.) added with 15 moles of ethylene oxide (LMAO (C12 / 14-15EO)).

<< Synthesis of B-1 >>
861.2 g of CO-1214 (trade name) 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. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the 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 then 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% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and LMAO (C12 / 14 -15EO).

  B-2: A coconut fatty acid methyl (a mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) added with 15 mol of ethylene oxide using an alkoxylation catalyst [MEE (C12 / 14-15EO)], a synthetic product. The synthesis was performed as follows.

≪B-2 synthesis method≫
The synthesis was carried out according to the synthesis method described in JP 2000-144179 A (corresponding to sample D).
Alumina-magnesium hydroxide (trade name: Kyoward 330, manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere. The resulting calcined alumina / magnesium hydroxide (unmodified) catalyst (2.2 g), 0.5 N potassium hydroxide ethanol solution (2.9 mL), lauric acid methyl ester (280 g), and myristic acid methyl ester (70 g) in a 4 L autoclave. First, the catalyst was reformed in an 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 × 10 ⁵ Pa, 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 were added as filter aids, respectively, and the catalyst was filtered off to obtain MEE (C12 / 14-15EO). .

B-3: A secondary alcohol having 12 to 14 carbon atoms added with 9 mol of ethylene oxide, Softanol 90 (trade name), manufactured by Nippon Shokubai Co., Ltd.
B-4: A product obtained by adding 9 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to a gerbet reaction, Lutensol XP90 (trade name), manufactured by BASF.

≪ (C) component: anionic surfactant≫
C-1: Linear alkylbenzene sulfonic acid (LAS), Raipon LH-200 (trade name), carbon number 10-14, average molecular weight 322, manufactured by Lion Corporation.
C-2: Sodium polyoxyethylene alkyl ether sulfate (AES), synthetic product, carbon number 12-13, average addition mole number 2 mol of EO, raw material alcohol: Neodol 23 (trade name, manufactured by Shell).
C-3: Secondary alkane sulfonate sodium (SAS), SAS30 (trade name), manufactured by Clariant Japan Co., Ltd.

≪ (D) component: protease≫
D-1: Coronase 48L (trade name), protease, manufactured by Novozymes.
D-2: Recanase Ultra 2.5XL (trade name), protease, manufactured by Novozymes.

≪pH adjuster≫
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.

≪Common ingredients≫
Hereinafter, “mass%” described at the end of the common component is the content in the liquid detergent of each example.
Sodium benzoate: 0.5% by mass produced by Toa Gosei Co., Ltd.
Sodium citrate: sodium citrate (trade name), manufactured by Miles Co., Ltd. 0.1 mass%.
Coconut fatty acid: NAA-415TC (trade name), manufactured by NOF Corporation, 1.0 mass%.
Monoethanolamine: Nippon Shokubai Co., Ltd .... 1.0% by mass.
Polyethylene glycol: PEG # 1000 (trade name), manufactured by Lion Corporation, 2.0% by mass.
Dibutylhydroxytoluene: SUMILZER BHT-R, manufactured by Sumitomo Chemical Co., Ltd. 0.05% by mass.
Dye: Green No. 3, manufactured by Hatake Kasei Co., Ltd. 0.0001% by mass
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP 2002-146399 A: 0.4% by mass
Purified water: Balance (amount so that the liquid detergent becomes 100% by mass).

(Evaluation method)
<Foam suppression during filling>
A pouch containing 900 g of the liquid cleaning agent in each example was allowed to stand at 20 ° C. for 1 hour, and then poured into an empty bottle (1000 mL capacity). At this time, 10 examinees evaluated the state of the spout according to the following evaluation criteria. The average score of 10 test subjects was calculated, 3 or more points were “◯”, 2 points or more and less than 3 points were “Δ”, and 2 points or less were “x”.

≪Evaluation criteria≫
4 points: No bubbles at all.
3 points: Slightly bubbling.
2 points: Pretty foamy.
1 point: Very foamy.

<Coating cleaning power>
≪Coating cleaning power for meat sauce stains≫
In a stainless steel bat, a mamma meat sauce (trade name, manufactured by Nisshin Foods Co., Ltd.) filtered with gauze was placed, and 100th cotton plain weave fabric (raw fabric) was immersed in it for about 1 hour. Then, the meat sauce dirt adhering excessively was removed by brushing, air-dried overnight, and 6 sheets cut into 10 cm × 10 cm were used as meat sauce dirt cloth (contaminated cloth).
The liquid detergent 0.1g of each example after 24 hours preservation | save at 25 degreeC was apply | coated to 6 sheets of contaminated cloth, and after leaving it for 5 minutes, this contaminated cloth was made to Terg-O-Tometer (made by UNITED STATES TESTING), A clean knitted cloth and 900 mL of 15 ° C. tap water (hardness 3 ° DH) (bath ratio 15 times) were added and stirred at 120 rpm for 10 minutes. Then, it moved to the 2 tank type washing machine (the Mitsubishi Electric Co., Ltd. make, CW-C30A1 type | mold), and spin-dry | dehydrated for 1 minute. Next, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.
Measure the Z value (reflectance) of the fabric before and after cleaning the meat source using a colorimetric colorimeter (Nippon Denshoku Co., Ltd., product name: SE2000). Was used to calculate the washing rate (%) for meat sauce stains.

  Cleaning rate for meat sauce stain (%) = (Z value of contaminated cloth after washing−Z value of contaminated cloth before washing) ÷ (Z value of raw cloth−Z value of contaminated cloth before washing) × 100 (1)

  The average value of the cleaning rate (%) with respect to the meat sauce stain was classified into the following evaluation criteria, and if “Δ”, “◯”, “◎”, the coating cleaning power was judged to be good.

[Evaluation criteria]
A: The cleaning rate is 20% or more.
○: The cleaning rate is 15% or more and less than 20%.
Δ: The cleaning rate is 10% or more and less than 15%.
X: The cleaning rate is less than 10%.

≪Coating and cleaning power against sebum dirt≫
A 100th cotton plain weave cloth (raw cloth) cut into a 10 cm square was rubbed against the sebum dirt on the face to prepare six sebum dirt cloths (dirt cloths).
The liquid detergent 0.1g of each example after 24 hours preservation | save at 25 degreeC was apply | coated to six sheets of dirt cloth, and after leaving for 5 minutes, this dirt cloth was made into Terg-O-Tometer (made by UNITED STATES TESTING). And 900 mL of 15 ° C. tap water (hardness 3 ° DH) was added and stirred at 120 rpm for 10 minutes. Then, it moved to the 2 tank type washing machine (Mitsubishi Electric Corporation make, product number: CW-C30A1-H1), and dehydrated for 1 minute. Next, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.
The Z value (reflectance) of the base cloth before adhering sebum dirt and the dirt cloth before and after washing is measured using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd., product name: SE2000). ) To calculate the cleaning rate (%) for sebum dirt.

  Cleaning rate for sebum stain (%) = (Z value of the soiled cloth after cleaning−Z value of the soiled cloth before cleaning) ÷ (Z value of the raw cloth−Z value of the soiled cloth before cleaning) × 100 ... (2)

  The average value of the cleaning rate (%) with respect to sebum dirt was classified into the following evaluation criteria. If “Δ”, “◯”, or “◎”, the coating cleaning power was determined to be good.

[Evaluation criteria]
A: The cleaning rate is 50% or more.
○: The cleaning rate is 40% or more and less than 50%.
Δ: The cleaning rate is 30% or more and less than 40%.
X: The cleaning rate is less than 30%.

≪Recontamination prevention performance≫
The liquid detergent 2.5g of each example preserve | saved at 25 degreeC for 1 month was put into 900 mL of 15 degreeC tap water (hardness 3 degree DH), and was set as the washing | cleaning liquid. Terg-O-meter (manufactured by UNITED STATES TESTING), washing liquid, 5 cotton knitted fabrics (manufactured by Tanigami Shoten) as cotton recontamination judgment cloth, and polyester tropical (manufactured by Tanigami shop as PE recontamination judgment cloth) ) 5 x 5 cm and wet artificially contaminated cloth (manufactured by Laundry Science Association, oleic acid 28.3 mass%, triolein 15.6 mass%, cholesterol oleate 12.2 mass%, liquid paraffin 2.5 20% by weight, a mixture of 2.5% by mass of squalene, 1.6% by mass of cholesterol, 7.0% by mass of gelatin, 29.8% by mass of mud, and 0.5% by mass of carbon black) Then, a skin shirt (LL size, manufactured by DVD) was cut into pieces (about 3 × 3 cm). 3 ° DH hard water was added to make the bath ratio 20 times, and washing was performed at 120 rpm and 25 ° C. for 10 minutes (cleaning treatment).
The cloth subjected to the washing treatment was dehydrated for 1 minute, and then rinsed with 900 mL of 25 ° C. 3 ° DH hard water at 120 rpm and 25 ° C. for 3 minutes. This rinsing was repeated twice. The second time was performed by adding a predetermined amount of a softening agent (rinse treatment). As the softener, room-dried saffron (manufactured by Lion Corporation) was used.
After the rinsed cloth is dehydrated for 1 minute, the cotton recontamination determination cloth and the PE recontamination determination cloth (which may be simply referred to as a recontamination determination cloth in general) are taken out and sandwiched between filter papers and dried with an iron ( Drying process).
The washing operation for performing the washing treatment, rinsing treatment and drying treatment was repeated three times.
The Z value of the recontamination determination cloth before and after washing was measured using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd., product name: SE2000), and ΔZ was determined by the following equation (3).

  ΔZ = Z value of the recontamination determination cloth before cleaning−Z value of the recontamination determination cloth after cleaning (3)

  The average value of ΔZ of the five recontamination determination cloths was classified into the following evaluation criteria, and if “Δ”, “◯”, “◎”, it was determined that the coating cleaning power was good.

[Evaluation criteria for cotton recontamination cloth]
A: ΔZ is less than 5.
○: ΔZ is 5 or more and less than 7.
Δ: ΔZ is 7 or more and less than 9.
X: ΔZ is 9 or more.

[Evaluation criteria for PE recontamination determination cloth]
A: ΔZ is less than 3.
○: ΔZ is 3 or more and less than 4.
Δ: ΔZ is 4 or more and less than 5.
X: ΔZ is 5 or more.

(Examples 1-19, Comparative Examples 1-4)
According to the composition of Tables 1-3, (B) component, (C) component, and a part of purified water were put into a 500 mL beaker, and it stirred with the magnetic stirrer (made by MITAMURA KOGYO INC.) Suitably. Subsequently, after adding the common components, after adding a pH adjuster (sodium hydroxide or hydrochloric acid) so that the pH at 25 ° C. is 7, the total amount is adjusted while adding the component (A) and stirring. Purified water was added so as to be 95% by mass and further stirred. Add component (D), add a pH adjuster (sodium hydroxide or hydrochloric acid) to the pH shown in the table, add purified water so that the total amount is 100% by mass, and wash the liquid in each example. An agent was obtained. In addition, the total amount of the pH adjuster used for pH adjustment was 0 to 2% by mass. Examples 1 and 9 are reference examples.

As shown in Tables 1 to 3, Examples 1 to 19 to which the present invention is applied have a foam-suppressing property at the time of filling of “Δ” or more, and the coating cleaning power against meat sauce stains and the coating cleaning power against sebum stains are “Δ”. ”To“ ◎ ”.
On the other hand, Comparative Example 2 which does not contain the component (C) and Comparative Example 4 which does not contain the component (D) had a foam detergency at the time of filling of “◯” but had a coating cleaning power of “x” for the meat sauce. It was. Moreover, the comparative example 3 which does not contain (A) component was "x" in the foaming suppression property at the time of filling, and the application | coating cleaning power with respect to sebum dirt.
In addition, about the comparative example 1 which does not contain (B) component, since (A) component could not be disperse | distributed to purified water, each evaluation was not performed.
From these results, it was found that by applying the present invention, it is possible to improve the coating cleaning power against all dirt and the foam suppression property during filling.

Claims (3)

(A) component: the compound represented by the following general formula (I),
(B) component: a nonionic surfactant excluding the component (A),
(C) component: an anionic surfactant;
(D) component: protease and
The liquid cleaning agent for textiles which contains 3 and the mass ratio represented by (B) component / (C) component is 3-20 .
R ¹ -COO-Y (I)
[In the formula (I), R ¹ is an alkyl group having 5 to 21 carbon atoms, and Y is an alkyl group having 3 to 16 carbon atoms or — (R ² O) _m —R ³ . R ² is an alkylene group having 2 to 4 carbon atoms, m is a number from 1 to 5, and R ³ is an alkyl group having 1 to 22 carbon atoms, a phenyl group, or a benzyl group. ] (I) The liquid cleaning agent for textiles according to claim 1, wherein Y is an alkyl group having 3 to 16 carbon atoms. (I) In the formula, Y is-(R ² O) _m -R ³ The liquid detergent for textiles according to claim 1, wherein m is 3.