JP5244382B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition.

  In washing, there is a problem of so-called “recontamination” in which a part of dirt once detached from the fibers of the object to be washed and dispersed in the washing liquid at the time of washing lowers the washing effect by depositing on the fibers again. is there.

2. Description of the Related Art In recent years, water-saving drum-type washing machines have become widespread in household washing machines from the viewpoint of increasing awareness of environmental measures and from the viewpoint of design.
However, in laundry using a drum-type washing machine at home, the bath ratio (ratio of the amount of the washing liquid to the amount of the washing object) is small, so dirt is likely to be recontaminated to the fibers. It has become clear that fiber re-contamination is likely to occur.
On the other hand, in the field of cleaning agents, it has been demanded to reduce the amount of surfactant used as a method for reducing the burden on the environment. In the washing using the drum type washing machine, when the amount of the surfactant used is reduced, there is a concern that the washing effect is reduced and the re-contamination is a problem as compared with the washing using the conventional vertical washing machine.

Examples of the detergent composition used in washing using a conventional vertical washing machine include those containing a polyoxyethylene (POE) type nonionic surfactant, which is a general-purpose surfactant. Can be mentioned.
For example, a liquid detergent composition has been proposed that contains a nonionic surfactant having a specific average number of moles of added ethylene oxide, an anionic surfactant, and a cationic surfactant in specific ratios (patents). Reference 1).
Japanese Patent Laid-Open No. 09-255988

  However, in a liquid detergent composition containing a conventional POE type nonionic surfactant such as the invention of Patent Document 1, in the case of washing using a drum-type washing machine having a low bath ratio, The effect of preventing contamination is not sufficient and the cleaning effect is low.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the liquid detergent composition excellent in the prevention effect of the recontamination to to-be-washed | cleaned object.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent composition of the present invention contains a nonionic surfactant (A) represented by the following general formula (I), a linear alkylbenzene sulfonate , and cellulase, and has a pH at 25 ° C. There wherein the 5-9 der Rukoto.

［式（Ｉ）中、Ｒ^１は炭素数９〜２１の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３は炭素数１〜３のアルキル基であり；ｎはアルキレンオキサイドの平均付加モル数を示し、５〜３０である。］

[In Formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 9 to 21 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is carbon. N represents an alkyl group having 1 to 3; n represents an average number of added moles of alkylene oxide, and is 5 to 30. ]

［式中、ｎ _ｍａｘ は全体のアルキレンオキサイド付加体中に最も多く存在するアルキレンオキサイド付加体のアルキレンオキサイドの付加モル数を示す。ｉはアルキレンオキサイドの付加モル数を示す。Ｙｉは全体のアルキレンオキサイド付加体中に存在するアルキレンオキサイドの付加モル数がｉであるアルキレンオキサイド付加体の割合（質量％）を示す。］
また、本発明の液体洗浄剤組成物においては、前記一般式（Ｉ）で表されるノニオン界面活性剤（Ａ）の割合が１５〜５０質量％であり、直鎖アルキルベンゼンスルホン酸塩の割合が１〜１５質量％であり、かつ、セルラーゼの割合が０．１〜３質量％であることが好ましい。 In the nonionic surfactant (A) represented by the general formula (I), a narrow ratio represented by the following formula (S), which indicates a distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide. Is preferably 20 to 45% by mass .

[ _Wherein n _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct. i represents the number of added moles of alkylene oxide. Yi represents the proportion (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the entire alkylene oxide adduct. ]
Moreover, in the liquid cleaning composition of this invention, the ratio of nonionic surfactant (A) represented by the said general formula (I) is 15-50 mass%, and the ratio of a linear alkylbenzene sulfonate is It is preferable that it is 1-15 mass%, and the ratio of a cellulase is 0.1-3 mass% .

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition excellent in the prevention effect of the recontamination to to-be-washed object can be provided.

≪Liquid detergent composition≫
The liquid detergent composition of the present invention comprises a nonionic surfactant (A) represented by the general formula (I) (hereinafter referred to as component (A)) and an anionic surfactant (B) (hereinafter referred to as ( B) component) and enzyme (C) (hereinafter referred to as component (C)).

<(A) component>
In the present invention, the component (A) is a nonionic surfactant represented by the general formula (I).
By using the component (A), in addition to improving the effect of preventing re-contamination of the article to be washed, it is excellent in solubility in water and high detergency can be easily obtained. In addition, a liquid detergent composition having good rinsability can be produced.

In the general formula (I), R ¹ is a linear or branched alkyl group having 9 to 21 carbon atoms, or a linear or branched alkenyl group having 9 to 21 carbon atoms.
In R ¹ , the carbon number of the alkyl group and the alkenyl group is preferably 11 to 17 carbon atoms from the viewpoint of improving the cleaning power and suppressing the formation of a film due to gelation of the liquid detergent composition itself. It is more preferable that it is several 11-13.
R ² is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. In the component (A), R ² may be a single alkylene group, or two or more alkylene groups may be mixed.
R ³ is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
n shows the average addition mole number of alkylene oxide, and is 5-30. Preferably, it is 12 to 18 from the viewpoint of improvement in detergency and liquid stability of the liquid detergent composition (particularly stability at low temperatures with time).

In the component (A), the narrow ratio indicating the proportion of the distribution of alkylene oxide adducts having different numbers of added moles of alkylene oxide is preferably 20% by mass or more, and the upper limit is substantially 80% by mass. % Or less is preferable. The narrow ratio is more preferably 20 to 60% by mass, and 30 to 45% by mass is more preferable because stability over time at low temperature is improved.
The higher the narrow rate, the better the cleaning power. Moreover, it becomes easy to obtain the liquid detergent composition with few raw material odors of surfactant as the said narrow rate is 20 mass% or more, especially 30 mass% or more. This is because, after the production of the component (A), the fatty acid ester which is the raw material of the component (A) coexisting with the component (A) and the alkylene oxide adduct of n = 1 and 2 in the general formula (I) are reduced. This is probably because of this.

  Here, the “narrow ratio” in the present specification means that represented by the following formula (S) indicating the distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.

［式中、ｎ_ｍａｘは全体のアルキレンオキサイド付加体中に最も多く存在するアルキレンオキサイド付加体のアルキレンオキサイドの付加モル数を示す。ｉはアルキレンオキサイドの付加モル数を示す。Ｙｉは全体のアルキレンオキサイド付加体中に存在するアルキレンオキサイドの付加モル数がｉであるアルキレンオキサイド付加体の割合（質量％）を示す。］

[ _Wherein n _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct. i represents the number of added moles of alkylene oxide. Yi represents the proportion (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the entire alkylene oxide adduct. ]

The narrow rate can be controlled by, for example, the method for producing the component (A).
The method for producing the component (A) is not particularly limited. For example, a method in which ethylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-2000-A). 144194179)).
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, Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a composite metal oxide catalyst such as magnesium oxide, and a hydrotalcite fired product whose surface is modified with a metal hydroxide and / or metal alkoxide Such as a catalyst.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

The component (A) used in the present invention has a molecular group with no hydrophilic group at the end of the molecule (end-capped type) and a highly polar carbonyl group in the molecule.
Because of these, the component (A) is a nonionic surfactant having a weak molecular orientation in an aqueous solution system and unstable micelles, so that it does not cause gelation even at high concentrations and has good liquidity. It is estimated that. Moreover, it is estimated that the solubility to water improves. Furthermore, it is thought that it contributes to good fluidity at a high concentration.
Therefore, after the component (A) is introduced into the water in the washing machine tub, the concentration of the component (A) in the washing liquid becomes uniform quickly and can contact the article to be washed at a predetermined concentration from the initial stage of washing. Therefore, it is considered that high detergency can be obtained. In addition, compared with a general-purpose polyoxyethylene (POE) type nonionic surfactant, it is considered that the rinsing property is excellent because the adsorptive power of the article to be washed to the fibers is low.

(A) A component can be used 1 type or in mixture of 2 or more types.
The content of the component (A) is preferably 15 to 50% by mass, more preferably 20 to 50% by mass, and further preferably 25 to 50% by mass in the liquid detergent composition. .
When the content of the component (A) is 15% by mass or more, the effect of preventing recontamination of the article to be washed is further improved. In addition, good detergency can be obtained. When the content of the component (A) is 50% by mass or less, sufficient detergency can be obtained. In addition, rinsability is improved. Furthermore, gelation of the liquid detergent composition on the liquid surface with time does not easily occur, and a film is hardly formed on the liquid surface.

<(B) component>
In the present invention, the component (B) is an anionic surfactant.
By using the component (B) in combination with the component (A) and the component (C) described later, an effect of preventing recontamination of the object to be washed can be obtained. In addition, the cleaning power is improved.

The component (B) is not particularly limited. For example, linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), polyoxyethylene alkyl ether sulfate (AES), α-olefin sulfonate (AOS), alkane sulfonate, α-sulfo fatty acid ester salt (α-SF), polyoxyethylene alkyl ether carboxylate, higher fatty acid salt (soap) and the like.
Specifically, an alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms, an alkyl sulfate having an alkyl group having 10 to 20 carbon atoms; an average of ethylene oxide having an alkyl group having 10 to 20 carbon atoms Polyoxyethylene alkyl ether sulfate having 1 to 10 addition moles; α-olefin sulfonate having an alkyl group having 10 to 20 carbon atoms, alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, carbon Α-sulfo fatty acid methyl ester salt having several 10 to 20 alkyl groups; polyoxyethylene alkyl ether carboxylate having 10 to 20 carbon atoms and an average addition mole number of ethylene oxide of 1 to 10; Preferred examples include higher fatty acid salts (soap) having 12 to 14 carbon atoms.
Among these, linear alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, and alkane sulfonate are preferable, and linear alkyl benzene sulfonate is more preferable.

  More specifically, the linear alkylbenzene sulfonate preferably has 8 to 16 carbon atoms in the alkyl group, and more preferably has 10 to 14 carbon atoms.

The polyoxyethylene alkyl ether sulfate preferably has 10 to 20 carbon atoms in the alkyl group, more preferably has 10 to 18 carbon atoms, and the average added mole number of ethylene oxide is 1 to 1. 10 are preferred, and the average added mole number is preferably 1-8.
In addition, as polyoxyethylene alkyl ether sulfate, the number of moles of ethylene oxide added in the ethylene oxide adduct that is the most present on the basis of mass in all ethylene oxide adducts constituting polyoxyethylene alkyl ether sulfate is expressed as “ n _1max ”, the total proportion of ethylene oxide adducts having an ethylene oxide addition mole number of (n _1max −1), n _1max and (n _1max +1) to the total ethylene oxide adduct is 55% by mass or more. Are also preferred, and those in the range of 55 to 75% by mass are more preferred. Within the above range, the yellowing suppression effect associated with the use of the softener product is further improved. In addition, on the liquid surface of the liquid detergent composition, the liquid detergent composition itself is hardly gelled and a film is hardly formed.

  As the alkane sulfonate, those having 10 to 20 carbon atoms of the alkyl group are preferable, those having 10 to 14 carbon atoms are more preferable, and secondary alkane sulfonates are preferable.

  Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Of these, alkali metal salts such as sodium salt and potassium salt are preferred.

(B) A component can be used 1 type or in mixture of 2 or more types.
In the liquid detergent composition of the present invention, the component (B) preferably contains a linear alkyl benzene sulfonate since the effect of preventing recontamination of the article to be washed is particularly good.
The content of the component (B) is preferably 1 to 15% by mass in the liquid detergent composition, more preferably 2.5 to 10% by mass, and 5 to 10% by mass. Further preferred.
When the content of the component (B) is 1% by mass or more, preferably 2.5% by mass or more, the effect of preventing recontamination of the article to be washed is further improved. In addition, good detergency can be obtained. When the content of the component (B) is 15% by mass or less, preferably 10% by mass or more, sufficient detergency can be obtained. In addition, rinsability is improved. Furthermore, gelation of the liquid detergent composition on the liquid surface with time does not easily occur, and a film is hardly formed on the liquid surface.

<(C) component>
In the present invention, the component (C) is an enzyme.
By using the component (C) in combination with the component (A) and the component (B), an effect of preventing recontamination of the object to be washed can be obtained. In addition, the cleaning power is improved.

 As the component (C), various types of enzymes that can be generally used in the liquid detergent composition can be used, and examples thereof include cellulase, protease, amylase, lipase, and mannanase. Of these, cellulase, protease, and mannanase are preferable, cellulase and protease are more preferable, and cellulase is particularly preferable because the effect of preventing recontamination of the object to be washed is good.

 Examples of the cellulase include commercially available products such as Carezyme 4500L (trade name, manufactured by Novozymes) and Endulase 5000L (trade name, manufactured by Novozymes).

 Examples of the protease include Evalase 16L Type EX, Sabinase 10 LCC, Sabinase 16L Type EX, Sabinase Ultra 16L, Sabinase Ultra EX, Alcalase 2.5L DX, Recanase 2.5L, Neutase 0.8L, Flavorzyme 1000L (and above Product name; all manufactured by Novozymes); Properase 1600L, Purefect 4000L, Purefect MA 500L, Purefect Prime 4000L, Purefect OX 4000L (above, product names; both manufactured by Genencor); MED-UM, MED-01 (above, Commercial products such as trade name; manufactured by Nippon Shokubai Co., Ltd.).

  Examples of the amylase include Termamyl Ultra 300L, Duramyl, Stainzyme, Promozyme 200L (above, trade names: all manufactured by Novozymes); Maxamyl (trade name, manufactured by Genencore), pullulanase Amano (trade name, manufactured by Amano Pharmaceutical), Commercial products such as DB-250 (trade name, Aerobacteraerogenes ATCC 9621-derived pullulanase: Crude or crystallized product, manufactured by Seikagaku Corporation) can be mentioned.

  Examples of the lipase include commercially available products such as Lipex 160L and Lipex 200L (above, trade names: all manufactured by Novozymes).

 Examples of mannanase include commercially available products such as Manaway 4.0L (trade name, manufactured by Novozymes).

(C) component can be used 1 type or in mixture of 2 or more types.
In the liquid detergent composition of the present invention, the component (C) preferably contains cellulase because the effect of preventing recontamination of the article to be cleaned is particularly good. A preferred commercially available product is Endolase 5000L (trade name, manufactured by Novozymes).
The content of the component (C) is preferably 0.1 to 3% by mass, more preferably 0.1 to 2% by mass, and preferably 0.1 to 1% by mass in the liquid detergent composition. More preferably.
When the content of the component (C) is 0.1% by mass or more, the effect of preventing recontamination of the article to be washed is further improved. In addition, good detergency can be obtained. When the content of the component (C) is 3% by mass or less, sufficient detergency can be obtained. It is also economically advantageous.

Moreover, in the liquid cleaning composition of this invention, the ratio of the said (A) component is 15-50 mass%, the ratio of the said (B) component is 1-15 mass%, and said (C ) The proportion of the component is preferably 0.1 to 3% by mass. When the proportion of the three components (A) to (C) is within the above range, the effect of preventing recontamination of the article to be washed is more excellent. Also, the cleaning effect is good.
The reason why such an effect can be obtained is not clear, but if the ratio of the three components (A) to (C) is within the above range, dirt attached to the back of the fibers of the object to be washed is removed. This is presumed to be because the dispersibility of the dirt once detached from the fibers of the article to be washed in the washing liquid is remarkably improved, so that the dirt is less likely to be deposited on the fibers.

<Optional component>
In the liquid detergent composition of the present invention, various optional components may be added to the liquid detergent composition of the present invention as necessary in addition to the above-mentioned components (A), (B), and (C) as long as the effects of the present invention are not impaired. It can mix | blend suitably.
For example, higher fatty acids, viscosity reducing agents (lower alcohols such as ethanol and isopropyl glycol; glycols such as ethylene glycol and propylene glycol), stabilizers (sodium benzoate, citric acid, sodium citrate, polyhydric alcohol, Polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc.), alkali agents (monoethanolamine, diethanolamine, alkanolamines such as triethanolamine), metal ion scavengers (malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid) , Citric acid or salts thereof), texture improver such as silicone, preservative, hydrotrope agent, fluorescent agent, dye transfer inhibitor, pearl agent, antioxidant (dibutylhydroxytoluene, distyrenated crezo) , Sodium sulfite, sodium hydrogen sulfite, etc.), additives such as general-purpose dyes and pigments, flavoring agents or emulsifying agents, solvents (water, alcohol, polyethylene glycol, etc.), pH adjusters, etc. It is done.

In the liquid detergent composition according to the present invention, examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide and alkanol Examples include amines, ammonia, and the like, and sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamines are preferable from the viewpoint of the temporal stability of the liquid detergent composition.
A pH adjuster can be used 1 type or in mixture of 2 or more types.
The pH adjuster is appropriately added in an amount that adjusts the pH of the liquid detergent composition at 25 ° C., preferably 5 to 9.

The pH of the liquid detergent composition of the present invention is preferably 5 to 9 at 25 ° C., more preferably 5 to 8. When the pH is 5 to 9, even when the liquid detergent composition is stored for a long period of time, the stability over time can be kept good.
The adjustment of the pH can be controlled, for example, by adding a certain amount of sulfuric acid, potassium hydroxide or the like. In addition, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide or sodium hydroxide can be further added for fine adjustment of pH.
In the present invention, the pH of the liquid detergent composition (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

The liquid detergent composition of the present invention can be produced based on a conventional method, preferably using water as a solvent.
The usage method is a normal usage method, that is, a method in which the liquid detergent composition of the present invention (product of the present invention) is poured into water together with the laundry during washing, and the product of the present invention is directly applied to mud and sebum soil. And a method of immersing clothing by dissolving the product of the present invention in water in advance. 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 decreased to substantially half or less rather than the usage-amount of the conventional liquid detergent composition.

As described above, according to the present invention, it is possible to provide a liquid detergent composition excellent in the effect of preventing recontamination of an object to be washed.
Even if the liquid detergent composition of the present invention contains a POE type nonionic surfactant, the effect of preventing recontamination of the washing object in washing using a drum-type washing machine having a low bath ratio It has excellent cleaning effect. Therefore, the liquid detergent composition of the present invention can be suitably used particularly for a drum-type washing machine having a low bath ratio.
In addition, the liquid detergent composition of the present invention has good liquid stability and excellent rinsing properties.
The liquid detergent composition of the present invention is particularly suitable for clothing.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. However, Examples 7 to 11 are reference examples.

≪Manufacture of liquid detergent composition≫
A liquid detergent composition having the composition shown in Table 1 was produced as follows according to a conventional method.
First, the component (A) was placed in a cylindrical glass bottle (diameter 50 mm, height 100 mm) containing a 2 cm stir bar. Next, the mixed solution of (C) component and arbitrary components was put, and the stirring bar was stirred at 400 rpm. Next, the component (B) was added and mixed with stirring. Thereafter, purified water is added so that the total amount (the total amount is 100 parts by mass) is 95 parts by mass, and after stirring and mixing, the pH is adjusted, and ethanol is added so that the total amount becomes 100% by mass. In addition, a liquid detergent composition was produced.
The pH was adjusted by adding an appropriate amount of a pH adjuster (potassium hydroxide or sulfuric acid) so that the pH of the liquid detergent composition at 7.0 was 7.0.
In addition, the unit of the compounding quantity in Table 1 is mass%, and shows the pure amount conversion amount.
Below, the measuring method of the narrow rate of (A) component and the component shown in the table | surface are demonstrated.

<Method for Measuring Narrow Rate of Component (A)>
About the (A) component shown below, distribution of the ethylene oxide adduct from which the addition mole number of ethylene oxide differs was measured on the following measurement conditions. And the narrow rate (mass%) of (A) component was computed based on the said Numerical formula (S).
[Conditions for measuring the distribution of ethylene oxide adducts 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 ° C

<Description of components shown in the table>.
· (A) component _{a-1: C 11 H 23} CO (OC 2 H 4) 15 OCH 3, narrow of 45 wt%; synthetic.

However, as a-1, a synthetic product produced according to Production Example 1 in Examples described in JP-A No. 2000-144179 was used.
That is, alumina hydroxide / magnesium hydroxide (product name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O, at 600 ° C. for 1 hour in a nitrogen atmosphere A 4-liter autoclave containing 2.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst obtained by calcining under pressure, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, and 350 g of lauric acid methyl ester The catalyst was reformed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and 1079 g of ethylene oxide was introduced while the temperature was maintained at 180 ° C. and the pressure was maintained at 3 atm, and the reaction was carried out with 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 the catalyst was filtered off to obtain a-1.
By controlling the amount of alkali added to the catalyst, a-1 having a narrow rate of 45% by mass was obtained.
The narrow ratio was calculated by measuring the distribution of ethylene oxide adducts having different numbers of moles of ethylene oxide added in the obtained synthetic product by the above-described method for measuring the narrow ratio.

-(B) component b-1: LAS, linear alkyl (C10-C14) benzenesulfonic acid [product name: Raipon LH-200 (LAS-H pure part 96 mass%)] made by Lion Corporation The compound neutralized with a 48% by mass aqueous sodium hydroxide solution during preparation of the surfactant composition and the compound neutralized with a 48% by mass aqueous potassium hydroxide solution instead of neutralizing with the sodium hydroxide Mixed at a ratio of 2: 1; average molecular weight 322. The compounding quantity in a table | surface shows the value (mass%) as these mixtures.

  b-2: SAS, secondary alkanesulfonic acid Na, manufactured by Clariant Japan, trade name “SAS30”.

  b-3: AES, carbon number C12-13 sodium polyoxyethylene alkyl ether sulfate (average added mole number of ethylene oxide 2); synthetic product.

[Method for synthesizing b-3 (AES)]
In a 4 liter autoclave, Neodol 23 alcohol [trade name, manufactured by Shell Chemicals; C12, 13 alcohol (mixture with a mass ratio of 1/1 C12 alcohol to C13 alcohol), branching ratio 20% by mass 400 g and potassium hydroxide catalyst 0.8 g were charged, the inside of the autoclave was purged with nitrogen, and the temperature was increased while stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide 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, 67 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain b-3 (AES).

-(C) component c-1: Endolase 5000L (trade name, manufactured by Novozymes).
c-2: Evalase 16L Type EX (trade name, manufactured by Novozymes).
c-3: Purefect Prime 4000L (trade name, manufactured by Genencor Corporation).
c-4: Manaway 4.0L (trade name, manufactured by Novozymes).

Optional component PEG: polyethylene glycol, trade name “PEG # 1000”, manufactured by Lion Chemical Co., Ltd .; concentration (AI) = 60 mass%.
DEA: Diethanolamine, manufactured by Nippon Shokubai Co., Ltd .; concentration (AI) = 100% by mass.
Citric acid 3Na · 2H ₂ O: trisodium citrate dihydrate, manufactured by Fuso Chemical Industries, Ltd .; concentration (AI) = 100 mass%.
Ethanol: Trade name “95 vol% synthetic ethanol”, manufactured by NEDO.
Sodium benzoate: trade name “Sodium benzoate”, manufactured by Fushimi Pharmaceutical Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.
Potassium hydroxide: Asahi Glass Co., Ltd .; concentration (AI) 48 mass%.
Purified water: Uses ion exchange water.

≪Evaluation method≫
About the obtained liquid cleaning composition, it evaluated by the method and evaluation criteria shown below, and the result was written together in Table 1.

<Evaluation of recontamination prevention effect>
1) Preparation of evaluation fabric (pretreatment)
Using a two-tub washing machine (product name: CW-C30A1-H, manufactured by Mitsubishi Electric; the same shall apply hereinafter) V. After washing 1 kg of D skin shirt (Fujibo Apparel Co., Ltd.) twice with 40% to 50 ° C. tap water in a 20% by weight nonionic surfactant aqueous solution (standard concentration of detergent), An evaluation cloth was prepared by thoroughly rinsing with tap water and drying at room temperature.
The above pre-treatment was repeated twice: 30 times bath ratio, washing condition: washing 10 minutes → water rinsing 10 minutes, and an alcohol with an average of 15 moles of ethylene oxide added per mole of lauryl alcohol as a nonionic surfactant. Ethoxylate (trade name: LMAO, manufactured by Lion Chemical) was used.

2) Evaluation of recontamination degree [Method of use test]
The liquid detergent composition of each example was placed in a container (evaluation detergent housed in a polyethylene container having a capacity of 1000 mL and the evaluation cloth), and the evaluation cloth was washed together during normal washing. The evaluation fabric was used, and the use test which collects it at the time of washing 20 times repeatedly was done.
Such a use test was conducted in 20 households (for example, 80 households with 4 detergent samples) for each detergent sample for evaluation.
In addition, when washing, a drum-type washing machine was used as a type of washing machine, and a softener product (the type thereof was not limited) was used.

[Measurement of recontamination degree ΔZ]
The recontamination degree ΔZ was measured as follows.
The evaluation cloth before the start of the use test in each home was used as a blank (control).
About the evaluation cloth collect | recovered by this blank evaluation cloth and the use test, Z value (reflectance) was measured using the colorimetric color difference meter (Nippon Denshoku Industries Co., Ltd. product name: 1001-DP; lens 30phi). . At this time, a filter that blocks the influence of the fluorescent agent must be attached.
The Z value was measured at a total of five locations, including the four corners of the front of the evaluation cloth (skin shirt) and the center at the back, and the average value thereof was taken as the Z value of each evaluation cloth.
From these Z values, ΔZ was determined from the following equation.
ΔZ = (Z value of blank evaluation cloth) − (Z value of evaluation cloth after use test)
Of the ΔZ values in the evaluation cloths collected from 20 households per sample of the detergent for evaluation, the average value of the remaining 18 data, excluding the maximum and minimum values, is the recontamination degree ΔZ of the evaluation cloths, Based on the following evaluation criteria, the effect of preventing recontamination was evaluated.
Evaluation criteria A: Recontamination degree ΔZ is less than 6 and the level at which recontamination is not noticeable at home.
○: Recontamination degree ΔZ is 6 or more and less than 9, and although recontamination is noticeable, it is an acceptable level.
Δ: Re-contamination degree ΔZ is 9 or more and less than 12, and the level of re-contamination is noticeable.
X: Recontamination degree ΔZ is 12 or more, and it is clearly understood that it is dark.

As is clear from the above results, it was confirmed that the liquid detergent compositions of Examples 1 to 11 according to the present invention were excellent in the effect of preventing recontamination of the objects to be cleaned.
On the other hand, among the components (A) to (C), the comparative example 2 lacking the component (C), the comparative example 3 lacking the component (B), and the comparative example 1 lacking both the component (B) and the component (C). It was confirmed that any liquid detergent composition has a low effect of preventing recontamination of the object to be cleaned.

<Evaluation of liquid stability>
150 ml of the liquid detergent composition of each example was placed in a cylindrical glass bottle having a diameter of 50 mm and a height of 100 mm, and the lid was closed and sealed. In this state, it was stored in a thermostatic chamber at 25 ° C., and the appearance of the liquid after 24 hours was visually observed to evaluate the liquid stability of the liquid detergent composition.
In addition, in the liquid detergent composition of Example 1, an example in which the pH of the liquid detergent composition was adjusted to 9.5 was made the liquid detergent composition of Comparative Example 4, and the evaluation of the liquid stability was carried out in Examples. 1 to 11 and Comparative Examples 1 to 4.
As a result, all of the liquid detergent compositions of Examples 1 to 11 had a uniform appearance, and it was confirmed that the liquid stability was good.
On the other hand, although the liquid detergent compositions of Comparative Examples 1 to 3 had good liquid stability, the liquid detergent composition of Comparative Example 4 was found to be separated, and the liquid stability was poor.

Claims (3)

Nonionic surface active agents represented by the following general formula (I) and (A), a linear alkyl benzene sulfonate contains a cellulase, wherein the pH is 5-9 der Rukoto at 25 ° C. Liquid detergent composition.

[In Formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 9 to 21 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is carbon. N represents an alkyl group having 1 to 3; n represents an average number of added moles of alkylene oxide, and is 5 to 30. ] In the nonionic surfactant (A) represented by the general formula (I), a narrow ratio represented by the following formula (S), which indicates a distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide. The liquid detergent composition according to claim 1 , wherein is 20 to 45% by mass .

[ _Wherein n _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct. i represents the number of added moles of alkylene oxide. Yi represents the proportion (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the entire alkylene oxide adduct. ] The ratio of the nonionic surfactant (A) represented by the general formula (I) is 15 to 50% by mass, the ratio of the linear alkylbenzene sulfonate is 1 to 15% by mass, and the ratio of cellulase The liquid detergent composition according to claim 1 or 2 , wherein is 0.1 to 3% by mass.