JP2020084141A - Liquid detergent composition for fiber product - Google Patents

Abstract

To add excellent detergency and excellent liquid stability to a liquid detergent composition under a situation that a liquid detergent composition less in content of a surfactant and excellent in detergency is required with consideration to environment, however detergency is reduced when content of the surfactant is just reduced, and the liquid detergent composition is required to hardly generate deposition, separation or the like (to be high in liquid stability).SOLUTION: A liquid detergent composition contains (A) component: an anionic surfactant (excluding higher fatty acid salt and a salt thereof) of 1 to 15 mass%, (B) component: amylase of 0.05 to 3 mass%, (C) component: an antioxidant, (D) component: a nonionic surfactant, and having total of the (A) component and the (D) component of 10 to 26 mass% and pH at 25°C of over 7.SELECTED DRAWING: None

Description

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

As a detergent composition for a textile product for which clothing or the like is to be washed, there are generally two types, a powder detergent composition and a liquid detergent composition. Demand for liquid detergent compositions has been increasing because there is no risk of undissolved liquid detergent and it can be applied to clothing and the like.
In the detergent composition, the surfactant acts as the main washing component, and various components such as enzymes are blended. Enzymes play an important role as components that exhibit various performances even in small amounts.

There is a so-called "compact-type" liquid detergent composition that contains a surfactant in a high concentration and is used in a small amount in consideration of convenience at the time of purchase. The compact type liquid detergent composition contains a small amount of water because the surfactant is contained in a high concentration. Therefore, when an enzyme is added to a compact liquid detergent composition, the enzyme is likely to be precipitated or denatured, and the storage stability is further reduced.
To address these problems, Patent Document 1 discloses that 40% by mass or more of a nonionic surfactant, at least one component selected from the group consisting of aminocarboxylic acids or salts thereof, and phosphonic acids or salts thereof, and α-hydroxy. -A liquid detergent composition containing a monocarboxylic acid or a salt thereof and an enzyme such as a protease has been proposed.

International Publication No. 2012/144601

In recent years, in consideration of the environment, there has been a demand for a liquid detergent composition containing a small amount of a surfactant and having excellent detergency.
However, if the content of the surfactant is simply reduced, the detergency is reduced.
In addition, the liquid detergent composition is required to be less likely to cause precipitation, separation, gelation, etc. (high liquid stability).
Then, this invention aims at the liquid detergent composition which is excellent in detergency and liquid stability.

The present invention has the following aspects.
[1] Component (A): 1 to 15% by mass of anionic surfactant (excluding higher fatty acid and its salt),
(B) component: amylase 0.05 to 3% by mass,
Component (C): an antioxidant,
Component (D): nonionic surfactant,
Containing
The total of the component (A) and the component (D) is 10 to 26% by mass,
A liquid detergent composition for textiles, having a pH at 25° C. of greater than 7.
[2] The liquid detergent composition for a textile product according to [1], wherein the mass ratio represented by the component (D)/the component (A) is 0.5 to 10.
[3] The liquid detergent composition for a textile product according to [1] or [2], wherein the mass ratio represented by the component (B)/the component (C) is 0.06 to 250.

[4] The liquid detergent for a textile product according to any one of [1] to [3], wherein the mass ratio represented by the component (A)/the component (B) is 0.33 to 300. Composition.
[5] The liquid detergent composition for a textile product according to any one of [1] to [4], wherein the content of the component (C) is 0.005 to 1% by mass.
[6] Liquid cleaning for textiles according to any one of [1] to [5], wherein the mass ratio represented by the component (C)/the component (A) is 0.0004 to 0.65. Agent composition.

The liquid detergent for textiles of the present invention has excellent detergency and liquid stability.

(Liquid cleaner)
The liquid detergent composition for textile products of the present invention (hereinafter, may be simply referred to as a liquid detergent composition) contains components (A) to (D).

<(A) component>
The component (A) is a higher fatty acid salt and an anionic surfactant excluding the salt.
As the component (A), an anionic surfactant that has been conventionally used in liquid detergent compositions can be used. For example, linear alkyl (C8-16) benzenesulfonic acid or a salt thereof; α-olefin (C10-20) sulfonic acid or a salt thereof; linear or branched alkyl (C10-20) sulfuric acid ester or a salt thereof. Polyoxyalkylene (on average 1 to 10 mol of oxyethylene) alkyl (C10-20) ether sulfate or salt thereof (that is, polyoxyethylene alkyl ether sulfate salt); Polyoxyalkylene (on average 1 to 10 mol of oxy) Ethylene) alkenyl (C10-20) ether sulfate or salt thereof (that is, polyoxyethylene alkenyl ether sulfate salt); alkanesulfonic acid having an alkyl group (C10-20) or salt thereof; α-sulfo fatty acid (C10 20) Esters or salts thereof and the like can be mentioned. Of these, linear alkylbenzene sulfonic acid or a salt thereof is preferable from the viewpoint of protein denaturing action which is a part of food stains. "COO-OO" in () represents the carbon number.
Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolammonium and diethanolammonium. The component (A) may be a single type or a combination of two or more types.
As the component (A), other than the above, for example, an alkyl ether carboxylic acid or a salt thereof, a polyoxyalkylene ether carboxylic acid or a salt thereof, an alkyl amide ether carboxylic acid or a salt thereof, an alkenyl amide ether carboxylic acid or a salt thereof, an acyl Carboxylic acid type anionic surfactants such as aminocarboxylic acid or salts thereof; alkyl phosphate esters or salts thereof, polyoxyalkylene alkyl phosphate esters or salts thereof, polyoxyalkylene alkylphenyl phosphate esters or salts thereof, glycerin fatty acid ester Examples thereof include phosphate ester type anionic surfactants such as monophosphate esters or salts thereof.
A commercial item may be used for these anionic surfactants.

The content of the component (A) is 1 to 15% by mass, preferably 3 to 10% by mass, and more preferably 4 to 6% by mass, based on the total mass of the liquid detergent composition. When the content of the component (A) is at least the above lower limit, the detergency for proteins that are a part of food stains can be further enhanced. When the content of the component (A) is at most the above upper limit value, the liquid stability of the liquid detergent composition can be further enhanced.

<(B) component>
The component (B) is amylase. By containing the component (B), the liquid detergent composition can enhance the detergency against starch which is a part of food stains.
The component (B) may be any enzyme that hydrolyzes α-1,4 bonds such as starch and glycogen. As the component (B), α-amylase, β-amylase, α-glucosidase, glucoamylase; glucoamylase, pullulanase, isoamylase, amylo-1,6 that hydrolyzes α-1,6 bonds such as starch and glycogen. Examples include glucosidase/4-α-glucanotransferase, oligo-1,6-glucosidase and the like.
These amylases may be used alone or in combination of two or more.

Examples of the commercially available enzyme (amylase preparation) as the component (B) include Termamyl Ultra 300L, Duramyl 16L, Stainzyme 12L, Promozyme 200L, and Amplify 100P. Medley Core 210L (trade name, mixed enzyme of amylase and protease, manufactured by Novozymes Co., Ltd.); Maxamyl (trade name, manufactured by Genencor Co., Ltd.), pullulanase Amano (trade name, manufactured by Amano Pharmaceutical Co., Ltd.), DB-250 (product) Name, pullulanase derived from Aerobacterium aerogenes ATCC 9621, crude or crystallized product, manufactured by Seikagaku Corporation) and the like. The activity per gram of these amylase preparations is preferably 1 to 800 (kAU/g), more preferably 20 to 600 (kAU/g), and further preferably 50 to 400 (kAU/g).
These amylase preparations may be used alone or in combination of two or more.

The content of the component (B) is 0.05 to 3% by mass, preferably 0.05 to 2% by mass, and more preferably 0.1 to 1% by mass, based on the total mass of the liquid detergent composition. .. When the content of the component (B) is at least the above lower limit value, the detergency can be further enhanced. When the content of the component (B) is at most the above upper limit value, precipitation can be further suppressed and liquid stability can be further enhanced.
The content of the component (B) is the content as a preparation.

The mass ratio (A/B ratio) represented by (A) component/(B) component is preferably 0.33 to 300, more preferably 1.5 to 200, further preferably 4 to 60, and 5 to 30. Is particularly preferable. When the A/B ratio is at least the above lower limit, the content of the component (A) will be sufficient, and the detergency for proteins can be further improved. When the A/B ratio is not more than the above upper limit value, it is possible to further suppress the decrease in the activity of the component (B), and it is possible to further improve the detergency for food stains containing starch and the like.

The amylase activity (AU/g) per 1 g of the liquid detergent composition is preferably 0.0005 to 24 (kAU/g), more preferably 0.001 to 16 (kAU/g), and 0.05 to 8 (kAU/g) is more preferable.

≪Amylase activity≫
Amylase activity is measured, for example, by the following method.
In the present specification, the “amylase activity unit (AU)” is the activity of α-amylase hydrolyzing the α-1,4-glucoside bond in starch. The amylase activity unit (AU) is a value converted from the absorbance calibration curve (supplied with the reagent) prepared by the standard enzyme of known activity "Phadebas human α-amylase control". Note that 1 U/L is 1 AU.

[Method for measuring amylase activity Ea per 1 g of detergent composition]
The amylase activity Ea per 1 g of the detergent composition is a value measured by the following method, for example. The amylase activity Ea is measured by using "Phadebas amylase test" (manufactured by Magle Life Sciences).

A standard enzyme solution diluted to each concentration is used for preparing the calibration curve. To a test tube containing the standard enzyme solution, 1 tablet containing 5 g of buffer solution and a blue starch polymer as a substrate is added. The buffer solution is 20 g of sodium sulfite, 5 g of potassium dihydrogen phosphate, 10 g of disodium hydrogen phosphate dodecahydrate, 0.05 g of calcium chloride dihydrate, and 1 mL of Brij35 (30% aqueous solution) with deionized water. This is a mixed solution of 1 L.
The tablets are mixed until they disintegrate, and the temperature is accurately kept in a constant temperature bath at 37°C for 15 minutes to carry out an enzyme reaction. After adding 1 mL of a 1 mol/L sodium hydroxide solution to stop the enzymatic reaction, insoluble components are filtered off with a filter paper to remove the filtrate. A calibration curve is obtained by measuring the absorbance of the collected filtrate at a wavelength of 620 nm.

0.1 g of the liquid detergent composition was diluted 300 times with a buffer solution, and this solution was used as a sample solution. The buffer solution was 20 g of sodium sulfite, 5 g of potassium dihydrogen phosphate, 10 g of disodium hydrogen phosphate dodecahydrate, 0.05 g of calcium chloride dihydrate, and 1 mL of Brij35 (30% aqueous solution) with deionized water. This is a mixed solution of 1 L.
To 1 g of the sample solution, 5 g of the above-mentioned buffer solution and 1 tablet of Fadebas amylase test (manufactured by Magle Life Sciences) were added, stirred with a vortex mixer for 10 seconds, and then allowed to stand at 37° C. for 15 minutes to proceed with the enzymatic reaction. Thereafter, 1 g of a 1N sodium hydroxide aqueous solution (manufactured by Kanto Kagaku) was added to the solution, and the reaction was stopped by stirring for 10 seconds with a vortex mixer. Then, this solution is allowed to stand at 37° C. for 15 minutes, insoluble components are filtered with a filter paper, and the filtrate is recovered. The absorbance (absorbance α) at 620 nm of the collected filtrate was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. In order to remove the influence of absorption other than the target component, 1 g of 1N sodium hydroxide aqueous solution was added separately to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, and then 5 g of phosphoric acid aqueous solution and 1 part of Fadebas amylase test 50T were added. Add a tablet, stir for 10 seconds with a vortex mixer, and leave at 37° C. for 15 minutes. Then, the insoluble component of the solution was filtered with a filter paper. The absorbance (absorbance β) of the filtrate at a wavelength of 620 nm is measured using UV-160. Then, the difference between the absorbance α and the absorbance β is obtained. This difference is taken as the absorption value of the detergent composition containing amylase.
Then, the protease activity (AU) per 1 g of the detergent composition is calculated from the concentration calculated based on the calibration curve prepared with the amylase enzyme of known activity.

[Method for measuring activity per gram of amylase preparation]
The activity per 1 g of the component (B) (amylase enzyme preparation) is a value measured by the following method, for example.
0.1 g of amylase enzyme preparation is dissolved in the above buffer solution and the volume is adjusted to 100 mL. 1 mL of this enzyme solution is dissolved in ion-exchanged water and the volume is adjusted to 100 mL to prepare an amylase enzyme preparation aqueous solution having a concentration of 0.001% by mass.
To 1 mL of this amylase enzyme preparation aqueous solution, 5 g of the above-mentioned buffer solution and 1 tablet of Fadebas amylase test (Maggle Life Sciences) were added, and after stirring with a vortex mixer for 10 seconds, the mixture was allowed to stand at 37° C. for 15 minutes for enzymatic reaction. Proceed. Then, 1 g of a 1N sodium hydroxide aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) was added to the above solution, and the reaction was stopped by stirring for 10 seconds with a vortex mixer. Then, this solution is allowed to stand at 37° C. for 15 minutes, insoluble components are filtered with a filter paper, and the filtrate is recovered. The absorbance at 620 nm (absorbance a) of the collected filtrate is measured with an UV-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. In order to remove the influence of absorption other than the target component, 1 g of 1N sodium hydroxide aqueous solution was added separately to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, and then 5 g of phosphoric acid aqueous solution and 1 part of Fadebas amylase test 50T were added. Add a tablet, stir for 10 seconds with a vortex mixer, and leave at 37° C. for 15 minutes. The insoluble component of the solution is filtered with filter paper. The absorbance (absorbance b) of the filtrate at a wavelength of 620 nm is measured by UV-160. Then, the difference between the absorbance a and the absorbance b is obtained. This difference is used as the absorbance value of the amylase preparation.
The amylase activity (AU) per 1 g of the component (B) is calculated from the concentration calculated based on the calibration curve prepared with the amylase enzyme having a known activity.

<(C) component: antioxidant>
The component (C) is an antioxidant. By containing the component (C), the liquid detergent composition can suppress the decrease in the activity of the component (B) and enhance the detergency. In addition, since the liquid detergent composition contains the component (C), it becomes difficult to absorb oxygen in the head space of the container that contains the liquid detergent composition. That is, it is possible to suppress a decrease in oxygen concentration in the head space. Furthermore, when the liquid detergent composition contains a pigment preparation, it is possible to suppress discoloration when the liquid detergent composition is exposed to light.

Examples of the component (C) include ascorbic acid, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), distyrenated cresol, sodium sulfite, and sodium hydrogen sulfite. Among them, the component (C) preferably contains at least one selected from the group consisting of ascorbic acid, BHT and BHA, and more preferably BHT. BHT is excellent in stabilizing the enzyme, and is also excellent in reducing the oxygen concentration in the headspace and suppressing fading.
These (C) components may be used alone or in combination of two or more.

The content of the component (C) is 0.005 to 1% by mass, preferably 0.008 to 0.8% by mass, and 0.01 to 0.6% with respect to the total mass of the liquid detergent composition. Mass% is more preferable. When the content of the component (C) is within the above range, a decrease in the activity of the component (C) can be suppressed and the detergency can be enhanced.

The mass ratio (B/C ratio) represented by the (B) component/(C) component is preferably 0.06 to 250, more preferably 0.2 to 100, further preferably 0.2 to 30. -20 are especially preferable. When the B/C ratio is at least the above lower limit, the content of the component (B) will be sufficient, and the cleaning power for food stains containing starch and the like can be further improved. When the B/C ratio is at most the above upper limit value, the component (C) can further suppress the decrease in the activity of the component (B), and the cleaning power for food stains containing starch and the like can be further improved.

The mass ratio (C/A ratio) represented by the (C) component/(A) component is preferably 0.0004 to 0.65, more preferably 0.0008 to 0.25, and 0.002 to 0. 15 is more preferable, and 0.01 to 0.12 is particularly preferable. When the C/A ratio is at least the above lower limit value, the content of the component (C) will be sufficient, the decrease in the activity of the component (B) will be suppressed further, and the cleaning power for food stains containing starch and the like will be further improved. Can be improved. When the C/A ratio is not more than the above upper limit value, the content of the component (A) will be sufficient, and the cleaning power for protein stains can be further improved.

<(D) component>
The component (D) is a nonionic surfactant. Examples of the nonionic surfactant include polyoxyalkylene type nonionic surfactants represented by the following general formula (d1).

^{_{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (d1)
(In the formula (d1), R ¹¹ represents a hydrocarbon group having 8 to 18 carbon atoms, X represents O, COO or CONH, R ¹² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. Represents an alkenyl group of 2 to 6. s represents an average number of repetitions of EO and is a number of 6 to 20. t represents an average number of repetitions of PO and is a number of 0 to 6. EO is an oxyethylene group. , PO represents an oxypropylene group, and EO and PO may be mixed and arranged.)

In the formula (d1), R ¹¹ is preferably a hydrocarbon group having 10 to 18 carbon atoms because it has good detergency, and may be linear or branched. Examples of the hydrocarbon group include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides.
As the alkyl group for R ¹² , an alkyl group having 1 to 3 carbon atoms is preferable. As the alkenyl group for R ^12, an alkenyl group having 2 to 3 carbon atoms is preferable. Further, X is preferably O or COO.

In the formula (d1), when X is O, the nonionic surfactant is an alkyl ether type nonionic surfactant. When X is O, R ¹¹ is preferably a hydrocarbon group having 10 to 18 carbon atoms from the viewpoint of improving detergency. Further, R ¹¹ may have an unsaturated bond. Further, s is preferably 10 to 20, more preferably 14 to 18, and R ¹² is preferably a hydrogen atom.

In the formula (d1), when X is COO, the nonionic surfactant is a fatty acid ester type nonionic surfactant. When X is COO, R ¹¹ is preferably a hydrocarbon group having 9 to 18 carbon atoms, and more preferably a hydrocarbon group having 11 to 18 carbon atoms, from the viewpoint of further improving the detergency. Further, R ¹¹ may have an unsaturated bond. Further, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

In the formula (d1), s is a number of 6 to 20, preferably 10 to 18, and more preferably 14 to 18. When s is within the above range, the cleaning power can be further improved.
In formula (d1), t is a number of 0 to 6, preferably 0 to 3, and more preferably 0. When t is within the above range, the liquid stability at high temperature tends to be good.
In [(EO) _s /(PO) _t ] in the formula (d1), EO and PO may be mixed and arranged. When EO and PO are mixedly arranged, they may be in a random shape or a block shape.

In the nonionic surfactant represented by the formula (d1), the distribution of the repeating number EO of EO (that is, the average addition mole number of ethylene oxide) or the repeating number t of PO (that is, the average addition mole number of propylene oxide) is It is not particularly limited as long as it has the effects of the present invention. The distribution of the number of added moles varies depending on the reaction method for producing the nonionic surfactant. For example, the distribution of the number of moles of added ethylene oxide or propylene oxide is determined by using ethylene oxide or propylene oxide as a hydrocarbon group raw material (primary or secondary higher alcohol) using an alkaline catalyst such as sodium hydroxide or potassium hydroxide. , Higher fatty acids, higher fatty acid amides, etc.) tend to have a relatively wide distribution. In addition, specific alkoxylation such as magnesium oxide added with metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-6-15038. When ethylene oxide or propylene oxide is added to the hydrocarbon group raw material using a catalyst, the distribution tends to be relatively narrow.

The component represented by formula (d1) may be a commercially available product. Specific examples of commercially available products include Diadol (registered trademark) manufactured by Mitsubishi Chemical (trade name, C13 and C represent carbon numbers. The same applies hereinafter), Neodol (registered trademark) manufactured by Shell (trade name, C12). And a mixture of C13) and Safol (registered trademark) 23 (trade name, a mixture of C12 and C13) manufactured by Sasol Co., etc., to which 12 mole equivalents or 15 mole equivalents of ethylene oxide have been added; A natural alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by P&G Co., to which 12 mol or 15 mol of ethylene oxide has been added; Examples thereof include those obtained by adding 15 moles of ethylene oxide to the primary alcohol (SOFTANOL (registered trademark) 150 (trade name) manufactured by Nippon Shokubai Co., Ltd.). Further, 15 mol of ethylene oxide was added to coconut fatty acid methyl (lauric acid/myristic acid=8/2) using an alkoxylation catalyst (polyoxyethylene coconut fatty acid methyl ester (15 mol EO)). ) Is mentioned.
These (D) components may be used alone or in combination of two or more.

From the viewpoint of improving the detergency of the liquid detergent composition, the component (D) is preferably a nonionic surfactant represented by the formula (d1), and among them, in the formula (d1), X is O and s is A polyoxyethylene alkyl ether having 6 to 20 and t of 0 is more preferable. From the viewpoint of sebum cleansing power, in the formula (d1), the average repetition number s of EO is preferably 10 to 20, and more preferably 14 to 18. If s is large, the stability of the component (B) tends to deteriorate. Therefore, from the viewpoint of further suppressing the decrease in the activity of the component (B), the average repetition number s of EO is preferably 6 to 16, and more preferably 8 to 16.

The content of the component (D) is preferably 6 to 20% by mass, more preferably 7 to 16% by mass, and even more preferably 8 to 12% by mass, based on the total mass of the liquid detergent composition. When the content of the component (D) is at least the above lower limit, the liquid stability can be further increased, and the cleaning power for food-derived stains can be easily improved. When the content of the component (D) is at most the above upper limit, gelation of the liquid detergent composition can be suppressed, other components can be sufficiently contained, and the synergistic effect with the component (A) is easily obtained.

The total amount (AD total amount) of the component (D) and the component (A) is 10 to 26% by mass, more preferably 12 to 18% by mass, based on the total mass of the liquid detergent composition. When the total amount of AD is equal to or more than the above lower limit, the cleaning power for sebum stains and proteins can be further improved. When the total amount of AD is not more than the above upper limit value, the liquid stability of the liquid detergent composition can be further improved and the rinsability can be enhanced. When the rinsability is increased, the number of rinsing treatments after the cleaning treatment can be reduced.

The mass ratio (D/A ratio) represented by component (D)/component (A) is preferably 0.5 to 10, more preferably 1 to 10, and even more preferably 1.5 to 5. When the D/A ratio is at least the above lower limit, it is possible to further suppress the decrease in the activity of the component (B), and it is possible to further improve the detergency for food stains containing starch and the like. When the D/A ratio is less than or equal to the above upper limit value, the cleaning power against protein stains can be further improved.

<Arbitrary ingredients>
The liquid detergent composition may contain optional components other than the components (A) to (D). As the optional component, water, a surfactant (optional surfactant) excluding the components (A) and (D), a chelating agent, an enzyme (optional enzyme) other than the component (B), an antibacterial agent, an alkaline agent, a chelate Agents, hydrotropes, fragrances, pigments and the like.

<<water>>
The liquid detergent composition may contain water. The content of water is preferably 60 to 90% by mass, more preferably 70 to 90% by mass, and even more preferably 75 to 85% by mass, based on the total mass of the liquid detergent composition.

≪Optional surfactant≫
Examples of the optional surfactant include higher fatty acids or salts thereof (higher fatty acids (salts)), cationic surfactants, amphoteric surfactants, and the like.
The "higher fatty acid" is a fatty acid having 8 to 22 carbon atoms. By containing a higher fatty acid (salt), the liquid detergent composition can have improved rinsability. When the rinsability is increased, the number of rinsing treatments after the cleaning treatment can be reduced.
When a higher fatty acid (salt) is blended, the liquid stability tends to decrease. When the pH of the liquid detergent composition exceeds 7, the liquid stability can be improved.
As the higher fatty acid, a chain monocarboxylic acid having 8 to 18 carbon atoms is preferable. The higher fatty acid is represented by the following formula (1).

R ¹ -COOH...(1)
[In the formula (1), R ¹ is an aliphatic hydrocarbon group having 7 to 17 carbon atoms. ]

In the formula (1), the aliphatic hydrocarbon group for R ¹ may be linear or branched. R ¹ is preferably a linear or branched alkyl group or a linear or branched alkenyl group.
The carbon number of R ¹ is 7 to 17, preferably 11 to 17. When the carbon number of R ¹ is at least the above lower limit value, the recontamination preventing effect is enhanced. When the carbon number of R ¹ is not more than the above upper limit value, the solubility in water is increased.

Examples of the salt form of the higher fatty acid (salt) include an alkali metal salt, an alkaline earth metal salt, an amine salt or an ammonium salt. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the alkaline earth metal salt include calcium salt and magnesium salt. Examples of the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.
These higher fatty acids (salts) may be used alone or in combination of two or more. The higher fatty acid (salt) may be a mixture having a single chain length or a mixture having two or more chain lengths.
The higher fatty acid (salt) preferably contains coconut fatty acid or a salt thereof.

The content of the higher fatty acid (salt) is preferably 0.5 to 3% by mass, more preferably 0.7 to 2% by mass, and 0.8 to 1.5 with respect to the total mass of the liquid detergent composition. Mass% is more preferable. When the content of the higher fatty acid (salt) is at least the above lower limit value, the rinsability can be further enhanced. When the content of the higher fatty acid (salt) is not more than the above upper limit value, the liquid stability can be further enhanced.

<<Chelating agent (sequestering agent)>>
Examples of the chelating agent include organic chelating agents. As the chelating agent, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethyl Ethylene tetraamine hexaacetic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, trisodium methylglycinediacetic acid, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1, Organic phosphonic acid derivatives such as 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetraxymethylenesulfonic acid or salts thereof. Etc. Of these, citric acid and trisodium methylglycine diacetate are more preferable from the viewpoint of low temperature stability. The chelating agent may be a single type or a combination of two or more types.

≪Arbitrary enzyme≫
When the liquid detergent composition contains an optional enzyme, sebum-cleansing power and protein-cleansing power can be further improved.
Examples of the arbitrary enzyme include protease, lipase, cellulase, mannanase, cellulase and the like. As the optional enzyme, a protease is more preferable from the viewpoint of proteolysis which is a part of food stains.

As the protease, a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease, is preferable.
In general, a preparation containing a protease (protease preparation) is commercially available. When preparing a liquid detergent, a protease is usually added using this protease preparation.
Examples of the protease preparation include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type Alex 2.5L, 2.5L, 2.5L, 2.5L, and 2.5L, which are available from Novozymes. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L Progress Uno 100L, Medley Core 210L (mixed enzyme of amylase and protease); trade name Purafect L, Purafect O. ..

Examples of the lipase preparation include Lipex 100L and Lipolase 100L, which are trade names available from Novozymes.

As the cellulase preparation, for example, Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (product name, manufactured by Novozymes), Endolase 5000L (product name, manufactured by Novozymes), Cellclean 4500T (product name, Novozymes). Manufactured by the company) and the like.

As the mannanase preparation, for example, the trade name Mannaway 4L available from Novozymes, etc. may be mentioned.

These arbitrary enzymes may be used alone or in combination of two or more.
The content of the optional enzyme is preferably 0.01 to 1.5% by mass with respect to the total mass of the liquid detergent composition as an enzyme preparation. The content of the optional enzyme is the content as a preparation.

<< antibacterial agent >>
The liquid detergent composition can impart antibacterial performance by containing an antibacterial agent.
Examples of the antibacterial agent include known quaternary ammonium salts, phenol derivatives and diphenyl compounds. Examples of the antibacterial agent include alkyl chloride (C12 to C16) trimethylammonium, 5-chloro-2-(2,4-dichlorophenoxy)phenol (conventional name: triclosan), 5-chloro-2-(4-). And chlorophenoxy)phenol (common name: diclosan).
The content of the antibacterial agent is preferably 0.05 to 5.0 mass% with respect to the total mass of the liquid detergent composition. The antibacterial agents may be used alone or in combination of two or more.

≪Alkaline agent≫
The liquid detergent composition can adjust the pH to a higher level by containing the alkaline agent. That is, the alkaline agent functions as a pH adjusting agent.
Examples of the alkaline agent include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; sodium hydroxide, potassium hydroxide; hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquicarbonate. The alkaline agents may be used alone or in combination of two or more.
By using the alkaline agent, the pH of the preparation can be increased, and the storage stability of the liquid detergent becomes good. Among these, alkanolamines are more preferable from the viewpoint of maximizing the effect of the component (B) by capturing chlorine in tap water.
The content of the alkaline agent is not particularly limited as long as the liquid detergent composition can be brought to a desired pH, but is preferably 0.5 to 5 mass% with respect to the total mass of the liquid detergent composition.

≪Hydrotrope agent≫
The liquid detergent composition can further improve the liquid stability by containing the hydrotrope agent.
Examples of the hydrotrope include glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, alcohol solvents such as ethanol, sulfonic acids such as paratoluene sulfonic acid and salts thereof. Among them, glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol can further improve the liquid stability and can further suppress the decrease in the activity of the component (B).

The content of the glycol solvent is preferably 2 to 5 mass% with respect to the total mass of the liquid detergent composition. When the content of the glycol solvent is at least the above lower limit value, the liquid stability can be further improved. When the content of the glycol solvent is not more than the above upper limit value, the decrease in the activity of the component (B) can be further suppressed.

The total amount of the components (A) to (D) and the optional component does not exceed 100% by mass.

<Physical properties>
The pH of the liquid detergent composition at 25° C. is more than 7, and more preferably 8 or more and 11 or less. When the pH is within the above range, it is possible to suppress the decrease in the activity of the component (B), enhance the cleaning power, and enhance the liquid stability.
The pH is a value measured with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) with a measurement target of 25°C.

(Production method)
Examples of the method for producing the liquid detergent include a method of mixing the components (A) to (D) and, if necessary, optional components and adjusting the pH to a desired pH with an alkaline agent that is a pH adjuster.

(how to use)
As a method of using the liquid detergent composition (that is, a washing method), for example, a method of adding the liquid detergent composition and an object to be washed to water and stirring the mixture with a washing machine (normal washing) can be mentioned. Further, for example, a method in which the liquid detergent composition is dissolved in water in advance to prepare a cleaning liquid, and the object to be cleaned is immersed in the cleaning liquid can be used. Alternatively, the liquid detergent composition may be directly applied to the article to be washed, allowed to stand for a certain period of time, and then washed normally (application washing).
Examples of the objects to be washed include textile products such as clothes, cloths, towels, and sheets. The liquid detergent composition is suitable as a liquid detergent for textile products.
When the liquid detergent composition is used by dissolving it in water, it is preferably diluted, for example, 5 to 5000 times (volume basis).

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following description.
(Raw materials used)
<(A) component: anionic surfactant>
A-1: linear alkylbenzene sulfonate (manufactured by Lion Corporation, trade name: Lypon LH-200).
-A-2: The average number of moles of polyoxyethylene alkyl ether sulfuric acid and ethylene oxide added is 1.0.
-A-3: The average addition mole number of polyoxyethylene alkyl ether sulfuric acid and ethylene oxide is 2.0.

<(B) component: amylase>
B-1: Amplify Prime 100L (trade name, manufactured by Novozymes), amylase activity: 350 kAU/g.
B-2: Medley Core 210L (trade name, mixture of protease and amylase, manufactured by Novozymes), amylase activity: 70 kAU/g, protease activity: 1440 kPU/g (“protease activity unit (PU)” is a protein molecule) The unit of the activity of hydrolyzing the peptide bond of 1. The activity of releasing 1 μg of tyrosine in casein per minute is 1 PU, which is calculated by the milk casein method.).

<(C) component: antioxidant>
C-1: dibutylhydroxytoluene (BHT) (Sumitomo Chemical Co., Ltd., trade name: SUMILZER BHT-R).
-C-2: Sodium sulfite.
-C-3: Sodium ascorbate.

<(D) component: nonionic surfactant>
D-1: polyoxyethylene alkyl (carbon number 12 to 14) ether (average number of moles of ethylene oxide added: 15) "AE (15EO)", a natural alcohol to which 15 moles of ethylene oxide have been added. In formula (d1), R ¹¹ is one or more alkyl groups selected from an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, R ¹² is hydrogen, X is O, and s is 15 And a compound in which t is 0. Those synthesized by the synthesis method described below.

≪Synthesis method≫
861.2 g of natural alcohol CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30 mass% NaOH aqueous solution were charged in a pressure resistant reaction vessel, and the inside of this reaction vessel was replaced with nitrogen. Next, after dehydrating at a temperature of 100° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160° C. Then, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blowing tube while controlling the addition rate so that the reaction temperature did not exceed 180°C.
After the addition of ethylene oxide was completed, the mixture was aged 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 and neutralized so that the pH of the 1% by mass aqueous solution of the reaction product was 7, to give D-1.

<Arbitrary ingredients>
-Palm fatty acid: manufactured by NOF CORPORATION, trade name "Palm fatty acid".
-Monoethanolamine (MEA): trade name "monoethanolamine" manufactured by Nippon Shokubai Co., Ltd.
Protease: manufactured by Novozymes Japan KK, Progress Uno 100L, protease activity: 1800 kPU/g.
-Antibacterial agent: 5-chloro-2-(4-chlorophenoxy)phenol (common name: diclosan), manufactured by BASF, trade name "Tinosan HP100".
-Polyethylene glycol: polyethylene glycol #1000 (PEG1000), product name "PEG#1000-60L" manufactured by Mitsui Chemicals.
-Sodium benzoate: product name "sodium benzoate" manufactured by Toagosei Co., Ltd.
・Citric acid: manufactured by Iwata Chemical Co., Ltd., trade name "anhydrous citric acid".
-Ethanol: manufactured by Nippon Alcohol Sales Co., Ltd., trade name "Specific alcohol 95 degree synthesis".
-Silicone emulsion: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KM-90".
-Fragrance: A fragrance composition A described in JP-A-2002-146399.
-Preservative 1: 1,2-benzisothiazolin-3-one (BIT), product name "ACTICIDE B20" manufactured by THOR.
-Preservative 2: 2-methyl-4-isothiazolin-3-one (MIT)/1,2-benzisothiazolin-3-one (BIT), manufactured by THOR, trade name "ACTICIDE MBS".
-Dye: manufactured by Kosumi Kasei Co., Ltd., trade name "Green No. 3".
-Alkaline agent: sodium hydroxide, manufactured by Tsurumi Soda Co., Ltd., trade name "sodium hydroxide".

(Evaluation methods)
<Method for measuring amylase activity>
0.1 g of the liquid detergent composition was diluted 300 times with a buffer solution, and this solution was used as a sample solution. The buffer solution is sodium sulfite 20.0 g, potassium dihydrogen phosphate 6.15 g, disodium hydrogen phosphate dodecahydrate 10.86 g, calcium chloride dihydrate 0.015 g, Brij35 (30% aqueous solution). This is a mixed solution of 0.75 mL made up to 1 L with ion-exchanged water.
To 1 g of the sample solution, 5 g of the phosphoric acid aqueous solution and 1 tablet of Fadebas amylase test 50T (manufactured by Magle Life Sciences) were added, and the mixture was stirred with a vortex mixer for 10 seconds, then allowed to stand at 37° C. for 15 minutes to carry out an enzymatic reaction. I advanced. Thereafter, 1 g of a 1N sodium hydroxide aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) was added to the above solution and stirred for 10 seconds with a vortex mixer to stop the reaction. Thereafter, this solution was allowed to stand at 37° C. for 15 minutes, insoluble components were filtered with a filter paper (No. 131 manufactured by Advantech), and the filtrate was recovered. The absorbance (absorbance α) at 620 nm of the collected filtrate was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. In order to remove the influence of absorption other than the target component, 1 g of 1N sodium hydroxide aqueous solution was added separately to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, and then 5 g of phosphoric acid aqueous solution and 1 part of Fadebas amylase test 50T were added. A tablet was added, the mixture was stirred with a vortex mixer for 10 seconds, and left at 37°C for 15 minutes. The insoluble matter of the solution was filtered through a filter paper (No. 131 manufactured by Advantech) to collect the filtrate. The absorbance at a wavelength of 620 nm (absorbance β) of the filtrate was measured using UV-160.

<Evaluation of storage stability of amylase>
After the production, the amylase activity was measured for the liquid detergent composition stored at 37°C for 1 week (stored at 37°C) and the liquid detergent composition stored at 5°C for 1 week (stored at 5°C). The amylase activity residual rate (%) was determined from the measurement result of the above by the following formula (s1).
Amylase activity residual rate (%)=(Absorbance at 37° C. stored product α−37° C. stored product absorbance β)/(5° C. stored product absorbance α−5° C. stored product absorbance β)×100 (s1 )
From the obtained residual rate (%) of amylase activity, the storage stability of amylase was evaluated according to the following evaluation criteria, and if "I" or "II", the storage stability was determined to be good.

I: 90% or more.
II: 80% or more and less than 90%.
III: less than 80%.

<Evaluation of liquid stability>
100 mL of the liquid detergent composition of each example was placed in a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, the product was placed in a constant temperature bath at 0° C. and stored for 1 month, and then the appearance of the liquid was visually observed, and “I” was accepted based on the following evaluation criteria.
I: Neither solidification nor precipitation is observed.
III: Solidification or precipitation was observed.

<Evaluation of protein detergency>
EMPA117 (manufactured by EMPA Testmaterialien), which is a protein soiled cloth, was cut into a size of 5×5 cm, and was referred to as “protein soiled cloth”. The liquid detergent composition has the same composition as the liquid detergent composition of each example immediately after production, except that the component (B) is not blended (component (B) component-free composition product). Were used respectively. As each liquid detergent composition, a liquid detergent composition immediately after production was used. The washing liquid was prepared by agitating both of them for 30 seconds at a ratio of 10 mL of the liquid detergent composition to 30 L of water. Then, using a Terg-O-meter (manufactured by UNITED STATES TESTING Co., Ltd.) as a washing tester, 10 pieces of the above-mentioned protein soiled cloth, a washing knitted cloth and the washing liquid were put into the washing tester, and a bath ratio of 30 was used. Washing was performed at 120 rpm and 15° C. for 10 minutes in accordance with the doubling.
After that, it was transferred to a two-tub type washing machine (Mitsubishi Electric Corp., product number: CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (15° C., 4° DH) for 3 minutes, and air-dried. ..
The reflectance of each of the unwashed contaminated cloth and the washed contaminated cloth is measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd., and the cleaning rate (%) is calculated by the following formula (s2). did.

Cleaning rate (%)=(K/S of the contaminated cloth before cleaning−K/S of the contaminated cloth after cleaning)/(K/S of the contaminated cloth before cleaning−K/S of the unstained cloth)×100・・(S2)
However, K/S is a value calculated by the formula: (1-R/100) ² /(2R/100), and R is the reflectance (%) of uncontaminated cloth, contaminated cloth or cleaning cloth.

Further, the cleaning rate (%) was calculated for five contaminated cloths, and the relative cleaning power (%) was calculated from the average value by the following formula (s3). The protein detergency was evaluated based on the obtained values according to the following evaluation criteria.

Relative cleaning rate (%)=(cleaning rate of liquid detergent composition)/(cleaning rate of composition without component (B))×100 (s3)

<<Evaluation criteria>>
I: The cleaning rate is 60% or more.
II: The cleaning rate is 50% or more and less than 60%.
III: Cleaning rate is less than 50%.

<Evaluation method of food stain cleaning power>
A medium density sauce (Otsuka Foods Co., Ltd.) was soaked in a cloth sticked to a glass rod, applied to a cotton plain weave cloth (No. 100, 5 cm×5 cm), and air-dried overnight to give a food stain-contaminated cloth.
Ten pieces of this contaminated cloth were put into 900 mL of tap water (15° C., 4° DH) in which 0.75 g of a liquid detergent composition stored at 37° C. for 1 week was dissolved, and Terg-O-Tometer was manufactured. (Manufactured by UNITED STATES TESTING Co., Ltd.) was used for washing at 120 rpm for 10 minutes. Then, after dehydration, it was rinsed in 30 L of tap water (15° C., 4° DH) for 3 minutes, and finally dried with an iron. The medium-dense sauce stain detergency was obtained by measuring the Z value (reflectance) of the original cloth before stain adhesion and the contaminated cloth before and after cleaning with a colorimetric color difference meter (SE2000 manufactured by Nippon Denshoku Co., Ltd.). The cleaning rate (%) for food stains was calculated by s4).

Cleaning rate for food stains (%)=(Z value of contaminated cloth after cleaning−Z value of contaminated cloth before cleaning)÷(Z value of original cloth−Z value of contaminated cloth before cleaning)×100... (S4)
The average value of the cleaning rate (%) for food stains was classified according to the following evaluation criteria, and if "I" or "II", the cleaning power was determined to be good.

<<Evaluation criteria>>
I: The cleaning rate is 60% or more.
II: The cleaning rate is 50% or more and less than 60%.
III: Cleaning rate is less than 50%.

(Examples 1 to 14, Comparative Examples 1 to 4)
According to the compositions shown in Tables 1 to 3, each component was put in water and mixed to prepare a liquid detergent composition of each example.
In addition, the compounding amount in the table is a pure content conversion value excluding the enzyme. The compounding amount of the enzyme is the amount as a preparation. However, regarding B-2, the blending amount of the preparation is described as the blending amount of the component (B).
In addition, components whose compounding amounts are not described in the table are not compounded.
In the table, the blending amount of water, “balance”, is the amount necessary to make the total 100% by mass. In the table, the "proper amount" of sodium hydroxide is the amount necessary to bring the pH of the liquid detergent composition to the value shown in the table.
With respect to the liquid detergent composition of each example, the amylase stability, liquid stability, protein soil cleaning power and food soil cleaning power were evaluated, and the results are shown in the table.

As shown in Tables 1 to 3, in Examples 1 to 14 to which the present invention is applied, the amylase stability is "I" or "II", and the protein detergency and food stain detergency are "I" or "II". "Met. In addition, in Examples 1 to 14, the liquid stability was "I".
In Comparative Example 1 lacking the component (C), the amylase stability was "III" and the food stain cleaning power was "III". In Comparative Example 2 in which the content of the component (A) was less than the lower limit value, the protein stain cleaning power was "III". The liquid stability of Comparative Example 3 having a pH of 7 or less was "III". In Comparative Example 4 in which the content of the component (B) was not more than the lower limit value, the food stain cleaning power was "III".
From these results, it was confirmed that by applying the present invention, a liquid detergent composition having excellent detergency and liquid stability can be obtained.

Claims (3)

(A) component: 1 to 15% by mass of anionic surfactant (excluding higher fatty acid salt and its salt),
(B) component: amylase 0.05 to 3% by mass,
Component (C): an antioxidant,
Component (D): nonionic surfactant,
Containing
The total of the component (A) and the component (D) is 10 to 26% by mass,
A liquid detergent composition for textiles, having a pH at 25° C. of greater than 7. The liquid detergent composition for a textile product according to claim 1, wherein a mass ratio represented by the component (D)/the component (A) is 0.5 to 10. The liquid detergent composition for a textile product according to claim 1, wherein a mass ratio represented by the component (B)/the component (C) is 0.06 to 250.