JP2020097657A - Liquid detergent composition for textile product - Google Patents

Abstract

To provide a liquid detergent composition having improved detergency than conventional liquid detergents; under the situation that in detergent compositions, surfactants function as the main detergent component and various components such as enzymes are mixed therein, and liquid detergents aiming to improve enzyme performance and stability have been disclosed; however, the conventional liquid detergents do not have enough detergency to stains derived from foods.SOLUTION: The liquid detergent composition contains (A) components which are surfactants other than higher fatty acids and salts thereof, (B) components which are 0.05-3 mass% of amylase, and (C) components which are hydrogen carbonates.SELECTED DRAWING: None

Description

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

As a detergent composition for a textile product whose clothes are to be washed, there are generally two kinds of detergent compositions, a powder detergent composition and a liquid detergent composition. The liquid detergent composition is in high demand because it has no fear of being left unmelted and can be used by being applied to clothing or 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.

For example, in Patent Document 1, a specific amount of a nonionic surfactant, at least one selected from an aminocarboxylic acid or a salt thereof and a phosphonic acid or a salt thereof, an α-hydroxy-monocarboxylic acid or a salt thereof, and an enzyme. A liquid detergent composition containing and has been proposed. According to the invention described in Patent Document 1, the performance and stability of the enzyme are improved.

International Publication No. 2012/144601

However, the conventional techniques have insufficient cleaning power for stains (food stains) derived from food.
Then, this invention aims at the liquid detergent composition excellent in detergency.

The present invention has the following aspects.
[1] Component (A): a surfactant excluding higher fatty acids and salts thereof,
(B) component: amylase 0.05 to 3% by mass,
(C) component: bicarbonate
A liquid detergent composition for a textile product, which comprises:
[2] The liquid detergent composition for a textile product according to [1], wherein the mass ratio represented by the component (B)/the component (C) is 0.01 to 1.5.
[3] The liquid detergent composition for a textile product according to [1] or [2], wherein the content of the component (A) is 10 to 26% by mass.
[4] The component (A) contains a nonionic surfactant and an anionic surfactant,
The liquid detergent composition for a textile product according to any one of [1] to [3], wherein the mass ratio represented by the nonionic surfactant/the anionic surfactant is 0.5 to 10.

The liquid detergent for textiles of the present invention is superior in detergency.

(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 (C).

<(A) component>
The component (A) is a surfactant excluding higher fatty acids and salts thereof. The liquid detergent composition exerts detergency by containing the component (A).
Examples of the component (A) include nonionic surfactants (component (a1)), anionic surfactants (component (a2)), cationic surfactants and amphoteric surfactants. From the viewpoint of further improving the detergency, it is preferable to contain the component (a1) and the component (a2).

<<(a1) component>>
The component (a1) is a nonionic surfactant. Examples of the nonionic surfactant include a polyoxyalkylene type nonionic surfactant represented by the following formula (a1-1) and a polyoxyalkylene type nonionic surfactant represented by the following formula (a1-2). To be

^{_{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (a1-1)
(In the formula (a1-1), 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 Represents an alkenyl group having 2 to 6 carbon atoms, s represents the average number of repetitions of EO and is a number of 6 to 20. t represents the average number of repetitions of PO and is a number of 0 to 6. EO is oxy Ethylene group and PO represent an oxypropylene group, and EO and PO may be mixed and arranged.)

In the formula (a1-1), R ¹¹ is preferably a hydrocarbon group having 10 to 18 carbon atoms because it has good detergency, and may be linear or branched. Good. 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.

When X is O in the formula (a1-1), the component (a1) 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. In addition, 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.

When X is COO in the formula (a1-1), the component (a1) 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. In addition, R ¹¹ may have an unsaturated bond. In addition, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

In formula (a1-1), s is a number of 6 to 20, preferably 10 to 18, and more preferably 14 to 18. If s is within the above range, the cleaning power can be further improved.
In formula (a1-1), t is a number from 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 (a1-1), EO and PO may be mixed and arranged. When EO and PO are mixed and arranged, they may be in a random shape or a block shape.

In formula (a1-1), the distribution of the repeating number s of EO (that is, the average number of moles of ethylene oxide added) or the repeating number t of PO (that is, the average number of moles of propylene oxide added) has the effect of the present invention. There is no particular limitation. 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 obtained by using a common alkali catalyst such as sodium hydroxide or potassium hydroxide to convert ethylene oxide or propylene oxide into a hydrocarbon group raw material (primary or secondary higher alcohol). , 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 the formula (a1-1) (component (a1-1)) may be a commercially available product. Specific examples of commercially available products include Diadol (registered trademark) manufactured by Mitsubishi Chemical Corporation (trade name, C13 and C are carbon numbers. The same applies hereinafter), Neodol (registered trademark) manufactured by Shell (trade name, C12). And C13), Sasol (registered trademark) 23 (trade name, a mixture of C12 and C13) manufactured by Sasol, and the like, to which 12 moles or 15 moles of ethylene oxide are added; P&G CO-1214 (trade name) or CO-1270 (trade name) manufactured by Co., Ltd., added with ethylene oxide equivalent to 12 mol or 15 mol to a natural alcohol; secondary alcohol having 12 to 14 carbon atoms On the other hand, those added with 15 mol of ethylene oxide (Softanol (registered trademark) 150 (trade name) manufactured by Nippon Shokubai Co., Ltd.) and the like can be mentioned. 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 (EO15 mol). ) Is mentioned.

^{_{R 13 -O - [(EO)}} p / (PO) q] - (EO) r -H ··· (a1-2)
(In the formula (a1-2), R ¹³ represents a hydrocarbon group having 8 to 18 carbon atoms. p represents the average repetition number of EO, q represents the average repetition number of PO, and r represents the average repetition number of EO. P, q, r are numbers satisfying p≧1, r≧7, 0<q≦3, p+r=8 to 20. EO represents an oxyethylene group, PO represents an oxypropylene group, EO and PO may be mixed and arranged.)

In formula (a1-2), R ¹³ is a hydrocarbon group having 8 to 18 carbon atoms, and is preferably an alkyl group or alkenyl group having 8 to 18 carbon atoms. These may be linear or branched.

In the formula (a1-2), the ratio of EO and PO is preferably 0.1 to 0.5, and more preferably 0.1 to 0.3 in terms of the ratio represented by q/(p+r). When the ratio represented by q/(p+r) is at least the above lower limit value, it is easy to optimize the foaming of the liquid detergent composition. When it is at most the above upper limit, an appropriate viscosity is likely to be obtained, and gelation is easily suppressed.

EO and PO in [(EO) _p /(PO) _q ] may be mixed and arranged. In that case, EO and PO may have a random shape or a block shape.

The component (a1) represented by formula (a1-2) can be produced by a known method. Specifically, ethylene oxide and propylene oxide were sequentially added to an alcohol having a hydrocarbon group of R ¹³ derived from natural fat and oil, or ethylene oxide and propylene oxide were mixed and added (random addition). After that, it can be produced by adding ethylene oxide.
When the component represented by the formula (a1-2) (component (a1-2)) is used, the liquid detergent composition can easily obtain an appropriate viscosity, and the gelation of the liquid detergent composition can be suppressed. Further, the foamability is improved and the biodegradability is also improved.
As the component (a1-2), one type may be used alone, or two or more types may be used in combination.

As the component (a1), the component (a1-1) is preferable, and among them, polyoxyethylene alkyl ether is more preferable. By using these components (a1), the detergency of the liquid detergent composition can be further improved.
As the component (a1), one type may be used alone, or two or more types may be used in combination.

The content of the component (a1) 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 (a1) is at least the above lower limit, the liquid stability and the cleaning power for food stains can be further enhanced. When the content of the component (a1) is not more than the above upper limit value, gelation of the liquid detergent composition can be suppressed, other components can be contained in a sufficient amount, and a synergistic effect with the anionic surfactant can be easily obtained.
In this paper, the fact that the liquid detergent composition is unlikely to change its properties such as less precipitation, less gelation, less separation, and less cloudiness is referred to as “high liquid stability”.

<<(a2) ingredient>>
The component (a2) is an anionic surfactant excluding higher fatty acids and salts thereof.
As the component (a2), an anionic surfactant 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 (average 1 to 10 mol of ethylene oxide) alkyl (C10-20) ether sulfate or salt thereof (that is, polyoxyethylene alkyl ether sulfate ester salt); Polyoxyalkylene (average of 1 to 10 mol ethylene oxide) Alkenyl (C10-20) ether sulfate or salt thereof (that is, polyoxyethylene alkenyl ether sulfate ester salt); Alkanesulfonic acid having alkyl group (C10-20) or salt thereof; α-sulfo fatty acid (C10-20) Esters or salts thereof may be mentioned. Among 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. As the component (a2), one type may be used alone, or two or more types may be used in combination.
As the component (a2), 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 ester or salt thereof, polyoxyalkylene alkyl phosphate ester or salt thereof, polyoxyalkylene alkylphenyl phosphate ester or salt thereof, glycerin fatty acid ester Examples thereof include phosphoric acid ester type anionic surfactants such as monophosphoric acid esters or salts thereof.
A commercial item may be used for these (a2) components.

The content of the component (a2) is preferably 1 to 15% by mass, more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, and 4 to 6 with respect to the total mass of the liquid detergent composition. Mass% is particularly preferred. When the content of the component (a2) 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 (a2) is at most the above upper limit, the liquid stability of the liquid detergent composition can be further enhanced.

The content of the component (A) (that is, the total amount of surfactant) is preferably 8 to 35% by mass, more preferably 10 to 26% by mass, and 12 to 18% by mass based on the total mass of the liquid detergent composition. Mass% is more preferable. When the total amount of the surfactants is at least the above lower limit value, the detergency can be further improved. When the total amount of surfactants is not more than the above upper limit value, the liquid stability can be further enhanced.

The total amount of the (a1) component and the (a2) component (a1a2 total amount) is preferably 8 to 35% by mass, more preferably 10 to 26% by mass, and 12 with respect to the total mass of the liquid detergent composition. -18 mass% is more preferred. When the total amount of a1a2 is not less than the above lower limit value, the detergency for sebum stains and proteins can be further improved. When the total amount of a1a2 is not more than the above upper limit value, the liquid stability of the liquid detergent composition can be further improved and the rinsing property can be enhanced. When the rinsing property is enhanced, the number of rinsing treatments after the cleaning treatment can be reduced.

The mass ratio (a1/a2 ratio) represented by the component (a1)/component (a2) is preferably 0.5 to 10, more preferably 1 to 10, and even more preferably 1.5 to 5. When the a1/a2 ratio is at least the above lower limit, it is possible to further improve the detergency for food stains containing starch and the like. When the a1/a2 ratio is less than or equal to the above upper limit, the cleaning power against protein stains can be further improved.

<(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 an 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 and oligo-1,6-glucosidase.
These (B) components may be used alone or in combination of two or more.

Examples of the commercially available enzyme (amylase preparation) as the component (B) include 300 L of Termamyl Ultra, 16 L of Duramyl, 12 L of Stainzyme, 200 L of Promozyme, AmplifyL Prime. Medley Core 210L (mixed enzyme of protease and amylase. Trade name: Novozymes Co., Ltd.); Maxamyl (trade name, Genencor Co., Ltd.), pullulanase Amano (trade name, Amano Pharmaceutical Co., Ltd.) , DB-250 (trade name, pullulanase derived from Aerobacterium aerogenes ATCC 9621, crude or crystallized product, manufactured by Seikagaku Corporation) and the like. Among them, as the component (B), 16 L of Duramil, 12 L of stainzyme, 300 L of Termamyl Ultra, 100 L of Amplify Prime (these are trade names; manufactured by Novozymes) are preferable, and 100 L of Amplify Prime is more preferable.
The activity of the component (B) per 1 g of the preparation is preferably 1 to 800 kAU/g, more preferably 20 to 600 kAU/g, still more 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. .. If the content of the component (B) is at least the above lower limit, 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 from 3 to 700, more preferably from 5 to 500, further preferably from 12 to 180, particularly preferably from 20 to 30. 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 at most 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.

Further, the amylase activity (kAU/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 further preferably 0.05 to 8 kAU/g. ..

<<Amylase activity>>
Amylase activity is measured by the following method, for example.
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 "Fadebass 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, for example, a value measured by the following method. 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 the buffer solution and a blue starch polymer as a substrate is added. As the buffer solution, 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) were 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 37° C. thermostat for 15 minutes to carry out an enzyme reaction. After 1 mL of a 1 mol/L sodium hydroxide solution was added to stop the enzymatic reaction, the insoluble matter was filtered off with a filter paper (N0.131 manufactured by Advantech Co., Ltd.) and the filtrate was recovered. 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 the buffer solution, and this solution was used as a sample solution. As the buffer solution, 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) were 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 the Fadebas amylase test (manufactured by Magle Life Sciences) were added, stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37°C for 15 minutes to proceed with the enzymatic reaction. Then, 1 g of a 1N sodium hydroxide aqueous solution (manufactured by Kanto Kagaku) 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 through a filter paper (N0.131 manufactured by Advantech), and the filtrate is recovered. The absorbance at 620 nm (absorbance α) of the collected filtrate is 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 separately added 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. After that, the insoluble component of the solution was filtered with a filter paper (N0.131 manufactured by Ad Antec Co., Ltd.). The absorbance at a wavelength of 620 nm (absorbance β) of the filtrate 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 having a 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 (manufactured by Magle 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. Thereafter, 1 g of a 1N sodium hydroxide aqueous solution (manufactured by Kanto Kagaku) was added to the solution, and the mixture was stirred for 10 seconds with a vortex mixer to stop the reaction. 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 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 separately added 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>
The component (C) is hydrogen carbonate. Since the liquid detergent composition contains the component (C), the synergistic effect with the component (B) can enhance the detergency for food stains.
Examples of the component (C) include sodium hydrogencarbonate, potassium hydrogencarbonate, sodium sesquicarbonate, and other alkali metal hydrogencarbonates.
These (C) components may be used alone or in combination of two or more.

The content of the component (C) is preferably 2.0 to 5.0% by mass, more preferably 2.2 to 4.0% by mass, and 2.5 to 5.0% by mass based on the total mass of the liquid detergent composition. 3.0 mass% is more preferable. When the content of the component (B) is at least the above lower limit value, it is easy to maintain the pH of the diluted solution after dispersing the liquid detergent composition in tap water into a cleaning solution to be weakly alkaline (more than pH 8 and 11 or less), Easy to enhance the cleaning power. When the content of the component (C) is at most the above upper limit value, the liquid stability at low temperatures will be excellent, and uniform and transparent appearance will be easily obtained.

The mass ratio (B/C ratio) represented by (B) component/(C) component is, for example, preferably 0.01 to 1.5, more preferably 0.02 to 1, and 0.03 to 0. 4 is more preferable. When the B/C ratio is at least the above lower limit, the detergency for protein stains can be further enhanced. When the B/C ratio is not more than the above upper limit, it is possible to further suppress the decrease in the activity of the component (B), and it is possible to further enhance the detergency for food stains containing starch and the like.

The mass ratio (C/A ratio) represented by the component (C)/component (A) is, for example, preferably 0.06 to 0.6, more preferably 0.08 to 0.4, and 0.1 to 0.3 is more preferable. If the C/A ratio is at least the above lower limit, the detergency can be further enhanced. When the C/A ratio is less than or equal to the above upper limit value, uniform transparency and a good appearance are likely to be obtained.

<Arbitrary ingredients>
The liquid detergent composition may contain optional components other than the components (A) to (C). As the optional component, water, higher fatty acid or salt thereof (higher fatty acid (salt)), chelating agent, enzyme (optional enzyme) other than component (B), alkaline agent (optional alkaline agent) other than component (C), hydro Examples include troping agents, fragrances, and dyes.

<<water>>
The liquid detergent composition may contain water. The content of water is preferably 60 to 90 mass% and more preferably 70 to 85 mass% with respect to the total mass of the liquid detergent composition.

≪Higher fatty acid (salt)≫
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 rinsing property is enhanced, 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. Among them, 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, the 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, 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 protease preparations include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L TypeAlexAl 2.5, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 8L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5 of the formula are available from Novozymes. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L Progress Uno 100L, Medley Core 210L (mixed enzyme of protease and amylase); trade name Purafect L, Purafecta, etc. available from Genecore. ..

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

Examples of cellulase preparations include 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.

Examples of mannanase preparations include the product name Mannaway 4L available from Novozymes, etc.

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 as an enzyme preparation. The content of the optional enzyme is the content as a preparation.

≪Optional alkali agent≫
The pH of the liquid detergent composition can be adjusted more easily by containing an optional alkaline agent. That is, the alkaline agent functions as a pH adjuster.
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 0.1 to 3 mass% with respect to the total mass of the liquid detergent composition.
When alkanolamine is used as the optional alkali agent, the mass ratio (amine/C ratio) represented by the alkanolamine/(C) component is preferably 0.03 to 3, more preferably 0.05 to 0.1. preferable. When the amine/C ratio is within the above range, the detergency can be further improved, and the pH of the liquid detergent composition can be easily kept alkaline.

≪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 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-based solvent is at most 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 (C) and the optional component does not exceed 100% by mass.

<Physical properties>
The pH of the liquid detergent composition at 25° C. is preferably more than 7, 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 detergency, 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 (C) and, if necessary, optional components and adjusting the pH to a desired pH with an alkaline agent which is a pH adjusting agent.

(how to use)
Examples of the method for using the liquid detergent composition (that is, the washing method) include a method (normal washing) in which the liquid detergent composition and the object to be washed are put into water and stirred with a washing machine or the like. Further, for example, a method in which the liquid detergent composition is previously dissolved in water 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).
In the normal cleaning, the pH of the cleaning liquid is preferably 8 to 10, and more preferably 8.5 to 9.5.
Examples of the article 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: surfactant>
A-1: polyoxyethylene alkyl ether (AE(15EO)), a natural alcohol to which 15 mol of ethylene oxide is added. In the above general formula (a1-1), compounds wherein R ¹¹ =C 12 alkyl group and C 14 alkyl group, X═O, s=15, t=0, and R ¹¹ =hydrogen. It was synthesized by the following synthesis method.

≪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 into 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 A-1.

-A-2: A linear alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms (LAS, manufactured by Lion Corporation, trade name: Lypon (registered trademark) LH-200).

<(B) component: amylase>
B-1: Amplify Prime 100L (trade name, manufactured by Novozymes, amylase preparation, amylase activity=350 kAU/g).

<(C) component: bicarbonate>
· C-1: NaHCO ₃ sodium hydrogen carbonate, Kanto Chemical Co., Ltd., trade name "Sodium bicarbonate".

<Arbitrary ingredients>
Protease: manufactured by Novozymes Japan, Progress Uno 100L, protease activity: 1800 kPU/g.
-Monoethanolamine: The product name "monoethanolamine" manufactured by Nippon Shokubai Co., Ltd.
-Sodium benzoate: product name "sodium benzoate" manufactured by Toagosei Co., Ltd.
-Ethanol: manufactured by Nippon Alcohol Sales Co., Ltd., trade name "Specific alcohol 95 degree synthesis".
-MGDA: Methylglycine diacetate trisodium, manufactured by BASF, trade name "Trilon M Liquid".
-Calcium chloride: The product name "calcium chloride" manufactured by Kanto Chemical Co., Inc.
Palm oil fatty acid: trade name "Palm fatty acid" manufactured by NOF CORPORATION.
-PEG1000: Polyethylene glycol #1000, manufactured by Mitsui Chemicals, Inc., trade name "PEG#1000-60L".
-Silicone emulsion: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KM-90".
-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 Konami Kasei Co., Ltd., trade name "Green No. 3".
-Fragrance: A fragrance composition A described in JP-A-2002-146399.
-PH adjuster: sodium hydroxide (NaOH), trade name "sodium hydroxide" manufactured by Tsurumi Soda Co., Ltd.

(Evaluation method)
<Cleaning power>
The cloth sticked to the glass rod was soaked with Nakano sauce (Otsuka Foods Co., Ltd.). A medium-thickness sauce impregnated in a cloth was applied to a cotton plain weave cloth (No. 100, 5 cm×5 cm), and this was air-dried overnight to obtain a food-dirt-contaminated cloth.
Ten contaminated cloths were put into 900 mL of tap water (15° C., 4° DH) in which 0.75 g of the liquid detergent composition of each example was dissolved. Using a Terg-O-Tometer (manufactured by UNITED STATES TESTING), 10 pieces of contaminated cloth were washed at 120 rpm for 10 minutes. After the contaminated cloth was dehydrated, it was rinsed in 30 L of tap water (15° C., 4° DH) for 3 minutes and dried with an iron. The Z value (reflectance) of the original cloth before the stain adhered and the contaminated cloth before and after the cleaning were measured by using a colorimetric color difference meter (SE2000 manufactured by Nippon Denshoku Co., Ltd.), and the source stain was obtained by the following formula (s). The cleaning rate (%) was calculated.

Cleaning rate (%)=(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...(s)

The average value of the cleaning rate (%) of the 10 contaminated cloths 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 70% or more.
II: The cleaning rate is 60% or more and less than 70%.
III: The cleaning rate is 50% or more and less than 60%.
IV: The cleaning rate is less than 50%.

<Liquid stability>
30 mL of the liquid detergent composition of each example was placed in a cylindrical glass bottle, and the lid was closed and sealed. In this state, it was stored for 1 month in a constant temperature bath at 0°C. Then, the liquid detergent composition was taken out from the thermostat and the appearance of the liquid detergent composition was visually observed, and the liquid stability of the liquid detergent was evaluated based on the following criteria. "I" was accepted based on the following evaluation criteria.
I: Neither solidification nor precipitation is observed.
II: Solidification or precipitation was observed.

(Examples 1 to 8, Comparative Examples 1 to 4)
According to the compositions shown in Tables 1 and 2, 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 in the table is the compounding amount as a preparation. 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 100% by mass as a whole. In the table, the compounding amount “appropriate amount” of sodium hydroxide is an amount necessary to bring the liquid detergent composition to the pH described in the table.
The liquid detergent composition of each example was evaluated for food stain cleaning power and liquid stability, and the results are shown in the table.

As shown in Tables 1 and 2, in Examples 1 to 8 to which the present invention was applied, the detergency was evaluated as "I" or "II" and the liquid stability was evaluated as "I".
In Comparative Examples 1 and 3 in which the content of the component (B) was less than the lower limit value of the present invention, the cleaning power was evaluated as "III" or "IV". In Comparative Examples 2 and 4 lacking either the component (A) or the component (C), the evaluation of the cleaning power was "IV".
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 (4)

Component (A): a surfactant excluding higher fatty acids and salts thereof,
(B) component: amylase 0.05 to 3% by mass,
(C) component: bicarbonate
A liquid detergent composition for a textile product, which comprises: 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 0.01 to 1.5. The liquid detergent composition for textiles according to claim 1 or 2, wherein the content of the component (A) is 10 to 26% by mass. The component (A) contains a nonionic surfactant and an anionic surfactant,
The liquid detergent composition for textiles according to any one of claims 1 to 3, wherein a mass ratio represented by the nonionic surfactant/the anionic surfactant is 0.5 to 10.