JP7138554B2 - Liquid detergent composition for textiles - Google Patents

Description

The present invention relates to liquid cleaning compositions for textiles.

There are generally two types of detergent compositions for textile products used for cleaning clothes, ie, powder detergent compositions and liquid detergent compositions. Demand for liquid detergent compositions is increasing because there is no concern that they will remain undissolved and they can be used by applying them to clothing and the like.
In detergent compositions, a surfactant acts as a main detergent ingredient, and various ingredients such as enzymes are blended. Enzymes play an important role as components that exhibit various performances in small amounts.

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

WO2012/144601

However, conventional techniques are insufficient in detergency against stains derived from food (food stains).
Accordingly, an object of the present invention is to provide a liquid detergent composition having excellent detergency.

The present invention has the following aspects.
[1] (A) component: a surfactant excluding higher fatty acids and salts thereof;
(B) component: 0.05 to 3% by mass of amylase,
(C) component: hydrogen carbonate;
A liquid detergent composition for textiles containing
[2] The liquid detergent composition for textiles according to [1], wherein the mass ratio represented by component (B)/component (C) is 0.01 to 1.5.
[3] The liquid detergent composition for textiles according to [1] or [2], wherein the content of 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 textile products according to any one of [1] to [3], wherein the nonionic surfactant/anionic surfactant mass ratio is 0.5 to 10.

According to the liquid detergent for textile products of the present invention, it is excellent in detergency.

(Liquid detergent)
The liquid detergent composition for textile products of the present invention (hereinafter sometimes simply referred to as liquid detergent composition) contains components (A) to (C).

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

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

R ¹¹ -X-[(EO) _s /(PO) _t ]-R ¹² (a1-1)
(In 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 An ethylene group and PO represent an oxypropylene group, and EO and PO may be mixed and arranged.)

In formula (a1-1), R ¹¹ is preferably a hydrocarbon group having 10 to 18 carbon atoms because of its good detergency, and may be linear or branched. good. Hydrocarbon groups include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides.
The alkyl group for R ¹² is preferably an alkyl group having 1 to 3 carbon atoms. The alkenyl group for R ¹² is preferably an alkenyl group having 2 to 3 carbon atoms. Moreover, X is preferably O or COO.

In formula (a1-1), when X is O, 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. Also, R ¹¹ may have an unsaturated bond. Also, s is preferably 10 to 20, more preferably 14 to 18, and R ¹² is preferably a hydrogen atom.

In formula (a1-1), when X is COO, 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, more preferably a hydrocarbon group having 11 to 18 carbon atoms, from the viewpoint of further improving detergency. Also, R ¹¹ may have an unsaturated bond. R ¹² is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

In formula (a1-1), s is a number of 6 to 20, preferably 10 to 18, more preferably 14 to 18. If s is within the above range, the detergency can be further improved.
In formula (a1-1), t is a number of 0 to 6, preferably 0 to 3, more preferably 0. When t is within the above range, liquid stability at high temperatures tends to be good.
In [(EO) _s /(PO) _t ] in formula (a1-1), EO and PO may be arranged in a mixed manner. When EO and PO are mixed and arranged, they may be in a random form or in a block form.

In the formula (a1-1), the distribution of the repeating number s of EO (that is, the average number of added moles of ethylene oxide) or the number of repeating points t of PO (that is, the average number of added moles of propylene oxide) has the effect of the present invention. is not particularly limited. The addition mole number distribution varies depending on the reaction method in producing the nonionic surfactant. For example, the addition mole number distribution of ethylene oxide or propylene oxide can be obtained by converting ethylene oxide or propylene oxide into a hydrocarbon group raw material (primary or secondary higher alcohol , higher fatty acids, higher fatty acid amides, etc.), the distribution tends to be relatively wide. In addition, specific alkoxylation of magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ are added as described in JP-B-6-15038 The catalytic addition of ethylene oxide or propylene oxide to the hydrocarbon radical starting material tends to result in a relatively narrow distribution.

The component represented by 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, where C indicates the number of carbon atoms; the same shall apply hereinafter), and Neodol (registered trademark) manufactured by Shell (trade name, C12). and C13), alcohols such as Safol (registered trademark) 23 (trade name, mixture of C12 and C13) manufactured by Sasol, and 12 moles or 15 moles of ethylene oxide added; P & G Natural alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by Co., Ltd. added with ethylene oxide equivalent to 12 mol or 15 mol; secondary alcohol having 12 to 14 carbon atoms to which 15 mol equivalent of ethylene oxide is added (Softanol (registered trademark) 150 (trade name) manufactured by Nippon Shokubai Co., Ltd.). Furthermore, to methyl coconut fatty acid (lauric acid / myristic acid = 8/2), using an alkoxylation catalyst, ethylene oxide equivalent to 15 moles was added (polyoxyethylene coconut fatty acid methyl ester (EO 15 moles) ).

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 number of repetitions of EO, q represents the average number of repetitions of PO, and r represents the average number of repetitions of EO. p, q, and r are numbers satisfying p≧1, r≧7, 0<q≦3, and p+r=8 to 20. EO represents an oxyethylene group, PO represents an oxypropylene group, EO and PO may be arranged in a mixed manner.)

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

In formula (a1-2), the ratio of EO to PO is preferably 0.1 to 0.5, more preferably 0.1 to 0.3, as expressed by q/(p+r). When the ratio represented by q/(p+r) is at least the above lower limit, the foaming of the liquid detergent composition is easily optimized. When it is at most the above upper limit value, it becomes easier to obtain an appropriate viscosity, and gelation tends to be suppressed.

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

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 fats and oils, or mixed addition (random addition) of ethylene oxide and propylene oxide was performed. After that, it can be produced by adding ethylene oxide.
When the component represented by formula (a1-2) (component (a1-2)) is used, the liquid detergent composition can easily obtain an appropriate viscosity and gelation of the liquid detergent composition can be suppressed. In addition, foamability is improved and biodegradability is improved.
The component (a1-2) may be used singly or in combination of two or more.

Component (a1) is preferably component (a1-1), and more preferably polyoxyethylene alkyl ether. By using these (a1) components, it is possible to further improve the detergency of the liquid detergent composition.
The component (a1) may be used alone or in combination of two or more.

The content of 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, relative to the total mass of the liquid detergent composition. When the content of component (a1) is at least the above lower limit, liquid stability and detergency against food stains can be further enhanced. If the content of the component (a1) is at most the above upper limit, gelation of the liquid detergent composition can be suppressed, other components can be contained in sufficient amounts, and synergistic effects with the anionic surfactant can be easily obtained.
In this specification, the term "high liquid stability" means that the properties of the liquid of the liquid detergent composition do not easily change, such as less precipitation, less gelation, less separation, less cloudiness, and the like.

<<(a2) component>>
Component (a2) is an anionic surfactant other than higher fatty acids and salts thereof.
As the component (a2), anionic surfactants conventionally used in liquid detergent compositions can be used. For example, linear alkyl (C8-16) benzenesulfonic acid or its salt; α-olefin (C10-20) sulfonic acid or its salt; linear or branched alkyl (C10-20) sulfate or its salt polyoxyalkylene (average 1 to 10 moles of ethylene oxide) alkyl (C10-20) ether sulfate or its salt (i.e., polyoxyethylene alkyl ether sulfate salt); polyoxyalkylene (average of 1 to 10 moles of ethylene oxide) Alkenyl (C10-20) ether sulfate ester or its salt (that is, polyoxyethylene alkenyl ether sulfate ester salt); alkanesulfonic acid having an alkyl group (C10-20) or its salt; α-sulfo fatty acid (C10-20) esters or salts thereof. Among these, straight-chain alkylbenzenesulfonic acids or salts thereof are preferred from the viewpoint of protein denaturing action, which is part of food stains. "C 〇〇 to 〇〇" in parentheses represents the number of carbon atoms.
Salt forms of anionic surfactants 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 (a2) may be used alone or in combination of two or more.
(a2) components other than the above include, for example, alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, acyl Carboxylic acid-type anionic surfactants such as aminocarboxylic acids or salts thereof; alkyl phosphates or salts thereof, polyoxyalkylene alkyl phosphates or salts thereof, polyoxyalkylene alkylphenyl phosphates or salts thereof, glycerin fatty acid esters Phosphate ester type anionic surfactants such as monophosphate esters or salts thereof, and the like are included.
A commercial item may be used for these (a2) components.

The content of 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% by mass, relative to the total mass of the liquid detergent composition. % by weight is particularly preferred. When the content of component (a2) is at least the above lower limit, the detergency against protein, which is part of food stains, can be further enhanced. (a2) Liquid stability of liquid cleaning composition is improved more as content of a component is below the said upper limit.

The content of component (A) (that is, the total amount of surfactant) is preferably 8 to 35% by mass, more preferably 10 to 26% by mass, more preferably 12 to 18% by mass, relative to the total mass of the liquid detergent composition. % by mass is more preferred. If the total surfactant amount is at least the above lower limit, the detergency can be further improved. If the total surfactant amount is equal to or less than the above upper limit, the liquid stability can be further enhanced.

The total amount of components (a1) and (a2) (a1a2 total amount) is preferably 8 to 35% by mass, more preferably 10 to 26% by mass, and 12 ~18% by mass is more preferred. When the a1a2 total amount is at least the above lower limit, the detergency against sebum stains and proteins can be further improved. When the a1a2 total amount is equal to or less than the above upper limit, the liquid stability of the liquid detergent composition can be further improved, and the rinsability can be enhanced. Improving the rinsability can reduce the number of rinsing treatments after the cleaning treatment.

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

<(B) Component>
(B) Component is amylase. By containing the component (B), the liquid detergent composition can have enhanced detergency against starch, which is part of food stains.
The component (B) may be an enzyme that hydrolyzes α-1,4 bonds of starch, glycogen and the like. (B) components include α-amylase, β-amylase, α-glucosidase, glucoamylase; glucosidase/4-α-glucanotransferase, oligo-1,6-glucosidase and the like.
These (B) components may be used singly or in combination of two or more.

Commercially available enzymes (amylase formulations) of component (B) include Termamyl Ultra 300L, Duramyl 16L, Stainzyme 12L, Promozyme 200L, Amplify Prime 100L, Medley Core 210L (mixed enzyme of protease and amylase, trade name; manufactured by Novozymes); Maxamyl (trade name, manufactured by Genencore), pullulanase Amano (trade name, manufactured by Amano Pharmaceutical Co., Ltd.) , DB-250 (trade name, pullulanase derived from Aerobacter aerogenes ATCC9621, crude or crystallized product, manufactured by Seikagaku Corporation), and the like. Among them, as the component (B), Duramil 16L, Stainzyme 12L, Termamyl Ultra 300L, and Amplify Prime 100L (manufactured by Novozymes, Inc.) are preferable, and Amplify Prime 100L is more preferable.
The activity of these components (B) per 1 g of the preparation is preferably 1 to 800 kAU/g, more preferably 20 to 600 kAU/g, even more preferably 50 to 400 kAU/g.
These amylase formulations may be used singly or in combination of two or more.

The content of component (B) is 0.05 to 3% by mass, preferably 0.05 to 2% by mass, more preferably 0.1 to 1% by mass, relative to the total mass of the liquid detergent composition. . (B) If content of a component is more than the said lower limit, detergency will be improved more. If the content of component (B) is equal to or less than the above upper limit, precipitation can be further suppressed, and liquid stability can be further enhanced.
In addition, content of (B) component is content as a formulation.

The mass ratio represented by component (A)/component (B) (A/B ratio) is preferably 3-700, more preferably 5-500, still more preferably 12-180, and particularly preferably 20-30. When the A/B ratio is at least the above lower limit, the content of component (A) is sufficient, and the detergency against proteins can be further improved. If the A/B ratio is equal to or less than the above upper limit, the decrease in the activity of the component (B) can be further suppressed, and the detergency against food stains containing starch and the like can be further improved.

Further, the amylase activity (kAU/g) per gram of the liquid detergent composition is preferably 0.0005 to 24 kAU/g, more preferably 0.001 to 16 kAU/g, even more preferably 0.05 to 8 kAU/g. .

≪Amylase activity≫
Amylase activity is measured, for example, by the following method.
As used herein, "amylase activity unit (AU)" is the activity of α-amylase to hydrolyze α-1,4-glucosidic bonds in starch. The amylase activity unit (AU) is a value converted from an absorbance calibration curve (provided with the reagent) prepared with a standard enzyme "Phadebas Human α-Amylase Control" of known activity. Note that 1U/L is 1AU.

[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 using the "Phadebas amylase test" (manufactured by Magle Life Sciences).

A standard enzyme solution diluted to each concentration is used to create a standard curve. To the test tube containing the standard enzyme solution, add 5 g of buffer solution and 1 tablet containing blue starch polymer as substrate. The buffer solution is 20 g of sodium sulfite, 5 g of potassium dihydrogen phosphate, 10 g of disodium hydrogen phosphate/12 hydrate, 0.05 g of calcium chloride/2 hydrate, and 1 mL of Brij35 (30% aqueous solution) with deionized water. It is a mixed liquid made to 1 L.
The tablet is mixed until it disintegrates, and is kept in a constant temperature bath at 37°C for exactly 15 minutes for enzymatic reaction. After adding 1 mL of 1 mol/L sodium hydroxide solution to stop the enzymatic reaction, the insoluble matter was removed by filtration through filter paper (N0.131 manufactured by Advantech, etc.), and the filtrate was recovered. A calibration curve is obtained by measuring the absorbance of the recovered filtrate at a wavelength of 620 nm.

0.1 g of the liquid detergent composition was diluted 300-fold with the buffer solution, and this solution was used as a sample solution. The buffer solution is 20 g of sodium sulfite, 5 g of potassium dihydrogen phosphate, 10 g of disodium hydrogen phosphate/12 hydrate, 0.05 g of calcium chloride/2 hydrate, and 1 mL of Brij35 (30% aqueous solution) with deionized water. It is a mixed liquid made to 1 L.
To 1 g of the sample solution, 5 g of the above buffer solution and 1 tablet of Phadebas amylase test (manufactured by Magle Life Sciences) are added, stirred for 10 seconds with a vortex mixer, and allowed to stand at 37° C. for 15 minutes to promote the enzymatic reaction. After that, 1 g of 1N sodium hydroxide aqueous solution (manufactured by Kanto Kagaku) is added to the above solution, and the mixture is stirred for 10 seconds with a vortex mixer to stop the reaction. After that, this solution is allowed to stand at 37° C. for 15 minutes, the insoluble components are filtered with filter paper (N0.131 manufactured by Advantech, etc.), and the filtrate is recovered. The absorbance (absorbance α) of the recovered filtrate at 620 nm is measured using a UV-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. In order to eliminate the influence of absorption of components other than the target component, 1 g of 1N sodium hydroxide aqueous solution was separately added to 1 g of each sample solution, and after stirring with a vortex mixer for 10 seconds, 5 g of phosphoric acid aqueous solution and Fadebas amylase test 50T were added to 1 g. Tablets are added, stirred with a vortex mixer for 10 seconds, and allowed to stand at 37° C. for 15 minutes. After that, the insoluble components of the solution were filtered with filter paper (N0.131 manufactured by Adantek Co., Ltd.). The absorbance of the filtrate at a wavelength of 620 nm (absorbance β) is measured using UV-160. Next, the difference between the absorbance α and the absorbance β is determined. This difference is taken as the absorbance 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 a calibration curve prepared with amylase enzymes of known activity.

[Method for measuring activity per 1 g of amylase preparation]
The activity per 1 g of component (B) (amylase enzyme preparation) is, for example, a value measured by the following method.
Dissolve 0.1 g of the amylase enzyme preparation in the above buffer and make up to 100 mL. By dissolving 1 mL of this enzyme solution in ion-exchanged water to a constant volume of 100 mL, an aqueous solution of amylase enzyme preparation having a concentration of 0.001% by mass is prepared.
To 1 mL of this amylase enzyme preparation aqueous solution, 5 g of the above buffer solution and 1 tablet of Phadebas 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 allow the enzymatic reaction. proceed. After that, 1 g of 1N aqueous sodium hydroxide solution (manufactured by Kanto Kagaku) is added to the solution, and the mixture is stirred for 10 seconds with a vortex mixer to stop the reaction. Thereafter, this solution is allowed to stand at 37° C. for 15 minutes, the insoluble components are filtered with filter paper, and the filtrate is recovered. The absorbance (absorbance a) of the recovered filtrate at 620 nm is measured with a UV-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. In order to eliminate the influence of absorption of components other than the target component, 1 g of 1N sodium hydroxide aqueous solution was separately added to 1 g of each sample solution, and after stirring with a vortex mixer for 10 seconds, 5 g of phosphoric acid aqueous solution and Fadebas amylase test 50T were added to 1 g. Tablets are added, stirred with a vortex mixer for 10 seconds, and allowed to stand at 37° C. for 15 minutes. The insoluble components of the solution are filtered with filter paper. The absorbance of the filtrate at a wavelength of 620 nm (absorbance b) is measured with UV-160. Next, the difference between absorbance a and absorbance b is determined. This difference is taken as the absorbance value of the amylase preparation.
Amylase activity (AU) per 1 g of component (B) is calculated from concentrations calculated based on a calibration curve prepared with amylase enzymes of known activity.

<(C) Component>
(C) A component is a hydrogen carbonate. By containing the component (C), the liquid detergent composition has a synergistic effect with the component (B) to enhance the detergency against food stains.
Component (C) includes, for example, alkali metal hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquicarbonate.
These (C) components may be used individually by 1 type, and may use 2 or more types together.

The content of component (C) is preferably 2.0 to 5.0% by mass, more preferably 2.2 to 4.0% by mass, more preferably 2.5 to 5.0% by mass, relative to 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, the pH of the diluted liquid after dispersing the liquid detergent composition in tap water to form a cleaning liquid is easily maintained at a weak alkalinity (more than pH 8 and 11 or less), Easy to increase detergency. When the content of the component (C) is equal to or less than the above upper limit, the liquid stability at low temperatures is excellent, and it is easy to obtain uniform transparency and a good appearance.

The mass ratio (B/C ratio) represented by component (B)/component (C) is, for example, preferably 0.01 to 1.5, more preferably 0.02 to 1, and 0.03 to 0.03. 4 is more preferred. If the B/C ratio is at least the above lower limit, the detergency against protein stains can be further enhanced. If the B/C ratio is equal to or less than the above upper limit, the decrease in activity of the component (B) can be further suppressed, and the detergency against food stains containing starch and the like can be further enhanced.

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

<Optional component>
The liquid detergent composition may contain optional components other than components (A) to (C). Optional components include water, higher fatty acids or salts thereof (higher fatty acids (salts)), chelating agents, enzymes other than component (B) (optional enzymes), alkaline agents other than component (C) (optional alkaline agents), hydro Tropic agents, fragrances, dyes and the like can be mentioned.

≪Water≫
The liquid detergent composition may contain water. The water content is preferably 60 to 90% by mass, more preferably 70 to 85% by mass, relative to the total mass of the liquid detergent composition.

≪Higher fatty acid (salt)≫
Examples of optional surfactants include higher fatty acids or salts thereof (higher fatty acids (salts)), cationic surfactants, amphoteric surfactants, and the like.
A "higher fatty acid" is a fatty acid having 8 to 22 carbon atoms. By containing a higher fatty acid (salt), the rinsability of the liquid detergent composition can be enhanced. Improving the rinsability can reduce the number of rinsing treatments after the cleaning treatment.
When a higher fatty acid (salt) is blended, liquid stability tends to decrease. Liquid stability can be improved by setting the pH of the liquid detergent composition to more than 7.
Chain monocarboxylic acids having 8 to 18 carbon atoms are preferred as higher fatty acids. A 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 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 7-17, preferably 11-17. If the number of carbon atoms in R ¹ is at least the above lower limit, the effect of preventing redeposition increases. If the number of carbon atoms in R ¹ is equal to or less than the above upper limit, the solubility in water will increase.

Salt forms of higher fatty acids (salts) include alkali metal salts, alkaline earth metal salts, amine salts and ammonium salts. Alkali metal salts include sodium salts, potassium salts, and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Amine salts include alkanolamine salts (monoethanolamine salts, diethanolamine salts, triethanolamine salts, etc.) and the like.
These higher fatty acids (salts) may be used singly or in combination of two or more. Further, the higher fatty acid (salt) may be a mixture of single chain lengths or a mixture of 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, more preferably 0.8 to 1.5% by mass, relative to the total mass of the liquid detergent composition. % by mass is more preferred. When the content of the higher fatty acid (salt) is at least the above lower limit, the rinsability can be further enhanced. If the content of the higher fatty acid (salt) is equal to or less than the above upper limit, the liquid stability can be further enhanced.

≪Chelating agent (sequestering agent)≫
Chelating agents include organic chelating agents. Chelating agents include 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, and triacetic acid. ethylenetetraaminehexaacetic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, trisodium methylglycine diacetate, 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 used singly or in combination of two or more.

≪Arbitrary enzyme≫
When the liquid cleansing composition contains an optional enzyme, the sebum cleansing power and protein cleansing power can be further improved.
Examples of optional enzymes include protease, lipase, cellulase, mannanase, cellulase, and the like. As an optional enzyme, proteases are more preferred from the standpoint of proteolytic degradation that is part of food soiling.

As the protease, a protease having serine, histidine and aspartic acid in the molecule, such as serine protease, is preferred.
In general, preparations containing protease (protease preparations) are commercially available. When preparing liquid detergents, proteases are usually formulated with this protease formulation.
Examples of protease preparations include Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase 2.5L, and Ultraq 2.5L, which are available from Novozymes. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L Progress Uno 100L, Medley Core210L (mixed enzyme of protease and amylase); Purafect L, Purafect OX, Properase L available from Genencore, etc. .

Lipase preparations include, for example, trade names Lipex 100L and Lipolase 100L available from Novozymes.

Cellulase preparations include, for example, Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (trade name, manufactured by Novozymes), Endrase 5000L (trade name, manufactured by Novozymes), and Cellclean 4500T (trade name, manufactured by Novozymes). company) and the like.

Mannanase preparations include, for example, Mannaway 4L (trade name) available from Novozymes.

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

≪Arbitrary alkaline agent≫
A liquid detergent composition can adjust pH more easily by containing an arbitrary alkaline agent. That is, the alkaline agent functions as a pH adjuster.
Examples of alkaline agents include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; sodium hydroxide, potassium hydroxide; and hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and sodium sesquicarbonate. Alkaline agents may be used alone or in combination of two or more.
By using an alkaline agent, the pH of the formulation can be increased, and the storage stability of the liquid detergent becomes good. Among these, alkanolamine is more preferable because the effect of the component (B) is maximized by trapping chlorine in tap water.
The content of the alkaline agent is not particularly limited as long as it can bring the liquid detergent composition to the desired pH, but is preferably 0.1 to 3% by mass relative to the total mass of the liquid detergent composition.
Further, when alkanolamine is used as an optional alkali agent, the mass ratio represented by alkanolamine/component (C) (amine/C ratio) is preferably 0.03 to 3, more preferably 0.05 to 0.1. preferable. If 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 maintained alkaline.

≪Hydrotropic agent≫
The liquid detergent composition can further improve the liquid stability by containing a hydrotrope agent.
Hydrotropic agents include glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, alcohol solvents such as ethanol, sulfonic acids such as p-toluenesulfonic acid, and salts thereof. Among them, glycol-based 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-based solvent is preferably 2 to 5% by mass with respect to the total mass of the liquid detergent composition. If the content of the glycol-based solvent is at least the above lower limit, the liquid stability can be further improved. If the content of the glycol-based solvent is equal to or less than the above upper limit, the decrease in activity of component (B) can be further suppressed.

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

<Physical properties>
More than 7 is preferable, and, as for the pH in 25 degreeC of a liquid detergent composition, 8-11 is more preferable. If the pH is within the above range, it is possible to suppress the deterioration of 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.) at 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 value with an alkaline agent as a pH adjuster.

(how to use)
The method of using the liquid detergent composition (that is, the washing method) includes, for example, a method of putting the liquid detergent composition and the article to be washed into water and stirring them in a washing machine or the like (ordinary washing). Further, for example, a method of dissolving a liquid detergent composition in water in advance to prepare a cleaning liquid, and immersing an object to be washed 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 normal washing may be performed (application washing).
In normal cleaning, the pH of the cleaning solution is preferably 8-10, more preferably 8.5-9.5.
The articles to be washed include, for example, textile products such as clothes, cloths, towels, and sheets. The liquid detergent composition is suitable as a liquid detergent for textiles.
When the liquid detergent composition is used by dissolving it in water, it is preferable to dilute it, for example, 5 to 5000 times (by volume).

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.
In addition, Examples 4 and 6 are reference examples.

(Raw materials used)
<(A) Component: Surfactant>
A-1: Polyoxyethylene alkyl ether (AE(15EO)), a product obtained by adding 15 moles of ethylene oxide to a natural alcohol. A compound wherein R ¹¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, X=O, s=15, t=0, and R ¹¹ = hydrogen in the general formula (a1-1). Synthesized by the synthesis method described below.

≪Synthesis method≫
A pressure-resistant reactor was charged with 861.2 g of natural alcohol CO-1214 (trade name) manufactured by Procter & Gamble and 2.0 g of a 30 mass % NaOH aqueous solution, and the inside of the reactor was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100°C and a pressure of 2.0 kPa or less, the temperature was raised to 160°C. Then, while stirring the reaction liquid, 760.6 g of ethylene oxide (gaseous) was slowly added into the reaction liquid. At this time, ethylene oxide was added through a blowing pipe while adjusting the addition rate so that the reaction temperature did not exceed 180°C.
After completion of the addition of ethylene oxide, 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 the temperature was cooled to 100° C. or lower, 70% by mass of p-toluenesulfonic acid was added to neutralize the reactant so that the pH of the 1% by mass aqueous solution of the reactant would be 7, and A-1 was obtained.

A-2: Linear alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms (LAS, manufactured by Lion Corporation, trade name: Lipon (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: hydrogen carbonate>
· C-1: NaHCO ₃ sodium hydrogen carbonate, manufactured by Kanto Chemical Co., Ltd., trade name "sodium hydrogen carbonate".

<Optional component>
· Protease: Novozymes Japan Co., Ltd., Progress Uno 100L, protease activity: 1800 kPU/g.
- Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
- Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name "sodium benzoate".
- Ethanol: trade name "specific alcohol 95 degree synthesis" manufactured by Nippon Alcohol Sales Co., Ltd.
- MGDA: Trisodium methylglycine diacetate, manufactured by BASF, trade name "Trilon M Liquid".
- Calcium chloride: manufactured by Kanto Kagaku Co., Ltd., trade name "calcium chloride".
- Coconut fatty acid: manufactured by NOF Corporation, trade name "coconut fatty acid".
- PEG1000: polyethylene glycol #1000, manufactured by Mitsui Chemicals, Inc., trade name "PEG #1000-60L".
・Silicone emulsion: Shin-Etsu Chemical Co., Ltd., trade name “KM-90”.
· Preservative 1: 1,2-benzisothiazolin-3-one (BIT), manufactured by THOR, trade name "ACTICIDE B20".
· Preservative 2: 2-methyl-4-isothiazolin-3-one (MIT)/1,2-benzisothiazolin-3-one (BIT), manufactured by THOR, trade name "ACTICIDE MBS".
• Pigment: trade name "Green No. 3" manufactured by Kisumi Kasei Co., Ltd.
Perfume: Perfume composition A described in JP-A-2002-146399.
- pH adjuster: Sodium hydroxide (NaOH), manufactured by Tsurumi Soda Co., Ltd., trade name "sodium hydroxide".

(Evaluation method)
<Detergency>
A cloth tied to a glass rod was impregnated with Chuno sauce (Otsuka Foods Co., Ltd.). The medium thick sauce soaked into the cloth was applied to a cotton plain weave cloth (No. 100, 5 cm x 5 cm), which was air-dried overnight to obtain a cloth contaminated with food stains.
10 stained cloths were placed in 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 stained cloths were washed at 120 rpm for 10 minutes. After dewatering the stained cloth, 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 raw cloth before dirt adheres and the dirty cloth before and after washing is measured using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd.: SE2000), and the source dirt is determined by the following formula (s). was calculated.

Cleaning rate (%) = (Z value of contaminated cloth after washing - Z value of contaminated cloth before washing) / (Z value of original cloth - Z value of contaminated cloth before washing) x 100 (s)

The average detergency rate (%) of 10 stained cloths was classified according to the following evaluation criteria, and "I" and "II" were judged to have good detergency.

≪Evaluation Criteria≫
I: Cleaning rate is 70% or more.
II: Cleaning rate is 60% or more and less than 70%.
III: Cleaning rate is 50% or more and less than 60%.
IV: Cleaning rate less than 50%.

<Liquid stability>
30 mL of the liquid detergent composition of each example was placed in a cylindrical glass bottle and sealed with a lid. This state was stored in a constant temperature bath at 0° C. for one month. Then, it was taken out from the constant temperature bath, the appearance of the liquid detergent composition was visually observed, and the liquid stability of the liquid detergent composition was evaluated based on the following criteria. "I" was set as a pass 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 composition shown in Tables 1 and 2, each component was added to water and mixed to prepare a liquid detergent composition of each example.
The compounding amounts in the table are pure content conversion values, except for enzymes. The amount of enzymes in the table is the amount of formulation. Ingredients whose blending amounts are not listed in the table are not blended.
In the table, the blending amount of water “balance” is the amount necessary to make the whole to 100% by mass. In the table, the "appropriate amount" of sodium hydroxide is the amount necessary to adjust the pH of the liquid detergent composition to the value shown in the table.
The liquid detergent composition of each example was evaluated for food stain detergency and liquid stability, and the results are shown in the table.

As shown in Tables 1 and 2, Examples 1 to 8 to which the present invention was applied were rated "I" or "II" for detergency and "I" for liquid stability.
Comparative Examples 1 and 3, in which the content of the component (B) was less than the lower limit of the present invention, were rated "III" or "IV" in detergency. Comparative Examples 2 and 4 lacking either the component (A) or the component (C) had an evaluation of "IV" in detergency.
From these results, it was confirmed that a liquid detergent composition having excellent detergency and excellent liquid stability can be obtained by applying the present invention.

Claims (4)

(A) component: 12 to 18% by mass of a surfactant containing a nonionic surfactant (component (a1)) and an anionic surfactant (component (a2)) excluding higher fatty acids and salts thereof;
(B) component: 0.05 to 3% by mass of amylase,
(C) component: 2.2 to 4% by mass of hydrogen carbonate,
contains
A liquid detergent composition for textile products, wherein the mass ratio of component (a1)/component (a2) is 1 to 10 . The liquid detergent composition for textile products according to claim 1, wherein the mass ratio represented by component (B)/component (C) is 0.01 to 1.36 . The liquid detergent composition for textile products according to claim 1 or 2 , wherein the content of the component (a1) is 8 to 12% by mass and the content of the component (a2) is 1 to 10% by mass. thing. The component (a1) is a polyoxyalkylene-type nonionic surfactant represented by the following formula (a1-1),
The liquid detergent composition for textile products according to any one of claims 1 to 3, wherein the component (a2) is a linear alkylbenzenesulfonic acid having an alkyl group of 10 to 14 carbon atoms or a salt thereof. .
R ¹¹ -X-[(EO) _s /(PO) _t ]-R ¹² (a1-1)
(In 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 10 to 20. t represents the average number of repetitions of PO and is a number of 0 to 6. EO is oxy An ethylene group and PO represent an oxypropylene group, and EO and PO may be mixed and arranged.)