CN110713866B

CN110713866B - Liquid detergent composition for clothing

Info

Publication number: CN110713866B
Application number: CN201810769068.4A
Authority: CN
Inventors: 朱叶; 倪樱嫣; 小暮荣一
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2018-07-13
Filing date: 2018-07-13
Publication date: 2022-05-03
Anticipated expiration: 2038-07-13
Also published as: CN110713866A

Abstract

The present invention provides a liquid detergent composition for clothing, which maintains excellent enzyme stability under the condition of weak pH, and has excellent smearing decontamination performance and low-temperature stability, and the liquid detergent composition for clothing comprises the following components (A) to (E): (A) 0.01 to 25% by mass of an anionic surfactant; (B) a protease; (C) an organic acid or a salt thereof having a molecular weight of 160 or less, in an amount of 0.01 to 3% by mass; (D) water; and (E) an amphoteric surfactant, wherein the mass ratio (C)/(B) of the component (C) to the component (B) is 70 or more and 521 or less, the mass ratio (E)/(B) of the component (E) to the component (B) is 31 or more, and the pH of the composition at 25 ℃ is 7 or less.

Description

Liquid detergent composition for clothing

Technical Field

The present invention relates to a liquid detergent composition for clothing.

Background

As liquid detergents, consumers generally expect excellent overall cleaning performance, and therefore, generally use enzymes in detergent formulations to improve detergency.

Since the acidic pH can cause enzyme instability in the detergent, and the enzyme denaturation can cause enzyme activity loss, most of the existing enzyme-containing liquid detergents select neutral or alkaline product pH, which is more favorable for enzyme stability. However, since a detergent composition having an acidic pH has a bactericidal and deodorant function and can neutralize stubborn stains such as urine alkali, it is preferable to select an acidic detergent in some use environments. At present, a small amount of enzyme-containing detergent products have an acidic pH, but a large amount of surfactants, solvents, stabilizers and the like are needed to stabilize enzymes under acidic conditions, but the smearing detergency of the detergent products is not ideal, and the detergent products are not environment-friendly.

Patent document 1 discloses an enzyme-containing low pH liquid cleaning composition containing a surfactant system containing an anionic surfactant, a cleaning enzyme, and an organic acidulant, and having a neat pH of 2 to 6. As a result, it was found that the effect of improving the stability of the enzyme at low pH can be obtained by selecting an appropriate acidifying agent.

Patent document 2 discloses a low pH compact fluid laundry detergent composition, and further, an enzyme is added to the composition, and the stability of the enzyme in the composition is evaluated. As a result, it was found that anionic surfactant-based concentrated laundry detergents can be formulated at low pH using branched anionic surfactants and can provide improved enzyme stability.

Patent document 1: CN104508103A

Patent document 2: CN105408461A

Disclosure of Invention

On the other hand, stubborn stains on the collar, the armpit and the like cannot be effectively removed only by washing with water, and the stains can be more effectively removed only by directly applying a detergent on the stains, namely, a liquid detergent with strong decontamination performance is required to be applied. While a large amount of nonionic surfactant or solvent is helpful to enhance the stability of the protease and maintain the activity of the protease, a large amount of nonionic surfactant and polyol solvent often also hinder the performance of the protease in the coating process, so that the coating decontamination performance is not enough. In addition, the low temperature stability of the liquid detergent is also a practically important property according to the environmental requirements.

However, the above patent documents 1 to 2 do not mention the low temperature stability and the smear removal performance of the enzyme-containing low pH detergents.

Accordingly, an object of the present invention is to provide a liquid detergent composition for clothing, which has excellent enzyme stability, smear detergency performance and low-temperature stability at acidic pH.

The inventor finds that: when the pH is weakly acidic, a certain amount of anionic surfactant and protease are mixed with amphoteric surfactant and organic acid in a certain proportion, so that the excellent enzyme stability can be maintained, and the smearing decontamination performance and the low-temperature stability are excellent.

The liquid detergent composition for clothing of the present invention contains the following components (a) to (E):

(A) 0.01 to 25% by mass of an anionic surfactant;

(B) a protease;

(C) an organic acid or a salt thereof having a molecular weight of 160 or less, in an amount of 0.01 to 3% by mass;

(D) water; and

(E) an amphoteric surfactant, and a surfactant component,

wherein the mass ratio (C)/(B) of the component (C) to the component (B) is 70 or more and 521 or less,

the mass ratio (E)/(B) of the component (E) to the component (B) is not less than 31,

the composition has a pH of 7 or less at 25 ℃.

According to the liquid detergent composition for clothing of the present invention, the anionic surfactant, the protease, the specific organic acid, and the amphoteric surfactant are blended in the above composition ratio and the specific content, so that excellent enzyme stability, smear detergency performance, and low-temperature stability can be obtained.

Detailed Description

The components used in the liquid detergent composition of the present invention will be described in detail below.

Component (A)

The component (a) in the liquid detergent composition for clothing of the present invention is one or more anionic surfactants. In the present invention, the component (a) can improve the detergency and rinsing performance of the liquid detergent composition for clothing.

The anionic surfactant as the component (a) is not particularly limited, and 1 or 2 or more kinds selected from commonly used anionic surfactants can be used. Specific examples include:

(a1) an alkyl/alkenyl sulfate having an alkyl group or an alkenyl group having an average carbon number of 10 to 20;

(a2) an alkylbenzenesulfonic acid having an alkyl group with an average carbon number of 10 to 16 or a salt thereof;

(a3) an alkyl/alkenyl sulfonic acid having an alkyl group or an alkenyl group having 10 to 20 carbon atoms on average or a salt thereof;

(a4) a fatty acid having 10 or more carbon atoms or a salt thereof;

(a5) polyoxyalkylene alkyl ether sulfate ester salts having an alkyl group having an average carbon number of 10 to 24 of a linear primary alcohol, a linear secondary alcohol or a branched alcohol and having an average number of moles of addition of oxyalkylene groups of 0.5 to 6, wherein the oxyalkylene groups contain oxyethylene groups and/or oxypropylene groups;

(a6) polyoxyalkylene alkyl ether carboxylate having an alkyl group with an average carbon number of 10 to 20 and an average number of addition mols of oxyalkylene groups of 1 to 10, wherein the oxyalkylene groups contain oxyethylene groups and/or oxypropylene groups.

From the viewpoint of improving detergency and rinsing property, the salt of the anionic surfactant as the component (a) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and further preferably a sodium salt.

The content of the component (a) in the liquid detergent composition for clothing is 0.01% by mass or more, preferably 0.2% by mass or more, and more preferably 2% by mass or more, from the viewpoints of improving the enzyme stability, the smear detergency performance, and obtaining an appropriate viscosity and a desirable rinsing performance of the liquid detergent composition for clothing; and 25% by mass or less, preferably 23% by mass or less.

From these viewpoints, the content of the component (a) in the liquid detergent composition of the present invention is preferably 0.01 to 25% by mass, more preferably 0.2 to 25% by mass, even more preferably 2 to 25% by mass, and even more preferably 2 to 23% by mass.

Ingredient (B)

The component (B) of the liquid detergent composition for clothing of the present invention is a protease. In the present invention, the protease mainly acts to improve the detergency and smear detergency of the detergent.

Examples of the protease used in the present invention include those manufactured by Novivin

International Bio-syntheticManufactured by s Corp Ltd

And

manufactured by Hangao corporation

Manufactured by Kao corporation

Etc.; produced by the company Biocatalysts

24L, 144L, and 671L; protease a and protease B produced by Amano corporation; and produced by Genencor corporation

GC 106 and Fungal Acid Protease 500000, etc. These proteases may be used alone, or 2 or more kinds may be used in combination.

The content of the protease in the liquid detergent composition for clothing of the present invention is 0.0001% by mass or more, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.01% by mass or more, from the viewpoint of improving the detergency and the smear detergency of the liquid detergent composition for clothing; and 5% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

The content of the protease refers to the content of the enzyme protein.

Ingredient (C)

The component (C) in the liquid detergent composition for clothing of the present invention is an organic acid or a salt thereof. The stability of the enzyme can be improved by containing the component (C) in the composition.

From the viewpoint of improving the stability of the enzyme, the organic acid as the component (C) of the present invention is an organic acid having a molecular weight of 160 or less, preferably 159 or less, more preferably 147 or less, and further preferably 135 or less; further, aliphatic carboxylic acids are preferable. Specific examples of the component (C) include formic acid, acetic acid, propionic acid, n-butyric acid, oxalic acid, succinic acid, lactic acid, malic acid, glutaric acid, adipic acid, pimelic acid, etc., preferably formic acid, acetic acid, propionic acid, n-butyric acid, succinic acid, lactic acid, malic acid, and more preferably formic acid, lactic acid, propionic acid, n-butyric acid, malic acid. The salt thereof is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and still more preferably a sodium salt.

The content of the organic acid of component (C) is 0.01 mass% or more, preferably 0.8 mass% or more, more preferably 1.0 mass% or more, and further preferably 1.15 mass% or more from the viewpoint of improving the stability of the enzyme and the smear detergency, and the content of the organic acid of component (C) is 3.0 mass% or less, preferably 2.5 mass% or less, and more preferably 2.0 mass% or less from the viewpoint of improving the low-temperature stability and the smear detergency of the liquid detergent composition. Therefore, the content of the organic acid as the component (C) is selected from 0.01 to 3.0 mass%, preferably 0.8 to 3.0 mass%, more preferably 1.0 to 3.0 mass%, still more preferably 1.15 to 2.5 mass%, and yet more preferably 1.15 to 2.0 mass%.

In addition, from the viewpoint of improving the enzyme stability of the composition, the ratio of the content of the component (C) to the content of the component (B), (C)/(B), is 70 or more, preferably 100 or more, and from the viewpoint of improving the low-temperature stability and the smear detergency of the liquid detergent composition, (C)/(B) is 521 or less, preferably 434 or less, more preferably 347 or less, further preferably 150 or less, and still further preferably 140 or less. Therefore, the ratio (C)/(B) of the contents of the component (C) and the component (B) is 70 or more and 521 or less, preferably 100 or more and 434 or less, more preferably 100 or more and 347 or less, further preferably 100 or more and 150 or less, and further preferably 100 or more and 140 or less.

Ingredient (D)

The liquid detergent composition for clothing of the present invention contains water as the component (D). Water constitutes the balance of the above-mentioned components and other components of the liquid detergent composition for clothing. The content of the component (D) is preferably 30% by mass or more, more preferably 65% by mass or more, in the entire composition, from the viewpoint of improving the smearing detergency of the liquid detergent composition, and is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of improving the enzyme stability of the composition. As the water, water having no influence on the composition, such as deionized water, is preferable.

Ingredient (E)

The component (E) in the liquid detergent composition for clothing of the present invention is an amphoteric surfactant, and in the present invention, the stability of the enzyme in the liquid detergent composition can be improved by containing the component (E) in a certain proportion in the liquid detergent composition.

The reason why the amphoteric surfactant can improve the stability of the enzyme in the liquid detergent composition is not clear, and is presumed as follows: the charge of the hydrophilic group of the anionic surfactant contained in the liquid detergent composition acts with the protease, the space structure of the protease is changed, the activity of the protease is reduced, and the action degree is in direct proportion to the charge intensity; in addition, the hydrophobic group of the anionic surfactant interacts with the nonpolar group inside the protease to inactivate the protease. By adding the amphoteric surfactant to the liquid detergent composition, the positive charge group of the amphoteric surfactant is electrostatically attracted to the hydrophilic group of the anionic surfactant, thereby preventing or inhibiting the interaction between the anionic surfactant and the protease, and improving the stability of the enzyme in the liquid detergent composition.

The amphoteric surfactant as the component (E) may be a betaine amphoteric surfactant or an amine oxide surfactant having a linear or branched hydrocarbon group, and among them, an amine oxide surfactant having a linear or branched hydrocarbon group is preferably used.

Examples of the betaine amphoteric surfactant include: alkyl imidazoline betaines such as lauryl imidazoline betaine and coco imidazoline betaine; amidopropyl betaines such as lauramidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, and coconut oil fatty acid amidopropyl betaine; alkyl sulfobetaines such as lauryl ethoxy sulfobetaine and stearyl ethoxy sulfobetaine; hydroxy sulfobetaines such as coconut oil fatty acid hydroxy sulfobetaine, lauryl hydroxy sulfobetaine, and tetradecyl hydroxy sulfobetaine; alkyl carboxybetaines such as dilauryl dimethyl carboxybetaine and stearyl hexyl methyl carboxybetaine.

As the amine oxide type surfactant having a linear or branched hydrocarbon group, the linear or branched hydrocarbon group is preferably a linear alkyl group. Examples of such amine oxide-type amphoteric surfactants include hexyldimethylamine oxide, octyldimethylamine oxide, decyldimethylamine oxide, dodecyldimethylamine oxide, tetradecyldimethylamine oxide, hexadecyldimethylamine oxide, N-octylmorpholine-N-oxide, N-decyldorpholine-N-oxide, N-dodecylmorpholine-N-oxide, and N-tetradecylmorpholine-N-oxide.

From the viewpoint of improving the enzyme stability and the smear-removing performance of the liquid detergent composition for clothing, the mass ratio (E)/(B) of the component (E) and the component (B) in the liquid detergent composition is 31 or more, preferably 35 or more. From the viewpoint of obtaining low-temperature stability and an appropriate viscosity of the liquid detergent composition, (E)/(B) is preferably 200 or less, and more preferably 100 or less.

pH value

The liquid detergent composition of the present invention has a pH of 7 or less at 25 ℃, and is preferably 4.7 or more, more preferably 5 or more, from the viewpoint of achieving both of bactericidal and deodorant properties, mildness to the skin, and enzyme stability.

Here, the pH may be adjusted to the above range using a pH adjuster, which is preferably 1 or 2 or more selected from alkali metal hydroxides, organic bases, inorganic acids, and organic acids other than the above components (a) and (C), more preferably 1 or 2 or more selected from sodium hydroxide, potassium hydroxide, alkanolamines, ammonia, sulfuric acid, hydrochloric acid, and the like; more preferably 1 or 2 or more selected from sulfuric acid, hydrochloric acid, and sodium hydroxide.

Other ingredients

In the liquid detergent composition of the present invention, other components may be blended in addition to the above components within a range not impairing the object or effect of the present invention. As other components, for example: nonionic surfactants, chelating agents, foam boosters, builders, rust inhibitors, viscosity modifiers, antioxidants, antibacterial/antifungal agents, preservatives, migration inhibitors, bleaching agents, bleach activators, solubilizers, fluorescent dyes, colorants, perfumes, amylases, cellulases, lipases and other types of enzymes, silicones and other antifoam agents, and the like, which are generally used in liquid detergent compositions.

Examples of the nonionic surfactant include: 1 or more than 2 of polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, alkyl polyglycoside, alkyl alcohol amide and glycerin fatty acid ester. Among them, polyoxyethylene alkyl ethers are preferred from the viewpoint of easy rinsing of the detergent.

The number of carbon atoms of the alkyl group of the polyoxyethylene alkyl ether is preferably 8 or more, more preferably 10 or more, and further preferably 12 or more from the viewpoint of detergency and product stability, and is preferably 18 or less, more preferably 16 or less, and further preferably 14 or less from the same viewpoint.

The content of the nonionic surfactant is preferably 0.4% by mass or more, more preferably 1.0% by mass or more, further preferably 1.2% by mass or more, and further preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less, from the viewpoint of easy rinsability of the detergent.

Examples of the chelating agent include: ethylenediaminetetraacetic acid, phosphonates, and the like.

Examples of the foam boosters include: fatty acid alkanolamides, and the like.

Examples of builders include: inorganic builders such as sodium tripolyphosphate, sodium silicate, sodium carbonate, sodium sulfate, and the like; organic builders such as sodium polyacrylate.

Examples of the rust inhibitor include: pentaerythritol esters, phytates, and the like.

Examples of the viscosity modifier include: hydroxyethyl cellulose, methyl cellulose, carboxyvinyl polymers, and the like.

Examples of the antioxidant include: butyl hydroxy toluene, distyrenated cresol, sodium sulfite, sodium bisulfite and the like.

Examples of the antibacterial and antifungal agents include: silver ion antibacterial agent, zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate, vanillin or vinyl vanillin compound, etc.

Examples of the preservative include: phenoxyethanol, methyl paraben, butyl paraben, 1, 2-benzothiazolin-3-one, and the like.

Examples of the migration inhibitor include polyvinylpyrrolidone.

Examples of the bleaching agent include hydrogen peroxide, sodium percarbonate, and sodium perborate.

Examples of the bleach activator include tetraacetylethylenediamine and the like.

Examples of the solubilizer include p-toluenesulfonic acid, cumenesulfonic acid, and m-xylenesulfonic acid.

Examples of the fluorescent dye include Tinopal CBS-X (manufactured by BASF SE).

The liquid detergent composition of the present invention is suitable for household washing, and is suitable for hand washing.

The present invention further discloses the following liquid detergent compositions according to the above embodiments.

[1] A liquid detergent composition for clothing, comprising the following components (A) to (E):

(A) 0.01 to 25% by mass of an anionic surfactant;

(B) a protease;

(D) water; and

(E) an amphoteric surfactant, and a surfactant component,

wherein the mass ratio (C)/(B) of the component (C) to the component (B) is 70 or more and 521 or less, the mass ratio (E)/(B) of the component (E) to the component (B) is 31 or more, and the pH of the composition at 25 ℃ is 7 or less.

[2] The liquid detergent composition for clothing as described in [1], wherein the component (A) is 1 or 2 or more kinds of anionic surfactants selected from the following (a1) to (a 6):

(a4) a fatty acid having 10 or more carbon atoms or a salt thereof;

[3] The liquid detergent composition for clothing according to [1] or [2], wherein the content of the component (A) is 0.01% by mass or more, preferably 0.2% by mass or more, and more preferably 2% by mass or more; and 25% by mass or less, preferably 23% by mass or less.

[4] The liquid detergent composition for clothing as claimed in any one of [1] to [3], wherein the content of the component (A) is preferably 0.01 to 25% by mass, more preferably 0.2 to 25% by mass, even more preferably 2 to 25% by mass, and even more preferably 2 to 23% by mass.

[5] The liquid detergent composition for clothing according to any one of [1] to [4], wherein the content of the component (B) is 0.0001% by mass or more, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more; and 5% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

[6] The liquid detergent composition for clothing according to any one of [1] to [5], wherein the component (C) is an organic acid or a salt thereof having a molecular weight of 160 or less, preferably 159 or less, more preferably 147 or less, still more preferably 135 or less, and still more preferably an aliphatic carboxylic acid or a salt thereof.

[7] The liquid detergent composition for clothing according to any one of [1] to [6], wherein the component (C) is formic acid, acetic acid, propionic acid, n-butyric acid, oxalic acid, succinic acid, lactic acid, malic acid, glutaric acid, adipic acid, pimelic acid, or a salt thereof. Further preferred as the component (C) are formic acid, lactic acid, propionic acid, n-butyric acid and malic acid.

[8] The liquid detergent composition for clothing according to any one of [1] to [7], wherein the content of the component (C) is 0.01% by mass or more, preferably 0.8% by mass or more, more preferably 1.0% by mass or more, further preferably 1.15% by mass or more, and is 3.0% by mass or less, preferably 2.5% by mass or less, more preferably 2.0% by mass or less.

[9] The liquid detergent composition for clothing according to any one of [1] to [8], wherein the content of the organic acid as the component (C) is 0.01 to 3.0% by mass, preferably 0.8 to 3.0% by mass, more preferably 1.15 to 2.5% by mass, and still more preferably 1.15 to 2.0% by mass.

[10] The liquid detergent composition for clothing according to any one of [1] to [9], wherein the content ratio (C)/(B) of the component (C) to the component (B) in the liquid detergent composition for clothing is 70 or more, preferably 100 or more, 521 or less, preferably 434 or less, more preferably 347 or less, further preferably 150 or less, and further preferably 140 or less.

[11] The liquid detergent composition for clothing according to any one of [1] to [10], wherein the content ratio (C)/(B) of the component (C) to the component (B) is 70 or more and 521 or less, preferably 100 or more and 434 or less, more preferably 100 or more and 347 or less, further preferably 100 or more and 150 or less, and further preferably 100 or more and 140 or less.

[12] The liquid detergent composition for clothing according to any one of [1] to [11], wherein the component (E) is a betaine-type amphoteric surfactant or an amine oxide-type surfactant having a linear or branched hydrocarbon group, preferably an amine oxide-type surfactant having a linear or branched hydrocarbon group.

[13] The liquid detergent composition for clothing according to any one of [1] to [12], wherein the component (E) is a betaine amphoteric surfactant selected from the group consisting of alkyl imidazoline betaine, amidopropyl betaine, alkyl sulfobetaine, hydroxysulfobetaine, and alkyl carboxybetaine, preferably a betaine amphoteric surfactant selected from the group consisting of lauryl imidazoline betaine, cocoyl imidazoline betaine, lauramidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, coco fatty acid amidopropyl betaine, lauryl ethoxysulfobetaine, stearyl ethoxysulfobetaine, coco fatty acid hydroxysulfobetaine, lauryl hydroxysulfobetaine, tetradecylhydroxysulfobetaine, dilauryl dimethylcarboxybetaine, and stearyl hexylmethyl carboxybetaine.

[14] The liquid detergent composition for clothing according to any one of [1] to [12], wherein the component (E) is an amine oxide type surfactant selected from the group consisting of hexyldimethylamine oxide, octyldimethylamine oxide, decyldimethylamine oxide, dodecyldimethylamine oxide, tetradecyldimethylamine oxide, hexadecyldimethylamine oxide, N-octylmorpholine-N-oxide, N-decyldorpholine-N-oxide, N-dodecylmorpholine-N-oxide, and N-tetradecylmorpholine-N-oxide.

[15] The liquid detergent composition for clothing according to any one of [1] to [14], wherein the mass ratio (E)/(B) of the component (E) to the component (B) in the liquid detergent composition is not less than 31, preferably not less than 35, and the mass ratio (E)/(B) is preferably not more than 200, more preferably not more than 100.

[16] The liquid detergent composition for clothing according to any one of [1] to [15], wherein the liquid detergent composition has a pH of 4.7 or more, more preferably 5 or more, at 25 ℃.

Examples

The following examples are illustrative and comparative of the present invention and are not intended to limit the present invention. Before specific examples and comparative examples, the following evaluation methods and evaluation criteria used in the experiments will be described.

The evaluation method comprises the following steps:

(1) evaluation of enzyme stability

100g of liquid detergent samples were sealed in approximately 110ml glass bottles, stored in a 40 ℃ incubator and tested for residual protease activity after 7 days. The activity of the enzyme after 7 days was expressed as% of the activity of the enzyme at the start of the test.

Method for determining AAPL protease activity:

the chromogenic group p-nitroaniline (pNa) was produced by using a substrate Glt-Ala-Pro-Leu-pNa (p-nitroaniline, Peptide Institute, inc.) as a catalyst in a protease (Progress Uno 100L, manufactured by novacin corporation), and the absorbance at 420nm was quantitatively determined by using an ultraviolet spectrophotometer (SHIMADZU VUmini1240) in the following experimental procedure.

The experimental steps are as follows:

1) taking 0.45mL of 1/15M phosphoric acid buffer solution (pH 7.4);

2) adding 0.025ml of 100mM AAPL solution (Glt-Ala-Ala-Pro-Leu-pNa) into the buffer solution;

3) pre-insulating for 5 minutes in a water bath at 50 ℃;

4) adding 0.025ml of the sample to be detected into the solution to be subjected to heat preservation;

5) then the solution is kept warm for 30 minutes in water bath at 50 ℃;

6) the solution was removed from the water bath and 1ml of citric acid (10%) solution was added;

7) and (3) quantitatively measuring the absorbance of the ultraviolet spectrophotometer at 420 nm.

Determination sequence of the absorbance a of the experimental samples: 1 → 2 → 3 → 4 → 5 → 6 → 7.

Measurement sequence of absorbance B of control blank sample: 1 → 2 → 3 → 6 → 4 → 5 → 7.

The calculation method comprises the following steps:

stability of enzyme (a1-B1)/(a0-B0) (%)

A1: the absorbance values obtained according to the experimental procedure described above were obtained for samples stored under certain conditions (i.e. after storage in a thermostat at 40 ℃ for 7 days);

b1: corresponding to the blank sample, and obtaining an absorbance value according to the experimental steps;

a0: the absorbance value of the sample at the beginning of the test is obtained according to the experimental steps;

b0: the absorbance values obtained in the above experimental procedure were obtained for the corresponding blank samples at the start of the experiment.

The stability of the enzyme was evaluated according to the following criteria (7 days/40 ℃):

very good: over 65 percent

O: more than 60 percent and less than 65 percent

X: less than 60 percent.

(2) Evaluation of smearing detergency

Preparing dirty cloth: STC EMPA117 (manufactured by testfabrics, inc., a protein cotton polyester cloth dyed with blood, milk, and carbon black) was prepared.

Before the soiled cloth was subjected to the wiping washing, the whiteness value Y1 of the soiled cloth was measured.

Smearing and washing: 0.5g of sample liquid detergent is measured and directly smeared on stains of 6cm multiplied by 6cm dirty cloth, placed for 10 minutes and then washed by a vertical type cleaning machine. At least 3 pieces of dirty cloth are respectively manufactured for each liquid detergent sample to carry out parallel experiments, each sample corresponds to 1 decontamination jar, at least 3 pieces of smeared dirty cloth are placed into each decontamination jar, and 1L of tap water for washing is added. The instrument was adjusted to maintain a temperature of 25. + -. 1 ℃ at a speed of 120 r/min, and the washing was stopped after 10 minutes. After rinsing, the cloth was dried, and the whiteness value Y2 of the cloth piece was measured.

The detergency calculation formula is:

the detergency of the smears was evaluated according to the following criteria

Very good: more than 24 percent

O: 20% or more and 24% or less

X: less than 20 percent

(3) Evaluation of Low temperature stability of detergent

The sample liquid detergent was placed at a constant temperature of 0 ℃ and observed with the naked eye, and the appearance stability at low temperature was evaluated according to the following criteria.

X: within 1 day, there was significant turbidity, precipitation or delamination.

In 2-7 days, a little turbidity, precipitation or delamination occurs, and the difference is obvious after the temperature is restored to the room temperature.

Good: in 2-7 days, there was a small amount of turbidity, precipitation or delamination, but there was no significant change after returning to room temperature from before the experiment. .

Very good: over 7 days, no obvious turbidity, precipitation or demixing.

(4) Method for measuring pH

The pH measurement was carried out using a pH meter (D-52) and a pH electrode (6367-10D) manufactured by horiba, Ltd., in the following order. The standard solutions were prepared by transferring a pH4 standard solution (product No. K9084KF), a pH7 standard solution (product No. K9084KG) and a pH9 standard solution (product No. K9084KH) manufactured by Yokogawa electric corporation to a 50ml beaker.

The pH electrode was thoroughly washed with ion-exchanged water and wiped with a tissue paper (tissue paper). The internal liquid replenishment port of the pH electrode was opened and the pH electrode was immersed in a beaker containing a standard solution of pH 7. In a state where the pH electrode was immersed in the sample for 3cm, the "CAL" key was pressed after 1 minute. After "HOLD" indicated stopping the blinking, the pH electrode was thoroughly washed with ion-exchanged water and wiped with tissue paper. Subsequently, the same operation was repeated using the pH4 standard solution and the pH9 standard solution, and three-point calibration was performed. After the calibration is completed, the electrode is immersed in a pH7 standard solution in a calibration mode, a 'ENTER' key is pressed, a pH reproducibility check is performed, and if the pH is within 0.05, the calibration is completed.

Next, the pH electrode was thoroughly washed with ion-exchanged water and wiped with a tissue paper. The liquid detergent compositions of examples and comparative examples and a diluted solution obtained by diluting the liquid detergent composition 100 times were used as samples, and the measurement was carried out by pressing the "MEAS" key 2 minutes after the pH electrode was immersed in the sample for 3cm after confirming that the internal liquid replenishment port of the pH electrode was opened.

Note: the compounding ingredients used in the examples and comparative examples are as follows.

< ingredient (A) >

(a-1): sodium alkyl sulfate, wherein the carbon atom number is 12-14: (trade name: AS-MEA; manufacturer: Jiangsu Fengyi chemical technology Co., Ltd.)

(a-2): alkyl benzene sulfonic acid, the number of carbon atoms is 10-16: (trade name: LAS-S; manufacturer: Shanghai Jingdi chemical Co., Ltd.)

(a-3): sodium alpha-alkenyl sulfonate, the number of carbon atoms is 14-16: (trade name: Sodium Alpha Olefin Sulfonate 35%; manufacturer: Jiangsu Fengyi chemical technology Co., Ltd.)

(a-4): c14 fatty acids: (trade name: POFAC 1498; manufacturer: Southern Acids (M) Bhd)

(a-5): sodium lauryl polyoxyalkylene ether (EO average addition mole number ═ 2) sulfate: (trade name: EMAL 270S, manufacturer: Kao corporation)

< ingredient (B) >

Protease: (trade name: Progress Uno 100L; manufacturer: Novexin (China) Biotechnology Co., Ltd.)

< ingredient (C) >

(c-1): formic acid, molecular weight 46.03 (trade name: formic acid; manufacturer: national pharmaceutical group)

(c-2): lactic acid having a molecular weight of 90.08 (trade name: lactic acid; manufacturer: national drug group)

(c-3): n-Butanoic acid, molecular weight 88.10 (trade name: n-Butanoic acid; manufacturer: national pharmaceutical group)

(c-4): succinic acid, molecular weight 118.09 (trade name: succinic acid; manufacturer: national drug group)

(c-5): malic acid, molecular weight 134.02 (trade name: malic acid; manufacturer: national group of drugs)

(c-6): adipic acid having a molecular weight of 146.14 (trade name: adipic acid; manufacturer: national pharmaceutical group)

(c-7): pimelic acid, molecular weight 158.15 (trade name: pimelic acid; manufacturer: national drug group)

(C'): suberic acid, molecular weight 174.2 (trade name: suberic acid; manufacturer: national pharmaceutical group)

< ingredient (E) >

(e-1): c8 amine oxide (trade name: BARLOX 8S; manufacturer: Lonza Inc.)

(e-2): dodecyl dimethylamine acetate betaine (trade name: AMPHITOL 20 BS; manufacturer: Shanghai flower King chemical Co., Ltd.)

(e-3): dodecyl hydroxysulfobetaine (trade name: AMPHITOL 20 HD; manufacturer: Shanghai flower King chemical Co., Ltd.)

(e-4): n, N-Dimethyldecyl-N-amine oxide (trade name: Barlox 10S; manufacturer: Lonza Inc.)

(e-5): coconut oil fatty acid amide propyl betaine (trade name: AMPHITOL 55 AB; manufacturer: Shanghai King Chemicals Co., Ltd.)

< other ingredients >

Branched fatty alcohol polyoxyethylene ether (EO ═ 20): (trade name: PANNOX 720; manufacturer: Pan Asia GmbH)

Branched fatty alcohol polyoxyethylene ether (EO ═ 9): (trade name: AEO-9; manufacturer: Shanghai Polylon chemical Co., Ltd.)

Phenoxyethanol: (trade name: NEOLONE PH 100; manufacturer: Dow chemical)

Sodium hydroxide: (trade name: NaOH (48%); manufacturer: Shanghai chlor-alkali chemical Co., Ltd., used as a pH adjuster for liquid detergent compositions.)

Sulfuric acid: (trade name: 98% SULFURIC ACID; manufacturer: Shanghai Jingteng chemical Co., Ltd., use as a pH adjuster for liquid detergent compositions.)

Examples 1 to 9 and comparative examples 1 to 3

The liquid detergent compositions for clothing of examples 1 to 9 and comparative examples 1 to 3 having a pH of 5.0 at 25 ℃ were prepared by blending the components shown in Table 1 (content unit of each component: mass%), and the enzyme stability, the smear detergency and the low-temperature stability of each of the examples and comparative examples were evaluated. The results are also shown in table 1.

As is clear from the results in table 1, by adjusting the respective components of the liquid detergent composition to appropriate ranges, and controlling the mass ratio (C)/(B) of the component (C) organic acid and the component (B) protease to 70 or more and 521 or less, and controlling the mass ratio (E)/(B) of the component (E) amphoteric surfactant and the component (B) protease to 31 or more, a liquid detergent composition excellent in enzyme stability at acidic pH (═ 5.0), stain removal performance at application, and low-temperature stability can be obtained. It is also found that when (C)/(B) is too low, the stability of the enzyme is adversely affected, and when (C)/(B) is too high, the stain removal performance and the low-temperature stability are adversely affected. If (E)/(B) is too low, the stability of the enzyme may be adversely affected.

(examples 10 to 12)

Liquid detergent compositions for clothing of examples 10 to 12 were prepared by mixing the components shown in Table 2 (content unit of each component: mass%) and adjusting the pH at 25 ℃ to evaluate the enzyme stability, the smear detergency and the low-temperature stability of each example. The results are also shown in table 2.

As is apparent from table 2, in the present invention, by adjusting the contents and proportions of the respective components of the liquid detergent composition to appropriate ranges, the stability of the enzyme can be maintained within the range of pH 4.7 to 7.0 of the composition, and excellent stain-removing ability by application and low-temperature stability can be obtained.

(examples 13 to 19, comparative example 4)

The liquid detergent compositions of examples 13 to 19 and comparative example 4 were prepared in the content ratio shown in table 3 below, and the pH was adjusted to 5.7, while changing the kind of the organic acid, and the enzyme stability, the smear detergency and the low-temperature stability of the detergent compositions of the examples and comparative examples were measured. The results are shown in Table 3.

As is clear from the results in table 3, in the liquid detergent composition of the present invention, by using an organic acid having a molecular weight of 160 or less, excellent enzyme stability, smear detergency and low-temperature stability can be obtained. In the case of suberic acid having a molecular weight of 174.2, the stability of the enzyme of the liquid detergent composition is affected.

Examples 20 to 22

The liquid detergent compositions of examples 20 to 22 in table 4 were prepared by changing the content of anions in the detergent compositions (content unit of each component: mass%), and the enzyme stability, the smear detergency and the low-temperature stability of the detergent compositions of the examples were measured. The results are shown in Table 4.

As can be seen from table 4, the liquid detergent composition of the present invention can obtain excellent enzyme stability, smear detergency and low temperature stability performance within a suitable range of anionic surfactant content.

(examples 23 to 26)

The liquid detergent compositions of examples 23 to 26 were prepared in the content ratios shown in table 5 below while changing the kinds of amphoteric surfactants, and the pH was adjusted to 6.0, and the enzyme stability, the smear detergency and the low-temperature stability of the detergent compositions of the respective examples were measured. The results are shown in Table 5.

[ Table 5]

As is clear from the results in table 5, in the liquid detergent composition of the present invention, excellent enzyme stability, smear detergency and low-temperature stability can be obtained by using various amphoteric surfactants.

Claims

1. A liquid detergent composition for clothing, wherein,

comprises the following components (A) to (E):

(A) 0.01 to 25% by mass of an anionic surfactant;

(B) a protease;

(C) an aliphatic carboxylic acid or pimelic acid having a molecular weight of 160 or less or a salt thereof, in an amount of 0.01 to 3% by mass;

(D) water; and

(E) an amphoteric surfactant, and a surfactant component,

the composition has a pH of 7 or less at 25 ℃.

2. The liquid detergent composition for clothing according to claim 1, wherein,

the component (C) is an aliphatic carboxylic acid having a molecular weight of 159 or less or a salt thereof.

3. The liquid detergent composition for clothing according to claim 1, wherein,

the content of the component (C) is 0.80 to 3 mass%.

4. The liquid detergent composition for clothing according to claim 1, wherein,

the composition has a pH of 4.7 or more at 25 ℃.

5. The liquid detergent composition for clothing according to claim 4, wherein,

the composition has a pH of 5.0 or more at 25 ℃.

6. The liquid detergent composition for clothing according to claim 1, wherein,

the mass ratio (C)/(B) of the component (C) to the component (B) is 100 to 434 inclusive.

7. The liquid detergent composition for clothing according to claim 1, wherein,

the mass ratio (E)/(B) of the component (E) to the component (B) is 35 or more.

8. The liquid detergent composition for clothing according to claim 1, wherein,

the component (E) is an amine oxide type surfactant having a linear or branched hydrocarbon group or a betaine type amphoteric surfactant.

9. The liquid detergent composition for clothing according to claim 1, wherein,

the content of the component (A) is 0.2 to 25 mass%.

10. The liquid detergent composition for clothing according to claim 1, wherein,

the content of the component (A) is 2 to 25 mass%.

11. The liquid detergent composition for clothing according to claim 1, wherein,

the content of the component (A) is 2 to 23 mass%.

12. The liquid detergent composition for clothing according to claim 1, wherein,

the component (C) is an aliphatic carboxylic acid having a molecular weight of 147 or less or a salt thereof.

13. The liquid detergent composition for clothing according to claim 1, wherein,

the component (C) is an aliphatic carboxylic acid having a molecular weight of 135 or less or a salt thereof.

14. The liquid detergent composition for clothing according to claim 1, wherein,

the component (C) is formic acid, acetic acid, propionic acid, n-butyric acid, oxalic acid, succinic acid, lactic acid, malic acid, glutaric acid, adipic acid, pimelic acid, or a salt thereof.

15. The liquid detergent composition for clothing according to claim 1, wherein,

the content of the component (C) is 1.15 to 2.5 mass%.

16. The liquid detergent composition for clothing according to claim 1, wherein,

the content of the component (C) is 1.15 to 2.0 mass%.

17. The liquid detergent composition for clothing according to claim 1, wherein,

the content ratio (C)/(B) of the component (C) to the component (B) in the liquid detergent composition for clothing is not less than 100 and not more than 347.

18. The liquid detergent composition for clothing according to claim 1, wherein,

the content ratio (C)/(B) of the component (C) to the component (B) in the liquid detergent composition for clothing is 100 to 150.

19. The liquid detergent composition for clothing according to claim 1, wherein,

the content ratio (C)/(B) of the component (C) to the component (B) in the liquid detergent composition for clothing is 100 to 140.

20. The liquid detergent composition for clothing according to claim 1, wherein,

the mass ratio (E)/(B) of the component (E) and the component (B) in the liquid detergent composition is 200 or less.

21. The liquid detergent composition for clothing according to claim 1, wherein,

the mass ratio (E)/(B) of the component (E) and the component (B) in the liquid detergent composition is 100 or less.