JPH0631427B2 - Enzyme-containing liquid detergent composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an enzyme-containing liquid detergent composition. More specifically, the present invention relates to an enzyme-containing liquid detergent composition for clothes, which is excellent in liquid stability and enzyme stability.

BACKGROUND ART Conventionally, in order to improve the detergency of a cleaning agent, for example, an enzyme such as amylase or protease is added, but when the enzyme is added to a liquid cleaning agent, the enzyme is gradually stored during storage. However, the enzyme activity is often almost lost during long-term storage.

Therefore, various proposals have hitherto been made in order to stabilize the enzyme activity of the enzyme-containing liquid detergent. For example, a method of selecting a specific anionic surfactant such as α-olefin sulfonate as a surfactant (Japanese Examined Patent Publication No. 48-3064).
No. 6), a method of combining a nitrogen compound and a lower carboxylic acid salt (JP-A-47-3733), a method of combining free calcium ions and a polyacid for appropriately chelating the calcium ions (special 52-128904
JP-A-53-57209, JP-A-53-57204, and method of adding a specific boric acid compound (JP-A-53-16012).
JP-A-55-27378) or a method of combining an antioxidant and a polyol has been proposed.

However, although these methods have a certain level of enzyme activity stabilizing effect, they are not capable of sufficiently exhibiting the purification performance of the enzyme, and when a builder is added, the oxygen activity is further deteriorated, and the stability of the liquid is further improved. There is a drawback such as damage.

Problems to be Solved by the Invention An object of the present invention is to overcome such drawbacks, to exert the effect of an enzyme remarkably, to have a great effect of removing stains on clothes, and to have an enzyme-containing liquid excellent in liquid stability. To provide a detergent composition.

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have used polyoxyethylene alkyl sulfate ester salt as an anionic surfactant, in which diglycolic acid or its salt is used. It was found that enzyme deactivation can be significantly suppressed by combining aminocarboxylic acid or an aminocarboxylic acid or a salt thereof at a specific ratio and adjusting the pH within a predetermined range, and the object can be achieved. The present invention has been completed based on the above.

That is, the present invention provides (A) a general formula RO (CH ₂ CH ₂ O) nSO ₃ M (I) (wherein R is an alkyl group or an alkenyl group having 11 to 15 carbon atoms, and n is 2 to 7). Number of range, M is an alkali metal or alkanol-substituted or unsubstituted ammonium group) 15 to 40% by weight of an anionic surfactant represented by
(B) diglycolic acid or a salt thereof in an amount of 5 to 15% by weight, (C) aminocarboxylic acid or a salt thereof in an amount of 0.001 to 1% by weight, and (D) an enzyme, and having a pH in the range of 9.0 to 11.0. A characteristic enzyme-containing liquid detergent composition is provided.

In the liquid detergent composition of the present invention, the anionic surfactant used as the component (A) is a polyoxyethylene alkyl sulfate ester represented by the general formula RO (CH ₂ CH ₂ O) nSO ₃ M (I) In the salt, R in the formula is a linear or branched alkyl group or alkenyl group having 11 to 15 carbon atoms. If the carbon number of R is less than 11, the detergency is inferior, and if it exceeds 15, the liquid property deteriorates, which is not preferable. The preferred carbon number is 12 to 13. In the formula, M is an alkali metal such as sodium or potassium, or an ammonium group, and the ammonium group may be substituted with 1 to 3 alkanols such as ethanol and propanol. Further, in the formula, n is the average number of moles of ethylene oxide added and is a number in the range of 2 to 7. If the average number of moles of ethylene oxide added is less than 2, the stability of the enzyme and the stability of the liquid will be reduced, and if it exceeds 7, the foamability will be reduced, such being undesirable. A desirable average added mole number is 3 to 7.

Such a polyoxyethylene alkyl sulfate ester salt is, for example, a synthetic or natural alkyl alcohol or alkenyl alcohol having a carbon chain length of C ₁₁ to ₁₅ in the presence of an alkali catalyst or an acid catalyst and 2 to 7 moles of ethylene oxide. It can be easily obtained by introducing the compound (1) to carry out an addition reaction, sulfating the resulting addition reaction product with a sulfonating agent such as sulfan, and then neutralizing the product.

The content of the polyoxyethylene alkyl sulfate ester salt must be contained in the detergent composition in an amount of 15 to 40% by weight, preferably 20 to 35% by weight. 1
If it is less than 5% by weight, the performance such as detergency and foaming is deteriorated, and if it exceeds 40% by weight, the liquid stability is deteriorated, which is not preferable.

The component (B) in the detergent composition of the present invention is diglycolic acid or a salt thereof, and the counterion in the diglycolic acid salt is, for example, an alkali metal such as sodium or potassium, monoethanol substitution, diethanol substitution, triethanol. Examples thereof include alkanol-substituted or unsubstituted ammonium residues such as substituted. The content of the diglycolic acid or its salt is 5 to 15% by weight, preferably 5 to 10% by weight, based on the detergent composition. If this amount is less than 5% by weight, the enzyme stability will decrease, and if it exceeds 15% by weight, the components in the composition will separate. By using this diglycolic acid or its salt in combination, it has become possible to add an aminocarboxylic acid or its salt, which has been difficult to add in the past.

In the cleaning composition of the present invention, as the aminocarboxylic acid or salt thereof used as the component (C), for example, ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, these And the like. As the counterion in the aminocarboxylic acid salt,
Examples thereof include alkali metal such as sodium ion and potassium ion, ion, ammonium ion, monoethanol-substituted ammonium ion, diethanol-substituted ammonium ion, triethanol-substituted ammonium ion, and other alkanol-substituted or unsubstituted ammonium ions. The compounding amount of the aminocarboxylic acid or its salt is selected in the range of 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, based on the detergent composition.
If this amount is less than 0.001% by weight, a precipitate will form in the composition, and if it exceeds 1% by weight, separation will occur.

Typical examples of the enzyme used as the component (D) in the detergent composition of the present invention include proteolytic enzymes, starch degrading enzymes, lipolytic enzymes and the like, among which bacterial proteolytic enzymes are preferred. Suitable proteolytic enzymes can include, for example, alcalase, savinase, esperase, maxatase, pioplase and the like.

Regarding the amount of the enzyme to be blended, when using a starch degrading enzyme, an amount having an activity of 10 ⁴ to ⁵ mannose units per 1 kg of the detergent composition, and when using a protein degrading enzyme, 1 to 30 anson per 1 kg of the detergent composition. It is desirable to choose an amount such that it has unit activity.

Furthermore, the detergent composition of the present invention needs to have its pH adjusted to the range of 9.0 to 11.0 in order to sufficiently exert the effect of the enzyme. It is desirable to adjust the pH with an alkanolamine having a pH buffering property.

The cleaning composition of the present invention further improves the cleaning power,
Further, a nonionic surfactant can be added for the purpose of reducing the viscosity of the liquid. Examples of the nonionic surfactant include general formula R′O (CH ₂ CH ₂ O) mH (II) (wherein R ′ is a linear or branched alkyl group having 11 to 15 carbon atoms). Or an alkenyl group, and m is an average number of moles of ethylene oxide added in the range of 7 to 25). Further, the blending amount of the nonionic surfactant can be applied in a wide range of 5 to 30% by weight with respect to the detergent composition, and particularly 5 to 20% by weight.
Is preferred.

Further, in the detergent composition of the present invention, various additives usually used in detergent compositions, for example, a foaming agent such as alkylamine oxide and fatty acid alkanolamide, lower alcohol, polyhydric alcohol, lower allyl. If necessary, a hydrotrope such as a sulfonate, an antifungal agent such as a benzoate, or a dye or a fragrance may be added. It is also possible to use other anionic surfactants in combination for the purpose of enhancing detergency and foaming performance, but since this anionic surfactant tends to deteriorate the stability of the enzyme, its combination Is not particularly preferable, and particularly, the combined use of an alkylbenzene sulfonate, an alkyl sulfate, an α-olefin sulfonate, etc., which is often used as a detergent surfactant, is not preferable.

EFFECT OF THE INVENTION The enzyme-containing liquid detergent composition of the present invention has a very small decrease in enzyme activity even after long-term storage, has a very large effect of removing stains on clothes, and is a liquid detergent composition having excellent liquid stability. As compared with the conventionally known enzyme-containing liquid detergent composition, it has a significantly improved enzyme activity stabilizing effect and detergency and has extremely high practicality.

EXAMPLES Next, the present invention will be described in more detail with reference to examples.
The various performance evaluations in each example were evaluated according to the following test methods.

Detergency US. Using a Terg-o-Tometer from Testing Company as a cleaning device, put 10 pieces of protein-containing wet artificial dirt cloth, sebum cloth, and clean knitted cloth into it, and adjust the bath ratio to 30 times.
Wash with rpm at 25 ° C for 10 minutes. The cleaning solution has a cleaning agent concentration of 0.1
% Of 900 m and rinse with 900 m of water for 3 minutes. The water used was 3 ° DH. The detergency is calculated by the following formula.

In addition, this detergency test method is based on Oil Chemistry 30,432, (1981) "Study on new artificial soil cloth (1st report)".

Oxygen stability Put 100m of the detergent composition under test in a wide-mouthed bottle and keep the temperature at 35 ° C.
After being stored for 2 weeks, the enzyme activity was measured and the degree to the enzyme activity before storage was expressed as a percentage. The enzyme activity was measured according to the Casein-275mμ absorption A method described on page 238 and below of “Enzyme Research Method 2” (edited by Shiro Akahori), published by Asakura Shoten.

Liquid stability Put 100m of the detergent composition under test in a glass bottle and set the temperature to -7.
After storing at 1 ° C for 1 month or at 45 ° C for 1 month, the appearance is visually observed.

◯: Uniformly transparent ×: White turbidity, separation or precipitate produced immediately after compounding or after storage Example 1, Comparative Example 1 Sodium polyoxyethylene alkyl sulfate as anionic surfactant (C ₁₃ , linearity 50%, average) n = 3) 20% by weight, as a nonionic surfactant
C ₁₃ and polyoxyethylene (average addition mole number 15) ether of alcohol having a linearity of 50% 10% by weight, ethanol 4% by weight, and sodium toluenesulfonate 2% by weight were used as the standard composition. As shown, various liquid detergent compositions containing an enzyme (esperase), diglycolic acid 2Na, aminocarboxylic acid or a salt thereof, and alcalamine and paratoluenesulfonic acid as a pH adjusting agent were prepared, and the respective compositions were prepared. The detergency, the enzyme stabilizer and the solution stability were evaluated, and the results are shown in Table 1.
The pH of each composition is also shown in the table. The abbreviations in Table 1 have the following meanings.

EDTA-4Na: Tetrasodium ethylenediaminetetraacetate DTPA-5Na: Disodiumtriaminepentaacetic acid pentasodium DTPA-5H: Diethylenetriaminepentaacetic acid HEDTA-3Na: Sodium hydroxyethylenediaminetriacetate Example 2 and Comparative Example 2 Liquid detergent compositions as shown in Table 2 were prepared using various surfactants, and the enzyme stability, detergency and liquid stability were evaluated.

Common composition is DTPA-5Na 0.1wt%, diglycolic acid 2Na 8wt
%, Diethanolamine 8 wt%, paratoluene sulfonic acid 2.5 wt%, alcalase 2.5 wt%, and the pH of the composition is all 10.0.

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Claims (1)

[Claims] 1. (A) General formula RO (CH ₂ CH ₂ O) nSO ₃ M (wherein R is a linear or branched alkyl or alkenyl group having 11 to 15 carbon atoms, and n is 2 A number in the range of ~ 7, M
Is an alkali metal or an alkar-substituted or unsubstituted ammonium group) 15 to 40% by weight of an anionic surfactant represented by
(B) diglycolic acid or a salt thereof in an amount of 5 to 15% by weight, (C) aminocarboxylic acid or a salt thereof in an amount of 0.001 to 1% by weight, and (D) an enzyme, and having a pH in the range of 9.0 to 11.0. A characteristic enzyme-containing liquid detergent composition.