JPH05179291A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To provide the subject composition prevented from enzyme activity depression, excellent in long-term preservability, formulated with a protein hydrolase, metal ion blocking agent, alkanolamine, etc., and specific calcium salt. CONSTITUTION:The objective detergent composition formulated with (A) pref. 0.1-2wt.% of a protein hydrolase, (B) pref. 2.5-3.5wt.% of a metal ion blocking agent like sodium ethane-1,1-diphosphonate, (C) pref. 0.5-3wt.% of an alkanolamine like monoethanolamine and/or pyrrolidonecarboxylate like sodium pyrrolidonecarboxylate, and (D) a calcium salt like calcium chloride capable of producing 0.1-15 (pref. 0.5-3) mmol per liter of free calcium ion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a liquid detergent composition containing a surfactant as a main component, which prolongs proteolytic enzyme (hereinafter protease) activity in the presence of a sequestering agent (hereinafter chelate builder). The present invention relates to a liquid cleaning agent that is stably held over a period of time.

[0002]

2. Description of the Related Art Enzymes such as proteolytic enzymes, lipolytic enzymes and starch degrading enzymes are incorporated into detergents for the purpose of improving detergency. However, it is known that an enzyme which is a protein itself is easily denatured and is extremely unstable especially in a detergent solution. As a technique for stabilizing an unstable enzyme as described above, conventionally, a method has been used in which enzyme-reachable calcium and a polyacid for appropriately chelating the calcium ion are used in combination (JP-B-60-9080). , A method of adding a special boric acid compound (JP-A-53-57209 and 53-5).
No. 6204) or a method using a special nonionic surfactant (Japanese Patent Laid-Open No. 58-80397). Especially when used as a cleaning agent, the enzyme-accessible calcium, which has a high enzyme stabilizing effect, and the chelating builder, the fatty acid soap, or both, which are the most frequently used cleaning aids and which have a high cleaning effect improving effect, are blended at the same time. In the above system, the enzyme is deprived of calcium necessary for retaining the activity and becomes extremely unstable, so that it is difficult to obtain a stable enzyme-containing liquid detergent.

[0003]

The object of the present invention is to stabilize the protease activity in a system in which a chelate builder coexists.

[0004]

The liquid detergent of the present invention comprises:
In a liquid detergent composition containing a surfactant as a main component,
It is characterized in that a protease, a chelate builder, an alkanolamine and / or a pyrrolidonecarboxylate, and a calcium salt which produces 0.1 to 15 mmol of free calcium ion per liter are blended.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As the protease of the present invention, a commonly used protease can be used. More specific examples include Alcalase, Esperase, Savinase manufactured by Novo Industry, and Maxacal manufactured by Ibis. In the present invention, it is preferable to use a bleach-resistant protease as the protease. As the bleach-resistant protease, the protease is 1.75 g / L zeolite, 1.0 g / L sodium perborate and 1.0 g / L. Tetraacetylethylenediamine (TA
The residual activity measured in casein protease units (CPU) after 30 minutes at pH 9.5 in a solution of ED) is at least 80% of the residual activity at 25 ° C. in the absence of sodium perborate and TAED (at 40 ° C. Of) or 6
It is a protease that holds 0% (at 50 ° C.). As the bleach-resistant protease, a protease usually used for bleaching resistance can be used, and more specifically, Durazyme manufactured by Novo Industry Co., Maxapem manufactured by Ibis and the like can be mentioned. These proteases may be used alone or in combination of two or more. These proteases are usually preferably present in the composition at 0.0
It can be added in an amount of 1 to 5% by weight, more preferably 0.1 to 2% by weight.

As the chelate builder, ethane-1,
Phosphonates such as 1-diphosphonate, amino acids such as aspartic acid and glutamic acid, hydroxycarboxylates such as succinate, tartrate, malate, oxalate, citrate and diglycolate, ethylenediamine Organic chelate builders such as tetraacetate, hydroxyethylenediamine triacetate, nitrilotriacetate, aminopolyacetate such as diethylenetriamine pentaacetate, and the like can be mentioned.

Examples of these chelate builder salts include alkali metal salts such as sodium salts and potassium salts, alkanolamine salts such as monoethanolamine salts, diethanolamine salts and triethanolamine salts, and sodium salts are preferred.

In the present invention, the chelate builder is used singly or in combination of two or more kinds, and it is preferably contained in the detergent composition in an amount of preferably from 5% to 5% by weight, more preferably 2.5% by weight.
˜3.5% by weight can be blended. When the amount of the chelate builder is more than 5% by weight, the storage stability of the composition deteriorates, so 5% by weight or less is preferable.

Examples of the alkanolamine include monoethanolamine, diethanolamine and triethanolamine, which may be used alone or in combination of two or more kinds. The content of the alkanolamine in the detergent composition is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. 0.1
If the amount is less than 5% by weight, the stabilizing effect is insufficient, and if the amount is more than 5% by weight, the stabilizing effect is not significantly increased.

Examples of the pyrrolidonecarboxylic acid salt include alkali metal salts such as sodium salt and potassium salt of pyrrolidonecarboxylic acid, and alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt. More specifically, sodium pyrrolidonecarboxylate manufactured by Ajinomoto Co., Inc. may be mentioned. The amount of the pyrrolidone carboxylate compounded in the detergent composition is preferably 0.1 to 5% by weight, more preferably 0.5 to 3%.
% By weight. If the amount is less than 0.1% by weight, the stabilizing effect is insufficient, and if the amount is more than 5% by weight, the stabilizing effect is not significantly increased.

Any water-soluble calcium salt can be used as the calcium ion source. Specific examples thereof include calcium chloride, calcium gluconate, calcium lactate and the like. The concentration of calcium ions in the composition is 0.1 to 15 mmol, preferably 0.5 to 3 mmol per liter of product.

Examples of the surfactant include the following, preferably anionic or nonionic surfactants. As the anionic surfactant, a non-soap anionic surfactant, for example, an organic compound having an alkyl group having about 10 to 20 carbon atoms and a sulfonate ester group, a sulfate ester group, a phosphate ester group or a carboxyl group in their molecular structure There are water-soluble salts of. As the salt of the anionic surfactant, sodium salt, potassium salt, ammonium salt, alkanolamine salt and the like are used.

Examples of the anionic surfactant include the following. 1) Linear alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms 2) Alkyl sulfate or alkenyl sulfate having 10 to 20 carbon atoms 3) Olefin sulfonate having 10 to 20 carbon atoms 4) 10 carbon atoms To 20 alkane sulfonate 5) Alkyl ether sulfate or alkenyl ether having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and added with an average of 0.5 to 8 mol of ethylene oxide Sulfate 6) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl etherisulfonate having 10 to 20 carbon atoms 7) α-sulfo fatty acid salt or ester 8) Acyl sarcosinate 9) Fatty acid having 8 to 24 carbon atoms Examples of the nonionic salt surfactant include the following. 1) Ethylene oxide (E) in primary or secondary alcohols having 8 to 18 carbon atoms or fatty acids having 6 to 22 carbon atoms
O) and / or propylene oxide (PO) added on average in an amount of 7 to 18 mol, EO / PO-addition type nonionic surfactant 2) Mono- or dialkanolamide which may be added with an ethylene oxide having 10 to 22 carbon atoms 3 ) Alkyl polyglycoside having 8 to 20 carbon atoms 4) Condensation product of propylene oxide and propylene glycol with ethylene oxide (Pluronic type surfactant) 5) Reaction product of propylene oxide and ethylenediamine with ethylene oxide Condensation product (Tetronic type surfactant) These alkyl or alkenyl groups may be linear or branched.

In the liquid detergent of the present invention, in addition to the above-mentioned essential components, if necessary, amphoteric, semi-polar, cationic surfactants, alkali builders, anti-soil redeposition agents other than the above,
It is also possible to use commonly used components such as hydrotropes, fluorescent agents, pigments and fragrances.

The method for preparing the liquid detergent of the present invention is not particularly limited, but for example, a chelate builder or / and a pyrrolidonecarboxylic acid salt and a water-soluble calcium salt are solubilized in water together with a surfactant. Then, after adjusting the pH, a protease can be added to obtain a liquid detergent composition having stable enzyme activity against long-term storage.

[0016]

INDUSTRIAL APPLICABILITY According to the present invention, in a liquid detergent composition containing a surfactant as a main component, a free calcium ion and an alkanolamine and / or pyrrolidonecarboxylic acid are allowed to coexist in the presence of a chelate builder. It is possible to prevent a decrease in protease activity and stabilize the protease activity for a long period of time.

[0017]

The present invention will be described in detail below with reference to actual examples. First, the evaluation methods used in the examples will be shown.

Enzyme residual rate A liquid detergent composition was prepared and stored for 4 weeks in an acceleration test at 35 ° C, and the residual rate was calculated from the ratio of the amount of enzyme before and after storage. The enzyme content was determined according to the following method. That is, the liquid detergent composition is precisely weighed so that the enzyme content becomes 60 to 120 μg / L, and 1% sodium sulfate solution is added to make 1 L. 5 ml of this solution is collected, 2 ml of dimethylcasein solution is added, and 0.5 ml of 0.1% sodium trinitrobenzenesulfonate aqueous solution is further added, followed by reaction for 25 minutes. Then, 5 ml of the reaction stop solution is added to stop the reaction, the generated Meisenheimer complex is measured using a spectrophotometer, and the enzyme content is calculated using a calibration curve prepared in advance. The enzyme residual rate was calculated from the following formula based on the measured enzyme content.

Table 1 below shows examples and Table 2 shows comparative examples. The compositions shown in each table were prepared and the protease activity was measured. The indicated blending amount is% by weight, and the enzyme residual ratio is%.

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiji Abe 1-3-7 Honjo, Sumida-ku, Tokyo Within Lion Corporation

Claims (1)

[Claims] 1. A liquid detergent composition containing a surfactant as a main component, wherein a protein hydrolase, a sequestering agent, an alkanolamine and / or a pyrrolidonecarboxylate and free calcium ions are added per liter. A liquid detergent composition containing 0.1 to 15 mmol of a calcium salt produced.