JPS61133296A - Oxygen-containing liquid detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an enzyme-containing liquid detergent composition, and more particularly to an inorganic builder-containing liquid detergent composition that has high enzyme residual activity and stable cleaning power over a long period of time. The invention relates to a liquid detergent composition.

Laundry detergent compositions containing detergent enzymes such as proteolytic enzymes have become common in recent years, and include surfactants,
Excellent cleaning power is obtained by using detergent builders and enzymes in combination. For enzymes for detergents, residual enzyme activity is important when blended into detergents, and in commercially available enzymes for detergents, in order to increase this residual enzyme activity, the enzymes are supported on a suitable carrier and In order to stabilize the detergent composition, various storage stabilizers are added to the detergent composition.

However, when a commercially available detergent enzyme is blended into a liquid detergent composition, especially a liquid detergent composition containing an inorganic builder, the enzyme activity is lost within a relatively short period of time, and the desired detergency is lost. It turned out that there was no improvement. The present inventors used stabilizers such as glycerin and other polyhydric alcohols, but in this case as well, it was difficult to increase the residual activity of the enzyme.

SUMMARY AND OBJECTIVES OF THE INVENTION The present inventors have discovered that when amino acids are added as a stabilizer to a liquid detergent composition containing a surfactant, an inorganic builder, and an enzyme, the residual activity of the enzyme in the liquid is dramatically increased. It has been found that the cleaning power of liquid detergents is also increasing significantly.

That is, an object of the present invention is to provide a liquid detergent composition containing inorganic pilgoo in which the residual activity of enzymes in the composition can be maintained at a high level and the detergency can be significantly improved.

Composition of the invention According to the invention, surfactants, mineral builders.

There is also provided an enzyme-containing liquid detergent composition, characterized in that the enzyme-containing liquid detergent composition contains from 1 to 5% by weight of amino acids as a stabilizer.

A favorable attack on inventions The invention will be explained in detail below.

In liquid detergent compositions containing a stabilizer surfactant, an inorganic builder, and an enzyme, the enzyme activity is lost after a relatively short storage period; for example, after 1 ton of storage at a temperature of 37°C, the enzyme activity It was found that the residual rate of activity was only less than 10%, resulting in significant deactivation.

A variety of substances have been known as stabilizers for detergent enzymes added to liquid detergents, etc., but most of them are not suitable for liquid detergent systems containing inorganic builders. It was recognized that it had no effect. The present invention is based on the discovery that amino acids, particularly those with an isoelectric point (PI) of 10 or less, exhibit unexpectedly excellent storage stabilizing effects on liquid detergent systems containing inorganic builders. be.

Table 1 below shows the addition of various substances known as stabilizers to a liquid detergent system containing a surfactant, an inorganic builder (soda carbonate), and an enzyme (commercially available proteolytic enzyme 1% by weight). The results of measuring the residual activity rate and cleaning efficiency of the enzyme after storage at 67° C. for 1 ton for the blended product are shown.

The measurement method is as follows.

(1) Measurement of residual activity rate (1) After storing the liquid detergent compositions with the composition shown in Table 1 at 37C for 1 ton, 2 ton of each sample detergent was added to 1001 nt.
The mixture was taken into a volumetric flask, diluted with deionized water, the diluted solution was used as an enzyme reaction solution, and the enzyme titer was measured by the casein-forelin method described below.

(11) Enzyme titer measurement method (casein foreign method) 2
% casein substrate solution and enzyme reaction solution 1-1 at 40C.
After reacting for 0 minutes under the optimum pH, a protein precipitant (mixture of 0.11 mol of trichloroacetic acid, 0.36 mol of acetic acid, and 0.22 mol of sodium acetate) 5- was added and left in a constant temperature bath at 40C for 60 minutes. did.

After standing, the P solution of 2- was separated and 0.5 mol Na, CO,
Add solution 5- and a 6-fold dilution of Folin's reagent 1-, and further react at 40C for 30 minutes.

After the reaction, the concentration of decomposition products in the F solution was measured by the f7 Olin coloring method (a method of determining absorbance at a wavelength of 660 nm). Further, 1 part of the enzyme solution, 5 parts of the protein precipitant, and 5 parts of the casein substrate solution were added in that order and reacted in the same manner.This was used as a blank, and the absorbance was subtracted from the absorbance of the measurement sample.

(++D The residual activity rate of the enzyme in the detergent is calculated using the following formula.

(2) Detergent power test For each detergent with the composition shown in Table 1, 0.81/, 20
Six pieces of EMPA116 protein-contaminated cloth (size 5 crr 1 x 5 crn) were soaked in a bath with a concentration of 28 to 0.
A cleaning test was carried out for 60 minutes at a temperature of 40°C.

The reflectance of the EMPA 116 contaminated cloth before and after cleaning was measured, and the cleaning efficiency was calculated from the following formula.

The results in Table 1 show that polyhydric alcohols, which are said to have the best storage stabilization of enzymes, are not suitable for liquid detergent systems containing inorganic builders, compared to ordinary liquid systems. It can be seen that the enzyme has no stabilizing effect (although the residual activity rate of the enzyme is low, less than 20 H), whereas only when amino acids are added, a high residual activity of 40 H or more can be obtained.

In addition, the cleaning power of the detergent after being stored at 67°C for one month roughly corresponds to the residual activity rate of the enzyme in the detergent, and is almost comparable to the initial cleaning efficiency of the detergent when amino acids are added as a stabilizer. It can be seen that a cleaning efficiency of 100% can be obtained.

In the present invention, as the amino acid, any known amino acid can be used, but the isoelectric point C
It is desirable to use amino acids with PJ) of 10 or less, particularly 7 or less, from the viewpoint of storage stability of the enzyme. Tube 2 below! ! indicates the equal weight of various amino acids〇Table 2 Amino acids -etc.
6.00 Leucine
974 Asparagine Il! 2.9
8 Glutamic acid 3.20 Arginic acid 11.55 Phenylalanine
5.40 Cysteine 4.70 Serif 5.68 Histidine 7.64 Tryptophan 5.8 (S.

Proline 6.60 Some amino acids have a syl group and/or an amino group in one carbo in addition to the carboxyl group and amino group preloaded to the α carbon atom, but glycine and valine are examples of neutral amino acids, Aspartic acid is an example of an acidic amino acid and arginine is an example of a basic amino acid, and these amino acids have isoelectric points that correspond to their category.

Amino acids suitable for the purpose of the present invention correspond to neutral and acidic amino acids, and specifically include glycine, valine, leucine, phenylalanine, cysteine, seri, and aspartic acid, which have a stabilizing effect. From the comprehensive viewpoint of price, glycine is most suitable.
Although the reason for this long-lasting and stable activity is probably due to the inherent properties of amino acids, it is also partly due to the fact that the pH of liquid detergents is suppressed to a relatively low range. It seems to belong to a certain turtle.

Liquid Detergent Composition The composition of the present invention contains 0.1 to 5 parts by weight, particularly 0.5 to 5 parts by weight of amino acids per 100 parts by weight of liquid detergent, although the content varies slightly depending on the content of the inorganic bilge. It is best to mix in amounts. When the amount of amino acids blended is less than the above range, the storage stability of enzyme activity tends to be considerably lower than in the case of the present invention; However, there is no particular advantage to this, and on the contrary, it is economically disadvantageous.

As the surfactant, any nonionic, anionic or amphoteric surfactant conventionally used in liquid detergents may be used alone or in combination of two or more.

Surfactants which are particularly suitable for the purposes of the present invention are those which are essentially nonionic surfactants and contain small amounts of anionic and/or amphoteric surfactants. Suitable examples of suitable surfactants include, but are not limited to: That is, as the nonionic surfactant, higher alcohol-based surfactants, higher alcohol ethylene oxide adduct-based surfactants, and alkylolamide-based surfactants are preferably used. Any known anionic surfactant can be used, but alkali metals such as alkyl sulfates, alkylbenzene sulfonates, α-olefin sulfonates, and alkyl ethoxy sulfates, and amine salts such as triethanolamine are used as anionic surfactants. used to advantage. As the amphoteric surfactant, a glycine type, betaine type or imidacillin type surfactant is used.

Examples of inorganic builders include alkaline builders such as sodium phosphate, sodium hydrogen phosphate, sodium polyphosphate, sodium carbonate, sodium sesquicarbonate, water glass (sodium silicate), bentonite, and zeolite, as well as sodium sulfate and common salt. Neutral Pilgoo is known, and these minerals and Rudada can be used alone or in combination with 28
The above combinations can be used in the present invention. There are many builders (
However, from the viewpoint of detergency, alkaline builders are preferable, and taking into consideration that soluble detergents are required for liquid detergents, sodium carbonate and sodium sesquicarbonate are particularly suitable for this purpose. However, in liquid detergent compositions containing sodium carbonate, the storage stability of enzymes is extremely low, but according to the present invention, the stability of enzymes can be significantly improved by incorporating amino acids.

As the enzyme, any enzyme known to facilitate the removal of dirt and stains from fibers during washing can be used, and enzymes that are particularly active in alkaline regions, such as proteolytic enzymes, are advantageous. used for.

In the present invention, the blending ratio of each of the above components can be varied within a wide range as long as the stability of the liquid is maintained;
0.1 to 20% by weight of inorganic virgoo, especially 1 to 5% by weight, and 0.05 to 5% by weight of enzymes, especially 0.
．． Contains 1 to 2 weights more.

In this case, excellent cleaning power and liquid stability can be obtained.

In addition to the above-mentioned essential ingredients, the enzyme-containing liquid detergent composition of the present invention may contain any compounds known per se, such as various dyes, fluorescent brighteners, fragrances, thickeners, and water-miscible organic solvents. etc. may be blended.

Example The invention is illustrated by the following example.

The liquid detergent composition shown in Table 1 containing 6% by weight of the various amino acids shown in Table 2 as a stabilizer was stored at 67°C for 4 weeks, and the residual activity rate of the enzyme was determined by the method described above. The cleaning efficiency was measured. The obtained results are shown in Section 6 below.
Shown in the table.

The results shown in Table 3 above indicate that when neutral amino acids and acidic amino acids are used, high residual activity and high cleaning efficiency can be obtained in the cargo.

Claims (4)

[Claims] (1) An enzyme-containing liquid detergent composition containing a surfactant, an inorganic builder, and an enzyme, the composition containing amino acids as a stabilizer. (2) The composition according to claim 1, wherein the amino acids are present in an amount of 0.1 to 5% by weight based on the liquid. (3) The composition according to claim 1, wherein the amino acids are neutral to acidic amino acids having an isoelectric point (PI) of 10 or less. (4) The composition according to claim 1, wherein the inorganic builder is sodium carbonate.