JPH05179299A - High-bulk density granular bleaching detergent composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in enzyme stability and preservability, with the ratio of potassium ion to the whole cation within a specified range, useful for clothing, etc., comprising a surfactant, alkali builder, granular peroxide and bleaching-resistant alkali protease at a specified proportion. CONSTITUTION:The objective composition comprising (A) 10-50wt.% of a surfactant, (B) 10-50wt.% of an alkali builder like potassium carbonate, (C) 2-20wt.% of a granular peroxide 250-2000mum in granule diameter capable of releasing hydrogen peroxide into the aqueous solution (e.g. sodium percarbonate), and (D) pref. 0.1-2wt.% of a bleaching-resistant alkali protease with the ratio of potassium ion to the total cations in the components A to C of 0.1 to 1.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high bulk density granular bleaching detergent composition having good stability of an enzyme in a cleaning liquid.

[0002]

2. Description of the Related Art Conventional detergents have a bulking agent of 0.3 g / cc added to the composition by adding an extender (usually, Bourne's salt is used) which hardly contributes to the cleaning performance and spray-drying the same. It was manufactured as bead-shaped hollow particles of a certain degree. However, since such a detergent has a low specific gravity and a low surfactant concentration, transportation costs are high, and a considerable space is required for storage and display. Therefore, there were drawbacks such as difficulty in weighing. Therefore, recently, a method for producing a high bulk density granular detergent that can be washed with a small amount of detergent has been proposed (JP-A-60-96698), which has already been put on the market and has become the mainstream of granular detergent. .. Further, clothes detergents containing a bleaching agent have been recently favored because they can remove sebum stains adhering to clothes and stain stains such as tea, coffee, fruit juice and blood. There are two types of bleaching agents, an oxidizing type and a reducing type, but an oxidizing type bleaching agent is commonly used because of its excellent bleaching effect. Oxidative bleaching agents are roughly classified into chlorine-based and oxygen-based bleaching agents, but the former have the drawbacks that they cannot be used for colored patterns because they discolor and discolor washed objects, and that they have a particular unpleasant odor. On the other hand, the oxygen-based bleaching agent is superior to the chlorine-based bleaching agent in that it can be used in a wider range and has no unpleasant odor, and is suitable as a base for a household bleaching detergent. Specifically, sodium percarbonate,
Sodium perborate is used. Furthermore, as a bleaching activator, TAED (tetraacetylethylenediamine), PAG (pentaacetylglucose), TMP-
Cl (1-chloro, 4-hydroxy, 2,2,6,6,
Tetramethylpiperidine), NOBS (nonanoyloxybenzene sulfonic acid), etc. are added to enhance the bleaching effect. An enzyme such as protease is added to such a bleaching detergent to synergistically remove stains. However, when the bleaching agent and the enzyme were added to the granular detergent, there was a problem that the enzyme activity was lowered in the cleaning liquid and the stain removing effect was deteriorated.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a high bulk density granular detergent composition which is excellent in enzyme stability in a cleaning liquid.

[0004]

[Means for Solving the Problems] In order to eliminate such problems in the presence of peroxide, the present invention has conducted various studies on enzyme stability, and as a result, a specific proteolytic enzyme was identified as potassium. It was found that the object of the invention can be achieved by using it in combination with a surfactant and compounding it with a surfactant, and the present invention has been completed based on this finding.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The detergent composition of the present invention is the following high bulk density granular bleaching detergent composition. a) Surfactant: 10-50% by weight b) Alkali builder: 10-50% by weight c) Hydrogen peroxide releasing particle size 250-20 in aqueous solution
00 μm granular peroxide: 2-20 wt% (hereinafter%) d) In a high bulk density granular detergent composition comprising a bleach-resistant alkaline protease, the above a + b
The ratio of potassium ion to cation in + c is 0.1
It is characterized by being ~ 1.0. The bleach-resistant alkaline protease of the present invention means that the protease is 1.75.
Residue measured in casein protease units (CPU) after 30 minutes at pH 9.5 in a solution of g / L zeolite, 1.0 g / L sodium perborate and 1.0 g / L tetraacetylethylenediamine (TAED). At least 80% of residual activity (at 40 ° C) at 25 ° C in the absence of sodium perborate and TAED
Or it is an alkaline protease which holds 60% (at 50 ° C.). Hereinafter, the present invention will be described in more detail.

Specific examples of the surfactant as the component a) include:
Although anionic, nonionic, polar nonionic and amphoteric surfactants can be used, the following anionic or nonionic surfactants are preferably used. These surfactants are exemplified below. 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.

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 sulfonates 5) Alkyl ether sulfates or alkenyl ethers 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 C10-20 alkyl glyceryl etherisulfonate 7) C10-22 α-sulfo fatty acid salt or α-
Sulfo fatty acid ester salt 8) Acyl sarcosinate As counter ions in these anionic surfactants, sodium, potassium ammonium, alkanolamine and the like can be mentioned, but potassium is preferred from the viewpoint of the stability of the enzyme of the present patent. The following are mentioned as a nonionic surfactant. 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) on average 7 to 30 mol and / or addition propylene oxide (PO) -added nonionic surfactant 2) Mono- or dialkanolamide 3-10 carbon atoms to which ethylene oxide having 10 to 22 carbon atoms may be added 8-20 alkyl polyglycoside 4) Condensation product of propylene oxide and propylene glycol with ethylene oxide (Pluronic surfactant) 5) Condensation product of ethylene oxide with reaction product of propylene oxide and ethylenediamine (Tetroninoc Surfactant) These alkyl or alkenyl groups may be linear or branched. Further, it is desirable to use one kind or a combination of two or more kinds of these surfactants. Further, the surfactant as the component a) is blended in the detergent composition of the present invention in an amount of 10 to 50%, preferably 20 to 40%. If this amount is less than 10%, the detergency is not sufficient,
On the other hand, if it exceeds 50%, the production becomes difficult. Among the components a), particularly preferable surfactants include potassium alkylbenzene sulfonate and potassium α-olefin sulfonate.

Examples of the alkali builder of component b) include carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, Na ₂ O / SiO ₂ = 1.
For example, silicates such as sodium silicate and potassium silicate which are 0 to 4.0 are used. As these counterions, sodium and potassium are preferable, and potassium carbonate is particularly preferable. The alkali builder as component b) is blended in an amount of 10-50%, preferably 20-40%. If this amount is less than 10%, the detergency deteriorates due to lack of alkali due to stamina cleaning, and
If it exceeds 0%, the pH of the cleaning solution becomes too high, which causes problems such as hand rash and is not preferable.

The base for releasing hydrogen peroxide of the component c) includes sodium percarbonate, sodium perborate and the like. 2-20% with respect to the detergent composition, preferably 4-15
% Is compounded. The particle size of this peroxide is 250 um
-2,000 um granules are used. Particle size is 250
If it is less than μm, the storage stability is deteriorated, and if it exceeds 2,000 um, the solubility is poor, which is not preferable.

As the enzyme of component d), the alkaline protease is PH9.P in a solution of 1.75 g / L of zeolite, 1.0 g / L of sodium perborate and 1.0 g / L of tetraacetylethylenediamine (TAED). 5
Residual activity measured in casein protease units (CPU) after 30 minutes at 25% of the residual activity at 25 ° C in the absence of sodium perborate and TAED.
% (At 40 ° C.) or 60% (at 50 ° C.) alkaline protease.

The bleach-resistant protease of the present invention includes
Proteases normally used for bleaching resistance can be used. More specific examples include Durazyme manufactured by Novo Industry and Maxapem manufactured by Ibis. These bleach-resistant proteases may be used alone or in combination of two or more. These bleaching-resistant proteases can be usually added to the composition in an amount of preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight.

Further, by setting the ratio of potassium ions to all cations in the components a), b) and c) to 0.1 to 1.0, the enzyme stability is dramatically improved, and the invention is completed. I arrived. If the ratio of potassium ions is less than 0.1, the enzyme stability is insufficient.

In the detergent composition of the present invention, in addition to the above-mentioned essential components, if necessary, common components such as anti-soil redeposition agents, bleach activators, fluorescent agents, pigments and fragrances may be used in combination. it can.

[0014]

According to the method of the present invention, a specific proteolytic enzyme is used in combination with potassium in a surfactant to form a bleaching detergent composition, thereby significantly improving the enzyme stability in a cleaning solution. be able to.

Hereinafter, the present invention will be described in more detail with reference to examples. Prior to this, the evaluation method adopted in the experiment will be described. In the composition, percarbonate-Na and enzyme were powder-blended in a later step.

(1) Enzyme activity 1.2 g of commercially available high-quality casein was weighed accurately in a 200 ml beaker, divided, and swelled by adding 6 ml of 1N caustic soda, and then 160 ml of 0.05M boric acid solution was added, and then 1N. Adjust to pH 10.5 with caustic soda,
An aqueous casein solution is then prepared by diluting with water to 200 ml. Separately, about 10 g of a granular detergent containing 0.5% by weight of enzyme was dissolved in pure water to make a total amount of 11 and a sample solution of 1 ml was distributed to each of four test tubes. Then, 5 ml of the above casein aqueous solution is heated to 37 ° C. in advance and added to two of them, stirred and stored in warm water of 37 ° C. After 30 minutes, 0.44 in each test tube
After adding 5 ml of M trichloroacetic acid aqueous solution, stirring, returning to warm water at 37 ° C. again, storing for 30 minutes, and then filtering.
On the other hand, to the remaining two test tubes, 5 ml of 0.44 M trichloroacetic acid aqueous solution was added as it was and stirred, and then 5 ml of the above casein aqueous solution was added and stored in a water bath at 37 ° C., taken out after 30 minutes and taken out. Filter to make a blank. The optical density values of these filtrates were measured with a colorimeter at a wavelength of 257 mμ (characteristic wavelength of the decomposition product of casein by an enzyme), and the optical density values of the blank were measured and compared with a calibration curve prepared in advance to obtain 10 g of the detergent. The amount of enzyme per hit is determined and evaluated according to the following five-step criteria. 5 ... Residual enzyme amount over 0.04 g and 0.05 g or less (concentration in detergent over 0.4%, equivalent to 0.5% or less) 4 ... Residual enzyme amount over 0.03 g and 0.04 g or less ( Concentration in detergent exceeds 0.3%, equivalent to 0.4% or less. 3 ... Residual enzyme amount exceeds 0.02 g, 0.03 g or less (concentration in detergent exceeds 0.2% to 0.3% or less) 2) The amount of residual enzyme exceeds 0.01 g and 0.02 g or less (concentration in detergent exceeds 0.1% and 0.2% or less) 1 ... The amount of residual enzyme 0.01 g or less (concentration in detergent 0 .1% or less) Incidentally, the calibration curve used in this case was prepared as follows. That is, 0.05 g of enzyme is precisely weighed and the total amount is 1 with pure water.
An enzyme aqueous solution is prepared by dissolving so as to be 1. Separately, 2.0 g of enzyme-free granular detergent is dissolved in water to a total amount of 200 ml to prepare an aqueous detergent solution. The above enzyme aqueous solution and detergent aqueous solution are mixed at a predetermined ratio to give 0.05 g, 0.04 g, 0.03 g, per 10 g of granular detergent.
Prepare solutions corresponding to concentrations of 0.02 g and 0.01 g, and add 1 ml of each to 5 ml of the casein aqueous solution previously heated to 37 ° C, stir, and hold at 37 ° C. React in warm water for 30 minutes. Then, 5 ml of 0.44 M trichloroacetic acid aqueous solution is added and stirred, and then returned to warm water at 37 ° C., stored for 30 minutes, and filtered. Each reaction sample thus obtained was measured at a wavelength of 275 using a colorimeter.
The optical density value in mμ was measured, and a calibration curve was prepared based on this result.

[0017]

EXAMPLES Examples 4, 6, 7, 8, 9 and Comparative Examples 1, 2, 3, 5 are shown below.

[Table 1]

[Table 2]

Claims (1)

[Claims] 1. a) Surfactant: 10-5
0% by weight b) Alkali builder: 10-50% by weight c) Particle size 250 to 20 releasing hydrogen peroxide in aqueous solution
00 μm granular peroxide: 2-20% by weight d) A high bulk density granular detergent composition comprising a bleach-resistant alkaline protease, wherein
The ratio of potassium ions to all cations in + c is 0.
A high-bulk-density granular bleaching detergent composition, which is 1 to 1.0.