KR20010058615A - Bleaching composition containing cellulase - Google Patents

Abstract

PURPOSE: An oxygen bleach composition containing cellulase enzyme is provided for increasing washing effect, inhibiting fluff and peeling off of washing and improving color protection effect by comprising a specific enzyme to degrade cellulose fibers. CONSTITUTION: The oxygen bleach composition comprises 60.0-99.9 wt.% of sodium percarbonate and cellulase as a cellulose degradable enzyme in an amount of 0.1 to 2000 CEVU per 1g of the oxygen bleach agent having pH8.0-12.0. The oxygen bleach agent is selected from hydrogen peroxide or its additive compound, inorganic peroxide salt including perborate, percarbonate, perphosphate and persilicate alkali metal salts. The composition further includes builder, anionic surfactant and proteases. The composition can increase washing and bactericidal effects while preventing fluff and peeling off of washing clothes.

Description

Bleaching composition containing cellulase

The present invention relates to an oxygen-based bleach composition, and more particularly, improves washing power in a repeated washing process, suppresses lint generation of washings, and prevents peeling and color protection. It relates to a novel oxygen-based bleach composition containing).

In the past, the use of enzymes for the purpose of improving the cleaning power of detergents and detergents has been known for a long time, and the first enzymes used for such purposes are proteases. Proteases hydrolyze protein contaminants such as eggs. It has been used to remove the contaminants, amylase is used to remove starch contaminants, and lipase is used to remove fatty components such as oil. However, such enzymes have been used to selectively remove only contaminants of specific components.

In order to make up for the shortcomings of enzymes that only remove contaminants of specific components, new compositions containing cellulase, a cellulose degrading enzyme, have been attempted. Cellulase, commonly called cellulose degrading enzyme, has been tried to bind β-D-glucoside in cellulose. Is an enzyme capable of hydrolysis. These cellulase enzymes have traditionally been classified into three classes, endoglucanase, exoglucanase or cellobiohydrocollase and β-glucosidase.

As described in international patent applications WO 89/04862, WO 93/02129, WO 96/023928 and WO 96/034092, cellulose degrading enzymes biodegrade cellulose pulp into sugar for the production of ethanol or stone washing. And detergent compositions having fabric treatment effects such as biopolishing.

A method of modifying the surface of cellulose-containing fabrics using cellulase has already been introduced in the following literature. (CL Chong, American Dyestuff Report. March, 1994 p54-p64 and H. Koo, Textile Research. July, 1994 p70-p74. International patent applications WO 96/034092 and WO 96/031583. Korean Patent Publication No. 96- 2870)

The present invention aims to obtain a new composition having improved properties as a bleaching agent by applying a cellulase previously used only as a detergent composition to an oxygen-based bleaching agent. In general, the oxygen-based bleach is limited to bleaching and sterilization only, and the cleaning and sterilizing ability can be improved only by the bactericidal and bleaching characteristics. The biggest disadvantage is that it is not possible to prevent the aging of the fabric according to the change.

Therefore, in addition to the basic bleaching and sterilization function of oxygen-based bleach, the oxygen-based bleach and alkaline stabilized cellulose degrading enzyme are used to give the function of maintaining color clarity on the fabric. Experiments have shown that color sharpening is superior to builders, antifouling agents, and bleach degradation activators.

Cellulase enzyme used in the present invention is a stable clone of oxygen-based bleach and alkalinity obtained from the same origin of the Cellulzyme (Celluzyme) produced by fermenting the wild type microorganism Aspergillus microorganism in a culture medium, care Cellulase, commercially available under the trademark Carezyme, was purchased and used. The activity of the used enzyme is determined by the following method.

(1) activity of cellulase

Endoglucanase decreases the viscosity by hydrolyzing the CMC solution. After the reaction between the standard cellulase and the CMC solution, the viscosity change is measured to prepare a calibration curve, and then the sample and the CMC solution are reacted to determine the cellulase activity of the sample by measuring the viscosity change. CEVU (CE llulase V iscosity U nit) units are measured relative to an enzyme standard for the standard enzyme (Novo, enzyme number: 17-1187) is 4400CEVU / g under the reaction conditions of the ligament.

Reaction condition

pH: 9.0

Buffer: Tris 0.1M

Substrate: CMC

Temperature: 40 ℃

Time: 30 minutes

(2) measuring reagent

①Tris 0.1M Buffer

Dissolve 121.9 g of Tris and Sigma 7-9 reagents in water to 9 l, adjust the pH to 9.0 with 2N-HCL, and 10 l with water.

② Substrate, CMC (Hercules 7 LFD)

35.0 g of CMC are added slowly under strong stirring conditions while 700 ml of buffer is heated to 85-90 ° C., heated to 85-90 ° C. for 30 minutes under constant stirring, and then cooled to 25 ° C.

③ Standard enzyme solution (A)

Accurately weigh 1.00 g of cellulase into a 100 ml volumetric flask and make 100 ml with a buffer to make standard enzyme solution (A). Dilute A as shown in Table 1 below to make a standard solution.

Table 1

No. A ml Buffer up to ml Enzyme Concentration (%) One 2 100 0.020 2 4 100 0.040 3 6 100 0.060 4 8 100 0.080 5 10 100 0.100

④ test solution

5 g and 10 g of oxygen-based bleach without cellulase and 5 g and 10 g of oxygen-based bleach containing cellulase are each taken in a 100 ml volumetric flask, which is made up to 100 ml with buffer and completely dissolved.

(3) measuring method

① Add 50 ml of substrate solution to a transparent cylinder (visible container) and add 2.5 ml of buffer, test solution and standard enzyme solution.

② After stirring, react for 30 minutes in a 40 ℃ water bath, cool to room temperature and measure the viscosity.

③ Substitute the viscosity into the calibration curve to find the concentration and CEVU.

(4) Formula

LnR (measured viscosity) = lnR ₀ + h (tilt) × C (enzyme concentration)

② CEVU / g = k (activity of standard enzyme solution) × C (enzyme concentration) × F (dilution factor of sample)

1 to 3 is an enlarged photograph of an electron microscope showing the anti-pilling effect of the wash when washing the fabric,

1 is a standard test piece,

2 is a conventional oxygen-based bleach (comparative example),

Figure 3 shows the case of using an oxygen-based bleach containing the cellulase of the present invention (Example 2)

Each picture is enlarged 200 times.

4 to 6 are enlarged photographs of electron microscopes showing the degree of peeling for the same fabric more clearly;

4 is a standard test piece,

5 is a comparative example,

6 is an enlarged photograph of Example 2 by 2000 times.

It is already known that when using cellulose degrading enzymes, the color remains clear, but a significant drawback in use is that these enzymes are biodegraded by the fabric containing cellulose, causing damage to the fabric by inadvertently causing loss of tension in the fabric. Will be given. However, it has already been found in the literature that weight loss due to damage to fabrics during washing is not of appreciable degree. Since these effects are common after only 30 washes, there is always a slight decrease in tensile strength due to mechanical forces when cleaning cellulose-containing fibers.

The present invention is a composition of oxygen based bleach containing bleach, builder, anionic surfactant, proteolytic enzyme and cellulose degrading enzyme.

The oxygen-based bleach composition containing the cellulase enzyme of the present invention is, for example, any compound of hydrogen peroxide or an addition compound of hydrogen peroxide, or an organic peracid or a mixture thereof as the oxygen-based bleach. As the inorganic peroxide salt, perborate, percarbonate, perphosphate and persilicate salts and the like can be used. These, referred to as inorganic peroxides, generally use sodium percarbonate, which is an alkali metal salt of percarbonate, as the alkali metal salt.

The oxygen-based bleach composition in the cellulase-containing bleach of the present invention contains 60.0 to 99.9% by weight, preferably 80.0 to 99.9% by weight of sodium percarbonate in consideration of the basic performance of the bleach and the bactericidal power.

The oxygen-based bleach of the present invention also contains cellulase as an essential component. Cellulose used can be purchased from Novo Nordisk Co., Kao Corp. or Genencer International, in the present invention an oxygen-based bleach purchased from Novo Nordisk Co., Ltd. Carryzyme, a cellulase strain with further improved stability in alkaline and alkaline, was used.

Oxygen-based bleach composition containing the cellulase enzyme of the present invention is 0.1 CEVU to 2000 CEVU, preferably 0.1 to 1000 CEVU, more preferably 0.1 per 1 g of oxygen-based bleach in consideration of stability and economy in bleach and alkalinity. To 200 CEVU. The pH of the composition of the oxygen-based bleach is 8.0 to 12,0.

The present invention can be prepared by uniformly mixing the known oxygen-based bleach composition and cellulose degrading enzyme, oxygen-based bleach composition among the components prepared by this method

And other components in addition to the cellulose degrading enzyme, and other components are not particularly proposed.

Hereinafter, the present invention will be described in detail by the following examples and comparative examples.

The following bleach composition is based on the presence or absence of cellulase in the oxygen-based bleach as a comparative example, the bleach composition comprising the cellulase is to contain the cellulase enzyme 0.9 to 9.0 CEVU per gram of bleach To prepare an oxygen-based bleach composition.

Comparative example

Percarbonate sodium 90.0%

Tetraacetylethylenediamine 0.6%

Lauryl sulfate sodium 0.2%

Protease (Novo, Everlase 6.0T) 0.5%

Other Supplements 8.7%

Example 1

Percarbonate sodium 90.0%

Tetraacetylethylenediamine 0.6%

Lauryl sulfate sodium 0.2%

Protease (Novo, Everlase 6.0T) 0.5%

Cellulase (Novo, Carezyme 900T) 0.1%

Other Supplements 8.6%

Example 2

Percarbonate sodium 90.0%

Tetraacetylethylenediamine 0.6%

Lauryl sulfate sodium 0.2%

Protease (Novo, Everlase 6.0T) 0.5%

Cellulase (Novo, Carezyme 900T) 0.5%

Other Supplements 8.2%

Example 3

Percarbonate sodium 90.0%

Tetraacetylethylenediamine 0.6%

Lauryl sulfate sodium 0.2%

Protease (Novo, Everlase 6.0T) 0.5%

Cellulase (Novo, Carezyme 900T) 1.0%

Other Supplements 7.7%

In this experiment, the washing time was 18 minutes, 2 times of rinsing, and 6 minutes of dehydration using a submerged bang washing machine (model name SEW-Y807) of Samsung Electronics Co., Ltd., and the total washing time was 45 minutes. Fixed. In addition, all test fabrics were completely dried at room temperature for one day, and then proceeded to the next washing process. The amount of bleach used was 30 g in 30 l of water, and the performance of the composition of the present invention after washing was evaluated by comparing panel evaluation, color difference, and peeling change for the fabric after 30 washes.

The fabrics tested were also made of green fabrics containing at least 50% of cellulose, checkered (red + white), checkered (black + orange + blue), socks (light blue), socks (black), black tops, etc. Various colors of clothing were used to evaluate primary color resiliency and peeling for the compositions of the present invention, and a white cotton towel was also used to assess the degree of softening of the fabric after washing.

Softening test result

For the bleach with or without cellulase, the softness of the white cotton towel was subjected to a simple comparative evaluation (comparable to superiority) for Comparative Examples and Examples 1 to 3 as the panel (7 persons) by the tactile feel. Values are expressed as percentages. The results are shown in Table 3. According to the evaluation thereon, Examples 1 to 3 of the present invention appeared to be very excellent.

TABLE 2

Bleach composition Evaluation Comparative example 10.00% Example 1 26.25% Example 2 31.25% Example 3 32.50%

Primary color resilience test

A panel comparison evaluation of the primary color resilience of the fabric after 30 wash cycles with or without cellulase (compared with 30 washes after the 10 washes) and color difference The color difference test was carried out using the system, and the test for the peeling property was carried out by KS K 0503 "ICI Box Method" to evaluate the change of fabric after washing. The results for the evaluation are shown in the following Tables 3, 4 and 5. As shown in Table 3, in the panel test results, Example 2 was found to be very good, while Example 3 was slightly better than Example 2 in the green and black phases, but the results were significantly lower than in Example 2. Appeared.

(1) panel test results

TABLE 3

Fabric type Comparative example Example 1 Example 2 Example 3 Green tops -9.84% -2.96% + 5.19% + 7.62% Checkered (red + white) -8.79% + 3.59% + 10.37% + 6.35% Checkered (black + orange + blue) -11.22% -4.23% + 12.17% + 0.74% Socks (light blue) -3.17% -2.21% + 5.71% + 2.23% Socks (black) -6.66% -1.69% + 9.95% + 0.32% Black tops -2.24% 0.22% + 1.06% + 1.37%

Therefore, the color difference test and the peeling test were compared and evaluated with respect to Comparative Example and Example 2.

(2) color difference test result

Table 4

Sample classification L a b ΔE Green tops Standard test piece 23.6 -16.4 -0.4 - Comparative example 5.0 Lighter 2.4 + a 0.7 + b 5.6 Example 2 0.16 lighter 0.75 + a 0.53 + b 0.94 Checkered (red + white) Standard test piece 20.0 43.3 10.7 - Comparative example 3.0 Lighter 2.4-a 3.4-b 5.1 Example 2 0.1 lighter 1.1-a 0.3-b 1.1 Checkered (black + orange + blue) Standard test piece 46.4 46.1 35.1 - Comparative example 1.0 Lighter 2.8-a 2.3-b 3.7 Example 2 0.6 Lighter 1.9-a 1.5-b 2.5 Socks (light blue) Standard test piece 46.9 -5.1 -13.9 - Comparative example 6.0 Lighter 0.7 + a 1.0 + b 6.2 Example 2 5.1 Lighter 0.2 + a 0.3 + b 5.1 Socks (black) Standard test piece 6.2 0.1 -3.3 - Comparative example 6.7 Lighter 0.8-a 0.5-b 6.7 Example 2 3.0 Lighter 0.6-a 0.5-b 3.1 Black tops Standard test piece 17.6 -0.2 -2.1 - Comparative example 5.8 Lighter 0.9-a 1.7-b 6.1 Example 2 2.6 Lighter 0.0 0.5-b 2.6

(3) Filling test result

Table 5

Sample classification Test result Green tops Comparative example 3.0 Example 2 4.0 Checkered (red + white) Comparative example 1.5 Example 2 2.0 Checkered (black + orange + blue) Comparative example 2.5 Example 2 3.0 Socks (light blue) Comparative example 3.0 Example 2 4.0 Socks (black) Comparative example 3.0 Example 2 3.5

The oxygen-based bleach composition containing the cellulase according to the present invention has a remarkably improved softening effect, primary color restoring power and anti-pilling effect on the fabric, compared to the conventional oxygen-based bleach, and has excellent function of suppressing lint generation of the washing and protecting color You can see. In particular, in the anti-pilling effect, as shown in Figure 1 to Figure 6 through the washing test of the bleach composition to remove the peeling, the present invention oxygen-based bleach composition can be confirmed that the peeling effect in the fiber itself is very excellent. is.

Claims (3)

An oxygen-based bleach composition, wherein the bleach composition contains 60.0 to 99.9% by weight of sodium percarbonate and contains cellulase, a cellulose degrading enzyme. The composition of claim 1, wherein the cellulase contains 0.1 to 2000 CEVU per gram of oxygen based bleach. The composition of the oxygen-based bleach according to claim 1, wherein the pH of the composition of the oxygen-based bleach is 8.0 to 12.0.