KR101454411B1 - Soluble Enzyme Sheet - Google Patents

Abstract

The present invention relates to a water-soluble enzyme sheet which is completely dissolved in water and does not need to be separately removed after use (particularly, washing), is excellent in washing activity by maintaining the washing enzyme activity, is easy to use, (Film). The present invention also provides a composite sheet comprising such an enzyme sheet and a product for cleaning (especially for laundry).

Description

Soluble Enzyme Sheet {Soluble Enzyme Sheet}

The present invention relates to a water-soluble sheet (film) comprising an enzyme which is particularly useful for laundry, which can be used in various cleaning applications, and a process for producing such a sheet. The present invention also relates to a composite sheet comprising such a water-soluble enzyme sheet and a cleaning product.

So far, powder detergent or liquid detergent has been used as a detergent to be used in a washing machine. In case of liquid detergent, it is relatively heavy and consumers are reluctant to use it. In case of powder detergent, there is a problem that powder is blown when used. Thus, the need for new types of detergents has been constantly being addressed, and alternatives to sheet-type detergents have been attempted. Conventional sheet type detergents have a drawback in that they are not completely dissolved in water and must be removed after washing. However, if the sheet type detergent can be completely dissolved in water and exhibit high washing performance in a washing process, But it is very convenient to use.

On the other hand, conventional detergents contain components such as surfactants, fluorescent brighteners and enzymes to effectively remove garment contamination. Among them, enzymes play an important role in eliminating various life pollution such as sebum, ink, milk and blood. Therefore, even in the case of a sheet-type detergent, it is highly desirable to include an enzyme component in terms of cleaning performance.

However, due to the high temperature drying process, which is essential in the process of manufacturing a water-soluble detergent sheet, denaturation of the enzyme contained in the sheet is caused, and as a result, the activity of the enzyme is weakened, There was a problem that the washing power was decreased.

To solve this problem, there is a method of post-treating the enzyme on a dried sheet. However, in the case of solid powdery enzymes, it is not easy to fix on a dried sheet. Further, when the liquid enzyme is post-treated on the dried sheet by spraying, coating, printing or the like, there is a drawback that the enzyme is dried while being dried.

Accordingly, a problem to be solved by the present invention is to provide a sheet-type laundry product containing a washing enzyme which is completely dissolved in the course of use such as washing, and in which the activity of the washing enzyme is kept high, and a method for producing the same.

In order to achieve the above object, the present invention provides a water-soluble enzyme sheet (film), which comprises a polymer for sheet formation and a washing enzyme and is substantially free of an anionic surfactant, an amphoteric surfactant and an alkali builder to provide.

In the present invention, "substantially not included" means not more than 5% by weight based on the total weight of the enzyme sheet, preferably not more than 3% by weight, more preferably not more than 1% . That is, the water-soluble enzyme sheet according to the present invention may contain an anionic surfactant, an amphoteric surfactant, and an alkali builder, but it should contain only a small amount so as not to adversely affect the stability of the washing enzyme in the manufacturing process and storage.

Preferably, the water-soluble enzyme sheet according to the present invention is used for washing, and can be used together with a conventional laundry detergent (preferably a laundry sheet).

Preferably, the present invention relates to a method for producing a polymeric film, which essentially comprises a sheet-forming polymer and a washing enzyme, and optionally comprises a nonionic surfactant, an incense, a coloring matter, an antiseptic, A water-soluble enzyme sheet substantially free of a surfactant and an alkali builder.

An enzyme has a three-dimensional structure as a protein. When a three-dimensional structure is deformed by heat or an external environment, it is inactivated (lost activity), and the inactivated enzyme does not recover its function again. The present inventors have conducted experiments to prevent such enzymes from being deactivated in a water-soluble detergent sheet. When an enzyme film is prepared by separating from some components of a water-soluble detergent sheet, enzyme activity is not inactivated even when subjected to a high- The inventors have made a remarkable invention that the enzyme function in the film is maintained. When such an enzyme film is washed with a water-soluble detergent sheet containing no enzyme or laminated with an enzyme film and a water-soluble detergent sheet, the decontamination ability of the enzyme exhibits its inherent functions and exhibits excellent detergency .

Accordingly, the present invention relates to a sheet-forming polymer; Washing enzyme; And optionally a non-ionic surfactant, an aroma, a coloring matter, an antiseptic, a repellency inhibitor or a mixture thereof.

The present invention also relates to an enzyme sheet comprising a polyvinyl alcohol, a vinyl alcohol-based copolymer or a mixture thereof and a washing enzyme as a polymer for forming a sheet, wherein the amphoteric surfactant and the anionic surfactant have a negative effect on the enzyme stability On the other hand, nonionic surfactants are based on the surprising discovery that they do not affect the stability of the enzyme, further improve the ease of making the sheet, and improve the sheet formability.

Therefore, more preferably, the present invention relates to a sheet-forming polymer; Washing enzyme; Nonionic surfactants; And optionally a perfume, a coloring matter, an antiseptic, a repellency inhibitor or a mixture thereof.

When the water-soluble enzyme sheet according to the present invention comprises a non-ionic surfactant, the above-mentioned effective amount of the non-ionic surfactant is preferably 50% by weight or less based on the total weight of the water-soluble enzyme sheet, and 5-40% More preferable.

Examples of such nonionic surfactants include LA5 (pentaoxyethylated lauryl alcohol), LA7 (heptaoxyethylated lauryl alcohol), LA9 (nonaoxyethylated lauryl alcohol), LC7 (Laureth-7-citrate), CA7 (polyoxyethylene stearyl ether), OA14 (polyoxyethylene oleyl ether), AG (Alkyl glucoside), C-MEA (Coconut Acid Monoethanol Amide) and the like can be used alone or in combination. More preferably, heptaoxyethylrated lauryl alcohol (LA7), nonaoxyethyl laiturated lauryl alcohol (LA9), alkyl glycoside (AG) or a mixture thereof is used for various purposes.

In the water-soluble enzyme sheet according to the present invention, the polymer for sheet formation may be a polyvinyl alcohol, a vinyl alcohol copolymer, a polyacrylic acid, a polyethylene glycol, a polyacrylamide, an acrylic acid / maleic acid copolymer, a polyvinylpyrrolidone, a poly ATC ([2- (Acryloyloxy) ethyl] trimethylammonium chloride, poly (DMAEMA), poly (HEA), hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose , Carboxymethyl cellulose, polyaspartic acid or a mixture thereof may be used. However, for the purpose of the present invention, the polyvinyl alcohol and / or the polyvinyl alcohol-based copolymer may be used as a sheet, for example, in terms of ease of sheet production, stability of the formed sheet, It is preferable to use it as a forming polymer.

Among the polyvinyl alcohol (PVA) or polyvinyl alcohol-based copolymers having various molecular weights and degree of saponification in the water-soluble enzyme sheet of the present invention, the film formation, solubility, ease of preparation, storage stability, Viscosity, etc.), the polymer having a number average molecular weight of 10,000 to 200,000 is preferable, more preferably a polymer having a molecular weight of 15,000 to 100,000 is used, and still more preferably a polymer having a molecular weight of 20,000 to 50,000 is used. The saponification degree is preferably 60-95%, more preferably 65-90%.

The polyvinyl alcohol-based copolymer according to the present invention includes a vinyl alcohol unit and an anionic monomer unit represented by the following general formula (1) or (2), wherein the content of the anionic monomer unit is 0.5-5 mol% For the purpose of the invention.

≪ Formula 1 >

(2)

In the general formulas (1) and (2), R1, R2, and R3 are independently H or methyl, and n is an integer of 0-3 independently from each other.

In the water-soluble enzyme sheet according to the present invention, as the washing or washing enzyme, amylase, protease, cellulase, lipase, mannanase, pectinase or a mixture thereof may be used.

In the water-soluble enzyme sheet of the present invention, the content of the polymer for sheet formation is preferably 20-98 wt%, more preferably 30-97 wt%, and even more preferably 40-90 wt% The content of the washing enzyme is preferably 2-40% by weight, more preferably 3-30% by weight, and more preferably 5-20% by weight based on the total weight of the sheet.

The present invention also relates to a laundry composite sheet (first sheet) in which the water-soluble enzyme sheet (first sheet) in which the activity of the enzyme according to the present invention is maintained is connected to a laundry sheet (second sheet) comprising a surfactant, an alkali builder or a mixture thereof to provide. More preferably, the present invention relates to a multi-layer (for example, a multi-layer, multi-layer, multi-layer, multi-layer) (For example, two layers).

The present invention also relates to a water-soluble enzyme sheet in which the activity of the enzyme according to the present invention is maintained, and a laundry substance (a liquid composition, a powdery composition, a sheet-like composition, preferably a laundry sheet) containing a surfactant, an alkali builder or a mixture thereof To provide a laundry detergent product.

The present invention also relates to a process for producing a polyvinyl alcohol / polyvinyl alcohol copolymer, comprising the steps of dissolving a polyvinyl alcohol / polyvinyl alcohol copolymer and a washing enzyme in water, molding the resulting blend into a sheet (film) Wherein the liquid is substantially free of an anionic surfactant, an amphoteric surfactant and an alkali builder.

In the production method of the present invention, the drying is preferably carried out at 70-120 ° C., more preferably at 80-110 ° C., in consideration of the drying efficiency of the sheet and the stability of the enzyme.

Examples of the anionic surfactant mentioned in the present invention include sodium laureth sulfate (SLES), SLES 3, sodium lauryl sulfate (SLS), sodium alkanesulfonate (SAS), ammonia lauryl sulfate (ALS), alpha- (LAS), Lauric acid-K (Potassium Laurate), Myristic acid-K (Potassium Myristrate), MES (sodium lauryl sulfate) (methyl ester sulfonate), and the like, but the present invention is not limited thereto.

Examples of amphoteric surfactants mentioned in the present invention include, but are not limited to, amine-oxide and cocamidopropyl betaine.

Alkali builders mentioned in the present invention include sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium sulfate, sodium metasilicate, sodium alkali silicate, sodium neutral silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium borate, zeolite Sodium silicate), sodium sesquicarbonate, MEA, TEA and the like, but are not limited thereto.

A laundry sheet comprising a surfactant and / or an alkali builder connected to (preferably laminated to) the enzyme sheet (film) according to the present invention does not inhibit film formation, storage stability, ease of manufacture, etc. of the sheet In addition to the surfactant and alkali builder, a fluorescent whitening agent may be added to improve the cleaning performance or film formability within the range. Disintegration / disintegration adjuvants (for example, starch, cellulose derivatives, sodium chloride, citric acid, glycerin, propylene glycol); Fiber softening agents (for example, quaternary ammonium salt based cationic surfactants, silicone-based fiber softeners); Bleaches (for example, perborates, percarbonates, superphosphates, diacyl, tetraacyl peroxides); Dispersants / emulsifiers (e.g., polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene polyoxypropylene block polymers); Sterilizing / disinfecting agents (for example, sodium hypochlorite, hydrogen peroxide, peroxide element); Spices; antiseptic; Pigment; Antimicrobial agents, and the like .

The water-soluble enzyme sheet according to the present invention and the multi-layer laundry product comprising such an enzyme sheet are (1) easily dissolved even in low temperature water and exhibit excellent washing performance, (2) (4) is not moisture absorbed by moisture in the air and thus has stable distribution stability, (5) has a washing performance Has excellent properties, in particular, the washing enzyme is inactivated and exhibits high cleaning power.

The present invention relates to a water-soluble enzyme sheet (film) which is completely dissolved in water and does not need to be separately removed after use such as washing, and which is excellent in washing performance by maintaining the washing enzyme activity, is easy to use, ) And a laundry product comprising such an enzyme sheet. The present invention also provides such a water-soluble enzyme sheet and a method for producing a laundry product comprising such an enzyme sheet.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example 1 Preparation of Water-Soluble Detergent Sheet and Enzyme Film

According to the prescriptions of Tables 1 and 2 below, a water-soluble detergent sheet or an enzyme film containing an enzyme together was prepared. Specifically, PVA was dissolved in an appropriate amount of distilled water to prepare a polymer solution, and a formulation was prepared so as to be the prescription shown in Table 1 below. After that, the compounding liquid was put on a release film, applied with a film thickness using an Elcometer film applicator, and dried in a drying oven at 105 ° C for 10 minutes to prepare a water-soluble detergent sheet or enzyme film for washing.

Preparation of water-soluble detergent sheet and enzyme film The composition of the formulation is shown in Table 1 below.

Item (Unit:% by weight) Water-Soluble Detergent Sheet Blend Enzyme film blend solution enzyme
Not included Enzyme included One 2-1 2-2 2-3 3-1 3-2 3-3 3-4 Polymer
matrix PVA 13 13 13 13 24 24 24 24 Surfactants Polyoxyethylene
Alkyl ether 5 5 5 5 - - - 2.0 SLS 15 15 15 15 - - - - additive Soldium
carbonate 4 4 4 4 - - - - Fluorescent dye 0.8 0.8 0.8 0.8 - - - - enzyme - 0.7 1.4 2.8 1.0 2.0 4.0 2.0 Incense and other 1.5 1.5 1.5 1.5 - - - water 60.7 60 59.3 57.9 75 74 72 72 Sum 100 100 100 100 100 100 100 100

The component content ratios of the water-soluble detergent sheet and the enzyme film after drying are shown in Table 2 below.

Item (Unit:% by weight) Water-soluble detergent sheet Enzyme film enzyme
Not included Enzyme included One 2-1 2-2 2-3 3-1 3-2 3-3 3-4 Polymer
matrix PVA 32.0 31.6 31.0 30.0 93.0 83.1 83.1 81.1 Surfactants Polyoxyethylene
Alkyl ether 12.3 12.1 11.9 11.5 - - - 7.1 SLS 37.0 36.4 35.8 34.6 - - - - additive Soldium
carbonate 9.9 9.7 9.5 9.2 - - - - Fluorescent dye 2.0 1.9 1.9 1.8 - - - - enzyme - 1.7 3.3 6.5 3.9 13.8 13.8 7.8 Incense and other (moisture) 6.8 6.6 6.6 6.4 3.1 3.1 3.1 4.0 Sum 100 100 100 100 100 100 100 100

PVA: polyvinyl alcohol (KL-506, Kuraray), degree of saponification 74-80%, average degree of polymerization 500

SLS: Sodium laureth sulfate

Fluorescent dye: Tinopal CBS-X (Ciba Specialty Chemicals)

Enzyme: Savinase (Novozymes)

<Example 2> Water-soluble detergent sheet - enzyme film lamination

A water-soluble detergent sheet containing no enzyme was prepared on a release film, and then a PVA-enzyme blend was applied on the detergent sheet to a certain thickness and dried to prepare a 2-layer sheet. In addition, an enzyme film was first formed on a release film, a detergent blend was applied thereon to a predetermined thickness, and then dried to prepare a two-layer sheet. In another method, a water-soluble detergent sheet and an enzyme film were separately prepared, followed by laminating with a pressing roller or the like to prepare a two-layer film.

Experimental Example 1 Evaluation of Enzyme Activity of Water-Soluble Detergent Sheet and Enzyme Film

Protease activity in the product was determined using NOVO's method and the content of the product was determined based on the standard proteinase.

That is, the activity of the enzyme was measured by measuring the absorbance of the peptide resulting from the decomposition of Azocasein by the activity of the protease, and the measurement was performed as follows. ① Preparation of Azocasein Substrate Solution: 0.6 g of Azocasein is dissolved in 10 ml of 50% urea solution. 10 ml of 2 M Tris-H2SO4 (pH 8.5) is added and distilled water is added to make 100 ml. ② Add 1 ml of the test product solution (1% solution) and Azocasein solution (5 ml) in a 15 ml test tube, react at 40 ° C for 30 minutes, and then add 5 ml of a 10% solution of trichloroacetic acid (TCA) ③ The precipitated proteins are removed by centrifugation and the absorbance of the filtrate is measured at 390 nm. ④ To check the blank of the test solution, first add 5 ml of TCA solution to 1 ml of test solution, add the substrate Azocasein solution, and measure the absorbance after removing the precipitate.

Table 3 shows the results of measuring the enzyme activity in the blend of the water-soluble detergent sheet and the enzyme film blend, and Table 4 shows the activity of the water-soluble detergent sheet, enzyme film and two-layer sheet (lamination sheet)

Sample Activity rate relative to enzyme loading Water-Soluble Detergent Sheet Blend 2-1 65% 2-2 62% 2-3 60% Enzyme film blend solution 3-1 95% 3-2 96% 3-3 98% 3-4 98%

Sample Activity ratio relative to the preparation before drying Water-soluble detergent sheet 2-1 25% 2-2 28% 2-3 29% Enzyme film 3-1 98% 3-2 99% 3-3 99% 3-4 98% Lamination A-1 86% A-2 89% B-1 82% B-2 85%

A-1, A-2: An enzyme film blend solution (Table 1, 3-1, 3-2) was applied to a water-soluble detergent sheet containing no enzyme (Table 2, No. 1) .

B-1 and B-2: A mixture of a water-soluble detergent sheet containing no enzyme (Table 1, No. 1) was coated on an enzyme film film (Tables 2, 3-1 and 3-2) box.

The enzyme activity in the aqueous solution of the detergent sheet was relatively low compared to the enzyme film blend. This is thought to be due to the enzyme deactivation (enzyme denaturation) caused by the specific surfactant and / or alkali builder (soda) in the detergent sheet blend. In addition, the degree of deactivation (enzyme denaturation) by the high temperature during drying was very high in the water-soluble detergent sheet, which has a great influence on enzyme deactivation (enzyme denaturation) due to the synergistic action of high temperature and specific surfactant / alkali builder I think.

On the other hand, in particular, the enzyme film made of the water-soluble polymer PVA and the enzyme alone, and the enzyme film made of the PVA, the enzyme and the nonionic surfactant showed little deactivation (enzyme denaturation) in the high temperature drying process.

On the other hand, the aqueous solution of the water-soluble sheet was coated on the enzyme film and dried (B-1 and B-B in Table 4) -2) layer sheet showed higher enzymatic activity than the water-soluble detergent sheet containing the enzyme (2-1, 2-2, 2-3 in Table 4), whereas the enzyme film (Table 4 3-1, 3-2, 3-3, 3-4). This is because when an enzyme film blend liquid or a blend of detergent sheets is applied onto a detergent sheet or an enzyme film, a part of the active ingredient (enzyme or alkali builder / surfactant) diffuses into the detergent sheet and the enzyme film to affect enzyme inactivation .

<Experimental Example 2> Evaluation of detergency of water-soluble detergent sheet and enzyme film

Washing power was evaluated by using a washing machine having the same condition. In this case, general tap water was used as a washing water channel. In addition, the washing temperature was the same as that used in ordinary households. The pollutants used for the detergency evaluation were the artificial wet pollutant and the protein contaminated poop EMPA 116 manufactured by the Japan Cleanup Association. In addition, the contaminated cloth was attached to an actual cotton T-shirt and evaluated. In addition, 16 specimens of 5 ㎝ × 5 ㎝ in size were used for statistical analysis.

At this time, the WB value indicating the whiteness of the contaminated cloth was measured using a colorimeter before and after washing. The laundry sheet prepared in the above example was cut into a size of 13 cm x 16 cm, and two pieces of the cleaned detergent were used. On the other hand, when the water-soluble detergent sheet not containing the enzyme and the enzyme film are washed together, the enzyme film is cut in an appropriate size considering the same amount of the enzyme, and the detergent sheet and the enzyme film prepared in the early stage of washing And the washing conditions were performed on a heavy water in a standard course (washing 20 minutes, rinsing twice) of the washing machine. The dehydrated polluted cloth was dried in a constant temperature and humidity room (25 ° C, 20% RH) for 1 day, ironed, and WB value was measured with the same color difference meter. The obtained results were substituted into the Cubelka munch equation represented by the following equation (1) to calculate the cleaning power. The results are shown in Table 5 below.

In the above formula (1), Rs represents the surface reflectance of the contaminated cloth, Rc represents the surface reflectance of the contaminated cloth after the washing process, and Ro represents the surface reflectance of the white cloth.

Example One 2-1 2-2 2-3 1+
3-1 1+
3-2 1+
3-3 1+
3-4 A-1 A-2 B-1 B-2 Cleaning power (%)
(Japan Cleanup Association contamination) 58 64 66 67 75 79 80 78 74 76 72 75 Cleaning power (%)
(Protein contamination, EMPA 116) 54 61 62 65 74 78 81 75 72 75 71 73

In the case of the detergent sheets (Examples 2-1, 2-2, and 2-3) prepared by adding the enzyme to the blend, the detergent force was somewhat higher than that of the detergent sheet containing no enzyme (Example 1) The improvement of detergency was small compared with the case of laminating the detergent sheet or the enzyme film and the detergent sheet separately in two layers. This is presumably due to the fact that the enzymatic activity can be maintained during the high temperature drying process by preparing the enzyme film or laminating two layers to the detergent sheet with the enzyme film.

Claims (13)

A polymer for sheet formation, and a washing enzyme,
An anionic surfactant, an amphoteric surfactant, and an alkali builder in an amount of 1% by weight or less. delete A polymer for forming a sheet; Washing enzyme; And optionally a non-ionic surfactant, an aroma, a colorant, an antiseptic, a repellentizer or a mixture thereof,
An anionic surfactant, an amphoteric surfactant, and an alkali builder in an amount of 1% by weight or less. delete 4. The sheet according to claim 3, wherein the sheet comprises: a sheet-forming polymer; Washing enzyme; And optionally a non-ionic surfactant, an aroma, a coloring matter, an antiseptic, an anti-fouling agent or a mixture thereof. 6. The sheet according to claim 5, wherein the sheet comprises: a sheet-forming polymer; Washing enzyme; Nonionic surfactants; And optionally a perfume, a coloring matter, an antiseptic, a repellency inhibitor or a mixture thereof. The nonionic surfactant according to any one of claims 3, 5 and 6, wherein the nonionic surfactant is at least one selected from the group consisting of heptaoxyethyltreated lauryl alcohol (LA7), nonaoxyethyl laiturated lauryl alcohol (LA9) (AG), or a mixture thereof. The water-soluble enzyme sheet according to any one of claims 1, 3, 5, and 6, wherein the polymer for sheet formation is a polyvinyl alcohol, a polyvinyl alcohol-based copolymer, . The water-soluble enzyme according to claim 8, wherein the copolymer comprises a vinyl alcohol unit and an anionic monomer unit represented by the following formula (1) or (2), wherein the content of the anionic monomer unit is 0.5-5 mol% Sheet.
&Lt; Formula 1 >

(2)

R 1, R 2, and R 3 are independently H or methyl; and n is an integer of 0-3 independently of each other. The method according to any one of claims 1, 3, 5, and 6, wherein the washing enzyme is an amylase, a protease, a cellulase, a lipase, a mannanase, a pectinase, Enzyme sheet. A process for producing a laundry detergent composition comprising the steps of washing a water-soluble enzyme sheet (first sheet) of any one of claims 1, 3, 5 and 6 with a laundry sheet (second sheet) comprising a surfactant, an alkali builder, Composite sheet for. A laundry sheet layer (second layer) comprising the water-soluble enzyme sheet layer (first layer) of any one of claims 1, 3, 5, and 6 and a surfactant, alkali builder, Wherein the multi-layered laundry composite sheet comprises: A laundry detergent product comprising a laundry sheet comprising the water-soluble enzyme sheet of any one of claims 1, 3, 5, and 6 and a surfactant, an alkali builder, or a mixture thereof.