KR102305171B1 - Laundry Detergent Sheet And Process For The Preparation Thereof - Google Patents

Abstract

The present invention provides a laundry detergent sheet to provide excellent cleaning power and a manufacturing method thereof. According to the present invention, the laundry detergent sheet is manufactured by using polyvinyl alcohol or a polyvinyl alcohol-based copolymer and contains surfactants and a proteolytic enzyme. The surfactant includes a main surfactant and an auxiliary surfactant. The main surfactant includes a first main surfactant and a second main surfactant, and the first main surfactant and the second main surfactant include two or more different C8 to C18 alkyl sulfate alkali metal salts. The auxiliary surfactant includes two or more different surfactants, one of these is a fatty acid alkyl ester alkoxylate, and another is a nonionic surfactant.

Description

Laundry Detergent Sheet And Process For The Preparation Thereof

The present invention relates to a laundry sheet and a method for manufacturing the same.

As detergents for washing machines, powder detergents and liquid detergents have been generally used. However, the powdered detergent has a disadvantage that the powder is blown, and the liquid detergent has a disadvantage in that it is heavy and inconvenient to carry or use.

Accordingly, as a new type of detergent, US Patent No. 4,605,509 discloses a detergent in which a liquid detergent component and a fabric softener are packaged in a water-soluble film bag. However, there is a problem in that the storage stability of the product is very poor, such as a phenomenon in which the seal bursts and the contents leak during storage or transportation of the product, and the phenomenon that active ingredients seep out to the surface of the film.

A sheet-type solid detergent was developed as a new laundry sheet by improving this, but there is a concern that it may cause irritation and damage to the skin due to alkalinity, and the solubility of the sheet itself was not very satisfactory.

US Patent No. 4,605,509

An object of the present invention is to provide a new laundry sheet having excellent washing power as a sheet detergent and excellent in various performances such as solubility and flexibility, and a method for manufacturing the same.

In order to achieve the above object, an example of the present invention is a laundry sheet prepared using polyvinyl alcohol (hereinafter 'PVA') or a polyvinyl alcohol-based copolymer, containing a surfactant, and containing a proteolytic enzyme. , the surfactant includes a main surfactant and a secondary surfactant, the main surfactant includes a first main surfactant and a second main surfactant, and the first main surfactant and the second main surfactant are different, and each independently includes an alkyl sulfate alkali metal salt having 8 to 18 carbon atoms, the auxiliary surfactant includes two or more different surfactants, one of which is a fatty acid alkyl ester alkoxylate, and the other provides a laundry sheet that is a nonionic surfactant.

Another example of the present invention comprises the steps of adding polyvinyl alcohol or polyvinyl alcohol-based copolymer, main surfactant, and auxiliary surfactant in a solvent and dissolving and mixing, and injecting the mixed raw material into a sheet shredder to form a preliminary sheet Step, a method of manufacturing a laundry sheet comprising the step of preparing a laundry sheet by applying a proteolytic enzyme to the preliminary sheet, wherein the main surfactant comprises a first main surfactant and a second main surfactant, The first main surfactant and the second main surfactant are different, and each independently comprises an alkyl sulfate alkali metal salt having 8 to 18 carbon atoms, and the auxiliary surfactant comprises two or more different surfactants, One of these is a fatty acid alkyl ester alkoxylate, and the other is a nonionic surfactant.

The laundry sheet according to the present invention is convenient to use as a sheet detergent, is completely dissolved in water, does not need to be removed after washing, and has excellent cleaning power, less irritation to the skin, and excellent flexibility.

1 to 2 show graphs showing the results of the cleaning power and skin irritation test according to the types of auxiliary surfactants, respectively.
3 is a graph showing the biodegradability test results when using FMEE.

Hereinafter, a laundry sheet according to an embodiment of the present invention will be described.

An example of the present invention is a laundry sheet prepared by using polyvinyl alcohol or a polyvinyl alcohol-based copolymer, containing a surfactant, and including a proteolytic enzyme, wherein the surfactant is a main surfactant and an auxiliary surfactant Including, wherein the main surfactant includes a first main surfactant and a second main surfactant, the first main surfactant and the second main surfactant are different, and each independently has 8 to 18 carbon atoms An alkyl sulfate alkali metal salt is provided, and the auxiliary surfactant includes two or more different surfactants, one of which is a fatty acid alkyl ester alkoxylate, and the other is a nonionic surfactant. .

Polyvinyl alcohol or polyvinyl alcohol-based polymer is used as a main component for forming a laundry sheet. As a sheet-forming substrate, polyvinyl alcohol or polyvinyl alcohol-based polymer has an advantage in that it has better sheet formability than polyacrylic acid, polyethylene glycol, and polyacrylamide, and superior solubility in water than cellulose. In addition, by using polyvinyl alcohol or polyvinyl alcohol polymer, which are water-soluble or water-dispersible materials, instead of non-woven fabrics and woven fabrics, which are insoluble or poorly soluble materials, as the main component for forming the sheet, the sheet can be easily dissolved in water during washing.

The molecular weight of the polyvinyl alcohol or polyvinyl alcohol-based polymer used is not particularly limited as long as it is suitable for use in forming a laundry sheet, but the number average molecular weight is preferably 10,000 to 100,000, and more preferably 20,000 to 60,000. Saponification of polyvinyl alcohol or polyvinyl alcohol-based polymer is also not particularly limited as long as it is suitable for use in forming a laundry sheet.

The polyvinyl alcohol or polyvinyl alcohol-based copolymer is preferably included in an amount of 20 to 42 wt%, more preferably 30 to 40 wt%, based on the total weight of the composition.

The surfactant includes a main surfactant and an auxiliary surfactant as cleaning active ingredients of the laundry sheet.

The main surfactant means a main cleaning active ingredient included in the laundry sheet, and the auxiliary surfactant means a cleaning active ingredient used as an auxiliary in addition to the main surfactant.

In one embodiment of the present invention, the content of the main surfactant is preferably 10% by weight or more, more preferably 20 to 36% by weight, based on 100% by weight of the entire laundry sheet.

The main surfactant comprises two or more surfactants. Among them, a higher content is referred to as a first main surfactant, and a lower content is referred to as a second main surfactant. It is preferable that the first main surfactant and the second main surfactant be included in an amount of 10 to 18 wt%, respectively, based on 100 wt% of the total laundry sheet.

The first main surfactant and the second main surfactant are different from each other, and each includes an alkyl sulfate alkali metal salt having 8 to 18 carbon atoms. The first main surfactant and the second main surfactant may have different carbon numbers, different types of alkali metals, or both, but preferably different types of alkali metals.

When the alkyl sulfate alkali metal salt has 12 to 16 carbon atoms, it is preferable because of its excellent compatibility with polyvinyl alcohol or polyvinyl alcohol-based polymer, which is a film-forming substrate. The metal is preferably an alkali metal, more preferably sodium or potassium. In particular, as the first main surfactant, lauryl sulfate alkali metal salt is preferable, and sodium lauryl sulfate is more preferable.

An example of the present invention further comprises a secondary surfactant in addition to the main surfactant. Here, the auxiliary surfactant is a component used as a cleaning active ingredient in addition to the main surfactant including the alkali metal salt of alkyl sulfate having 8 to 18 carbon atoms, and includes two or more different surfactants. When two or more types of surfactant are included as the auxiliary surfactant, the first auxiliary surfactant and the second auxiliary surfactant are named in order from the one with the highest content.

Such cosurfactants include an alkyl ester alkoxylate, and further include a nonionic surfactant in addition to the alkyl ester alkoxylate. In addition, a buffer (buffer) may be used as a co-surfactant.

In the fatty acid alkyl ester alkoxylate used as a cosurfactant, there is no particular limitation on the alkyl group, but it is preferable to have a C1-C6 alkyl group. Although there is no particular limitation on the alkoxylate, methoxylate, It is preferable that they are oxylate and propoxylate. In particular, it is preferably a fatty acid methyl ester ethoxylate (hereinafter 'FMEE' or 'FAMEE'). This is because fatty acid alkyl ester alkoxylate is more advantageous in cleaning power and skin irritation than alkyl ethoxylates (AEO) and alkyl polyglucoside (APG).

Nonionic surfactants that can be used as cosurfactants include, for example, polyoxyethylene alkyl ether, coconut diethanolamide, fatty acid alkanolamine, amine oxide ( amine oxide), alkyl polyglucoside, methyl polyethylene alkyl ether, or sugar ether may be at least one selected from the group consisting of. Examples of the polyoxyethylene alkyl ether include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and alkyl polyglucoside (APG). Preference is given to including, in particular, coconut diethanol amide as nonionic surfactant.

When two or more types of mutually used surfactants are used as auxiliary surfactants, the content of each auxiliary surfactant may be appropriately selected in consideration of the formability or cleaning power of the sheet.

The auxiliary surfactant may also be used as a component used as a buffer in addition to the nonionic surfactant, and there is no particular limitation, but 2-morpholinoethanesulfonic acid (MES) Monohydrate), N-tris ( Hydroxymethyl)methyl-2-aminoethanesulfonic acid (N - Tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid; TES) is preferably used, and MES monohydrate is particularly preferable.

The sum of the content of the auxiliary surfactants is preferably 14 to 22 wt% based on the total weight.

When three or more kinds of surfactants are used as the auxiliary surfactant, the content of the first auxiliary surfactant is preferably 10 to 13% by weight based on the total weight, and the content of the second auxiliary surfactant is 5 based on the total weight It is preferable that the amount is 9 wt% to 9 wt%, and the content of the third auxiliary surfactant is preferably 1 wt% to 2 wt% based on the total weight. The type of surfactant used as the first auxiliary surfactant, the second auxiliary surfactant, and the third auxiliary surfactant is not particularly limited as long as it is the above-mentioned auxiliary surfactant, but for example, it is used as a buffer as the first auxiliary surfactant It is preferable to use a component to be used, for example, MES monohydrate, a fatty acid alkyl ester alkoxylate as the second cosurfactant, and a nonionic surfactant as the third cosurfactant.

The proteolytic enzyme is preferably at least one selected from the group consisting of papain, bromelin, pancreatin, thermolysin, collagen-degrading enzyme, and subtilisin. Particularly preferred is subtilisin. Proteolytic enzymes are used to enhance the decomposition power of proteins and fats. Here, the protease is a proteolytic enzyme. Papain enhances the protein cleaning effect, and bromelain enhances the proteolytic effect while increasing nourishment absorption. Although pancreatin is used as a digestive enzyme, it has excellent protein digestibility and thus has excellent protein decomposition ability. Arazyme does not cause skin troubles because it has high protein degradation efficiency even at high salinity and excellent thrombus disintegration ability.

Among them, the protease, for example, Bacillus subtilis ( Bacillus subtilis ), Bacillus licheniformis ( Bacillus licheniformis ), Streptomyces griseus ( Streptomyces griseus ) It can be obtained from. Protease enzymes are also available as serine endoproteases.

The content of the proteolytic enzyme is preferably 0.01 to 1.5% by weight, more preferably 1.0 to 1.4% by weight, based on the total weight, in consideration of the efficiency and washing effect of the manufacturing process.

It is preferable that these proteolytic enzymes are firstly applied after preparing a preliminary sheet rather than added when manufacturing a sheet through a sheet making machine. In particular, when the content of the protein enzyme is high, for example, 1.0 wt% or more, it is preferable to apply after preparing the preliminary sheet. Because it may not function.

Other following ingredients may be included, and the preferred content thereof is as follows (see Table 1).

ingredient content (wt%) glycerin 0.5~6.0 water soluble silicone oil 1.0~3.0 Spices 0.3~1.0 Phenoxyethanol 0.2~1.0 Citric acid 0.1~1.5

The laundry sheet according to an embodiment of the present invention provides a disintegrant, a disintegrant aid, a fragrance, an optical brightener, an alkali builder, and a fabric softener in a range that does not impair storage stability, ease of manufacture, etc. in order to improve washing performance or film formability. , may further include other ingredients such as bleach, disinfectant, and the like.

For example, starch, cellulose derivatives, sodium chloride, citric acid, glycerin, propylene glycol, etc. may be used as the disintegrant/disintegrant aid. The alkali builder includes, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium metasilicate, alkali sodium silicate, neutral sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium borate, zeolite (sodium aluminosilicate), sesqui Sodium carbonate, MEA, TEA, etc. can be used. In addition, as the bleaching agent, for example, perborate, percarbonate, superphosphate, diacyl, tetraacyl peroxide, etc. may be used, and as the disinfecting agent, for example, sodium hypochlorite, hydrogen peroxide, urea peroxide, etc. have.

The thickness of the laundry sheet according to the present invention is preferably 1 μm to 1 cm, and more preferably 5 μm to 0.5 cm. If the thickness of the sheet is less than 1 μm, the strength is not sufficient and it is difficult to sufficiently contain the active ingredient, so it is difficult to have the desired performance.

Hereinafter, a manufacturing process of a laundry sheet according to an example of the present invention will be described.

1) First, add polyvinyl alcohol or polyvinyl alcohol-based copolymer, main surfactant, and auxiliary surfactant to a solvent, dissolve and mix.

The main surfactant includes a first main surfactant and a second main surfactant, the first main surfactant and the second main surfactant are different, and each independently an alkyl sulfate alkali metal salt having 8 to 18 carbon atoms Including, The auxiliary surfactant includes two or more different surfactants, one of which is a fatty acid alkyl ester alkoxylate, and the other is a nonionic surfactant.

This step can proceed through the following steps.

A. Put polyvinyl alcohol (PVA) or polyvinyl alcohol-based copolymer into the emulsifier and add a main surfactant to it while stirring so that the raw materials are uniformly completely dissolved and mixed. Water may be used as the solvent.

B. When the raw materials are uniformly mixed, add other ingredients such as fragrances and preservatives, dissolve and mix.

C. After that, add auxiliary surfactants and, if necessary, additional additives in order, and dissolve them evenly while stirring.

(In principle, all raw materials in A.~C. are added after the previously formulated raw materials are sufficiently dissolved).

2) The mixed raw material is injected into a sheet shredder to form a preliminary sheet.

After washing and heating the sheet maker, the raw materials mixed through 1) to 3) are injected to produce a sheet.

3) A laundry sheet is prepared by applying a proteolytic enzyme to the preliminary sheet.

After drying the preliminary sheet, it is preferable to apply a proteolytic enzyme thereto.

Hereinafter, examples and the like will be described in detail to help the understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

The components and contents of the sheet prepared according to the above manufacturing process are shown in Table 2 below.

ingredient content (wt%) PVA 39.1 Sodium Lauryl Sulfate 15.8 Potassium Lauryl Sulfate 12.1 MES monohydrate 11.0 FMEE 8.0 Amide-based or amine-based auxiliary surfactants 1.7 glycerin 0.7 water soluble silicone oil 2.6 Spices 0.5 Phenoxyethanol 0.3 citric acid 0.8 proteolytic enzyme 1.3 water Balance (6.1)

Example 2

The components and contents of another sheet prepared according to the above manufacturing process are shown in Table 3 below.

ingredient content (wt%) PVA 39.9 Sodium Lauryl Sulfate 16.2 Potassium Lauryl Sulfate 12.6 MES monohydrate 11.0 FMEE 8.0 Amide-based or amine-based auxiliary surfactants 1.7 glycerin 0.7 water soluble silicone oil 2.6 Spices 0.5 Phenoxyethanol 0.3 citric acid 0.8 proteolytic enzyme 0.01 water Balance (5.69)

Comparative Example 1

Based on the total weight of the composition, 2 wt% of sodium lauryl polyoxyethylene ether sulfate, 8 wt% of dodecylbenzenesulfonic acid, 4 wt% of Laureth-9 as a cosurfactant, and other triethanolamine 0.5 A liquid laundry formulation comprising % by weight, 0.5% by weight of sodium citrate anhydrous, and the remainder of water was used as Comparative Example 1.

Experimental Example 1 - Detergency test according to auxiliary surfactant

(1) A detergency test for carbon black, protein, and lipid was performed using 15% FMEE as a co-surfactant. In addition, using 15% APG (alkyl polyglycoside) as an auxiliary surfactant, a detergency test for carbon black, protein, and lipid was performed. The results are shown in FIG. 1 .

(2) Using 15% FMEE, 15% AEO, and 15% APG as auxiliary surfactants, each skin irritation test was performed, and skin irritation levels were measured and recorded for 9 days. The results are shown in FIG. 2 .

(3) Using FMEE as a cosurfactant and performing a biodegradability test (OECD 301, B test), the results are shown in FIG. 3 .

(4) Ecotoxicity experiments were performed on various alkyl polyglucosides. The results are shown in Table 4 below.

test
Way parameter C ₁₂ C ₁₄ -alkyl pg (mg/L) C ₁₀ C ₁₂ -alkyl pg (mg/L) C ₈ C ₁₀ -alkyl pg (mg/L) Ref.a FMEE (mg/L) AEO (12A8N) (mg/L) fish test LC50 (96h) 3.0 - 101 12 70.5 3.0 2.5-5.5 - - 13 5.5 39.8 167 14 water flea test EC50
(49h) 7.0 - 20 12 79.2 1.9 12 - - 13 14.9 53.6 60 14 Algal test EC50
(72h) 6.0 - 21 12 >100 1.2 11b - - 13 7.4 43.9 75 14

As a result of the test, FMEE showed superior cleaning power compared to APG. In particular, it was found that the cleaning effect of proteins and lipids was excellent. It has been shown to be eco-friendly with less irritation to the skin as well as high biodegradability and low biotoxicity.

Experimental Example 2 - Rolling (rolling) and flexibility test

Part of the sheets of Examples 1 and 2 were cut and wound around a 50 mm diameter cylinder, and cracks or damage were observed after 30 seconds. No cracks or damage were found anywhere in the sheet. In addition, the softness was also found to be good.

Experimental Examples 3-6 - Detergency Test

According to the method of GB/T13174-2008, after washing using the sheets of Examples 1, 2, and Comparative Example 1 for 6 x 6 cm of contaminated clothes while stirring at 20HZ for 15 minutes, the whiteness before and after washing was measured. to evaluate the cleaning power (after repeating the experiment twice, the number of contaminated parts was digitized and the average value was shown.)

Experimental Example 3

First, the cleaning power against carbon contamination was evaluated, and the results are shown in Table 5.

before washing after washing difference Example 1 13.8 24.4 10.6 Example 2 13.6 23.6 10.1 Comparative Example 1 13.8 19.5 5.7

As a result of evaluation of washing power on clothes contaminated with carbon black, it was found that the sheet of Example 1 had the highest washing power. Next, Example 2 showed high cleaning power, and Comparative Example 1 showed relatively low cleaning power.

Experimental Example 4

The cleaning power against protein contamination was evaluated, and the results are shown in Table 6.

before washing after washing difference Example 1 17.9 36.9 19.0 Example 2 18.3 21.7 3.4 Comparative Example 1 17.8 19.9 2.1

As a result of evaluation of cleaning power on clothes contaminated with protein, it was found that the sheet of Example 1 had the highest cleaning power. With the next big difference, Example 2 showed the highest cleaning power, and Comparative Example 1 showed the lowest.

Experimental Example 5

Table 7 shows the results of evaluating the cleaning power against Sebum contamination.

before washing after washing difference Example 1 30.0 40.8 10.8 Example 2 29.7 39.2 9.5 Comparative Example 1 29.9 36.0 6.1

As a result of evaluation of the washing power on clothes contaminated with Sebum, it was found that the sheet of Example 1 had the highest washing power. Next, Example 2 and Comparative Example 1 appeared in the order.

Experimental Example 6

The cleaning power was comprehensively evaluated in consideration of the cleaning power of Experimental Examples 3 to 5. That is, the total cleaning power was evaluated by adding all the cleaning power values of Experimental Examples 3 to 5, and the results are shown in Table 8.

Comprehensive cleaning power Example 1 40.4 Example 2 22.9 Comparative Example 1 13.9

As a result of the comprehensive evaluation, it was found that the sheet of Example 1 had the highest cleaning power. Next, Example 2 and Comparative Example 1 showed high cleaning power.

Claims (15)

A laundry sheet prepared using polyvinyl alcohol or a polyvinyl alcohol-based copolymer, containing a surfactant, and comprising a proteolytic enzyme,
The surfactant includes a main surfactant and an auxiliary surfactant,
The main surfactant includes a first main surfactant and a second main surfactant,
The first main surfactant and the second main surfactant are different and each independently contain an alkyl sulfate alkali metal salt having 8 to 18 carbon atoms,
The auxiliary surfactant includes two or more different surfactants, one of which is a fatty acid alkyl ester alkoxylate, and the other is a nonionic surfactant as a laundry sheet,
The proteolytic enzyme is at least one selected from the group consisting of papain, bromelin, pancreatin, thermolysin, collagen-degrading enzyme, and subtilisin,
The nonionic surfactant is included in an amount of 1% by weight or more and less than 2% by weight based on the total weight, laundry sheet. The laundry sheet according to claim 1, wherein the first main surfactant comprises sodium lauryl sulfate. The laundry sheet according to claim 1, wherein the second main surfactant comprises an alkali metal other than sodium. The laundry sheet according to claim 1, wherein the second main surfactant comprises potassium dodecyl sulfate. According to claim 1,
The polyvinyl alcohol or the polyvinyl alcohol-based copolymer is 20 to 42 wt%,
The main surfactant is 20 to 36% by weight,
The auxiliary surfactant is included in 14 to 22% by weight of the laundry sheet. The laundry sheet according to claim 1, wherein the polyvinyl alcohol or the polyvinyl alcohol-based copolymer is included in an amount of 30 to 40 wt%. The laundry sheet according to claim 1, wherein the first main surfactant is included in an amount of 10 to 18% by weight based on the total weight. According to claim 1, wherein the nonionic surfactant is polyoxyethylene alkyl ether (polyoxyethylene alkyl ether), coconut diethanol amide (coconut diethanolamide), fatty acid alkanolamine (fatty acid alkanolamine), amine oxide (amine oxide), alkyl One or more laundry sheets selected from the group consisting of polyglucoside (alkylpolyglucoside), methyl polyethylene alkyl ether (methyl polyethylene alkyl ether), and sugar ether. The laundry sheet according to claim 1, wherein the fatty acid alkyl ester alkoxylate is a fatty acid methyl ester ethoxylate. delete According to claim 1,
The auxiliary surfactant includes three or more different surfactants, one of which is a fatty acid alkyl ester alkoxylate, the other is a nonionic surfactant, and the other is MES monohydrate. 12. The method of claim 11,
The auxiliary surfactant, relative to the total weight,
5 to 9% by weight of the fatty acid alkyl ester alkoxylate,
1 wt% or more and less than 2 wt% of the nonionic surfactant;
A laundry sheet comprising the MES monohydrate in an amount of 10 to 13% by weight. The laundry sheet according to claim 1, wherein the proteolytic enzyme is applied. Putting polyvinyl alcohol or polyvinyl alcohol-based copolymer, main surfactant, and auxiliary surfactant in a solvent, dissolving and mixing;
Forming a preliminary sheet by injecting the mixed raw material into a sheet shredder;
A method of manufacturing a laundry sheet comprising the step of preparing a laundry sheet by applying a proteolytic enzyme to the preliminary sheet,
The main surfactant includes a first main surfactant and a second main surfactant,
The first main surfactant and the second main surfactant are different and each independently contain an alkyl sulfate alkali metal salt having 8 to 18 carbon atoms,
The auxiliary surfactant includes two or more different surfactants, one of which is a fatty acid alkyl ester alkoxylate, and the other is a nonionic surfactant. 15. The method of claim 14,
A method of manufacturing a laundry sheet in which the solvent is water.

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