KR20130124261A - Sheet for laundry - Google Patents

Abstract

The present invention provides a sheet for washing which completely dissolves in water and does not need to be removed after washing. In addition, the sheet for washing has good cleaning performance, is simple to use, has storage stability and does not inconvenience a user in a usage. The sheet for washing of the present invention is manufactured by using polyvinyl alcohol polymer/copolymer, a main surfactant, which is lauryl sulfate alkali metal salt, and optionally, LA7, LA9, which are an auxiliary surfactant, or a mixture thereof. [Reference numerals] (AA) Fair;(BB) Minimum

Description

{Sheet for laundry}

The present invention relates to a detergent for use in a washing machine. And more particularly to a sheet or film type detergent which is a formulation different from a common powder detergent or liquid detergent.

Powder detergent or liquid detergent has been used as a detergent used in a washing machine. Liquid detergents are relatively heavy and consumers are reluctant to use them. In the case of powder detergents, there is a phenomenon in which powder is blown, which necessitates a new type of detergent.

In order to improve this problem, US Patent No. 4,605,509 discloses a technique for packaging a liquid detergent component and a fabric softener in a water-soluble film bag. However, when the fractional packaging using water-soluble polymer films, the sealing is broken during storage or transportation of the product, the contents leaked. In addition, the storage stability of the product, such as active ingredients seeping into the surface of the film was very low. In addition, the water-soluble film used as a packaging material is designed to have stability against the moisture in the air and durability of the contents, but it takes a considerable time to dissolve at low temperatures, and the residue of the film remains because it is not completely dissolved. This occurred.

In addition, although a laundry sheet for use by adsorbing a liquid detergent to the water-insoluble adsorption sheet has been developed, there has been a disadvantage in that the water-insoluble adsorption sheet has to be removed after washing.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a washing sheet for use in a washing machine that is completely dissolved in a washing process, has excellent washing performance, is easy to manufacture, and has good storage stability.

In order to solve the above problems, the present invention provides a laundry sheet produced by using a sheet-forming polymer, a washing surfactant, etc., wherein the sheet-forming polymer is a polyvinyl alcohol or polyvinyl alcohol- Characterized in that the surfactant comprises an alkylsulfate salt having from 8 to 18 carbon atoms, preferably a laurylsulfate salt (alkali metal salt, preferably sodium or potassium salt, most preferably sodium salt) do.

The laundry film according to the present invention is excellent in (1) easy dissolving even in low-temperature water, exhibiting excellent washing performance, (2) preventing the active ingredients of the liquid from leaking out of the sheet until entering the washing machine, (3) (4) moisture-absorbing ability by moisture in the air, and (5) excellent flowability, and (5) excellent washing performance.

When the polyvinyl alcohol or the polyvinyl alcohol copolymer is used as the main substrate of the laundry sheet, the present invention is very particularly useful among a wide variety of surfactants such as a nonionic surfactant, an anionic surfactant and an amphoteric surfactant, Based on the surprising discovery that alkali metal salts of alkyl sulfates, preferably alkali metal salts of lauryl sulfate (more preferably sodium lauryl sulfate), are difficult to predict for the purposes of the present invention, such as film forming, washing performance, do.

In the laundry sheet of the present invention, in particular, among the polyvinyl alcohol or polyvinyl alcohol-based copolymers having various molecular weight and saponification degree, film forming, solubility, ease of manufacture, storage stability, washing performance, process (compound Viscosity) and the like, a polymer having a number average molecular weight of 10,000 to 100,000 is preferable, more preferably a polymer of 20,000 to 50,000 is used, even more preferably a polymer of 20,000 to 30,000 is used.

In addition, the saponification degree of the polyvinyl alcohol or polyvinyl alcohol-based copolymer was different from the saponification degree preferred for the purpose of the present invention depending on whether the polymer is a copolymer, whether or not an alkali builder is used. More specifically, when the polymer is polyvinyl alcohol and no alkali builder is used, the degree of saponification is preferably 80-90%, and the polymer comprises a comonomer of the following formula (1) or (2), which is a specific copolymer preferred according to the present invention. When the copolymer is used and an alkali builder is used, the degree of saponification is preferably 60-90%, more preferably 70-85%, and even more preferably 70-82%.

The present invention also provides a laundry sheet comprising a polymer, a surfactant and an alkali builder, wherein the polymer is a polyvinyl alcohol copolymer containing an anionic monomer unit having a carboxyl group, and the surfactant is an alkyl sulfate And a salt (preferably an alkali metal salt of lauryl sulfate).

Such a copolymer includes a vinyl alcohol monomer unit and an anionic monomer unit represented by the following Chemical Formula 1 or 2, and a copolymer having an anionic monomer unit content of 0.5-5 mol% is particularly preferable.

≪ Formula 1 >

(2)

In Formulas 1 and 2, R1, R2, and R3 are each independently H or methyl, and n is independently an integer of 0-3.

When PVA is used as the main formulation agent, there is a problem of being cured by alkali builders. When polyvinyl alcohol-based copolymer is used as a film forming substrate instead of PVA, film forming may be performed even if an alkali builder, which is one of washing active ingredients, is included. And the solubility is not deteriorated and the washing efficiency of the washing sheet can be improved. However, not all anionic monomers are preferable as such monomers for copolymers, and only anionic monomer-containing copolymers having a carboxyl group are preferable for the purposes of the present invention. For example, PVA copolymers having an anionic monomer having -SO ₃ H have been gelled by alkali builders, making it difficult to dissolve the sheet after sheet production.

In addition, very particularly, in the laundry sheet including the alkyl sulfate metal salt, alkali builder and PVA copolymer, the saponification degree of the PVA copolymer is preferably 60-90%, unlike PVA, more preferably 70-85%. Preferred, 70-82% even more preferred. Specifically, when the degree of saponification is too high, for example, when it exceeds 90%, there is a phenomenon that the solubility of the sheet is greatly reduced after the sheet is manufactured. When the degree of saponification is too low, for example, when the degree of water solubility of the copolymer is less than 60%, Degraded.

The laundry sheet detergent according to the present invention is characterized by using an alkali metal lauryl sulfate as a surfactant component for a cleaning effect and preferably the main surfactant is used in an amount of 50 to 50 parts by weight based on the total weight of the surfactant, By weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more.

As mentioned above, in the laundry sheet prepared using the polyvinyl alcohol or polyvinyl alcohol copolymer, the main surfactant in the surfactant system for the cleaning effect is specifically the lauryl sulfate salt (more preferably sodium Lauryl sulfate) is highly desirable for the purpose of the present invention, and since such lauryl sulfate salt is used as a main surfactant, it is preferably contained in an amount of 50 wt% or more (more preferably 60 wt% or more) based on the total amount of the surfactant.

Although not limited to theory, the lauryl sulfate salt has good compatibility with the polyvinyl alcohol polymer / copolymer which is the film-forming base, so that even when containing a high amount of surfactant, It is presumed to be particularly preferable, but the present invention is not limited to this theoretical assumption.

In the case of a laundry sheet prepared using a polyvinyl alcohol polymer / copolymer and a major surfactant, an alkali metal salt of lauryl sulfate (preferably sodium lauryl sulfate), the total content of the surfactant is (after drying) The content of the polyvinyl alcohol polymer / copolymer is 20 to 50% by weight (more preferably 30 to 50% by weight, more preferably 30 to 70% by weight) relative to the total weight of the sheet, Preferably 35 to 50% by weight).

As shown in the experimental results described below, when the polyvinyl alcohol polymer / copolymer content is less than 35% by weight, the physical properties, or strength, of the sheet may be good, but the surfactant components may be buried depending on the storage conditions. In this case, the strength of the sheet may be significantly reduced along with the above problem, thereby causing a problem in use.

Such laundry sheets may include other additives, such as fluorescent dyes, enzymes, etc., which are described in detail below in addition to polyvinyl alcohol polymers / copolymers and surfactants. When the content of the surfactant is lower than the above range, the washing performance is lowered, and when the content of the surfactant is higher than the content, the content of the polyvinyl alcohol or the polyvinyl alcohol-based copolymer is inevitably reduced, making it difficult to prepare the sheet formulation.

Preferably, the present invention relates to a laundry sheet containing a polyvinyl alcohol polymer / copolymer and a surfactant, wherein the surfactant is selected from the group consisting of (a) an alkali metal salt of lauryl sulfate as a main surfactant (preferably sodium or potassium salt, Most preferably sodium salt) and (b) an auxiliary surfactant, heptaoxy ethyl lait lidyl alcohol (LA7), nonaoxyethyl laiturated lauryl alcohol (LA9), or mixtures thereof. For example.

The present invention also relates to a laundry sheet prepared by using a polyvinyl alcohol or polyvinyl alcohol copolymer and a surfactant as a laundry effective ingredient, wherein a lauryl sulfate salt is used as a main surfactant and a nonionic surfactant It is based on the surprising discovery that using LA7 or LA9 (preferably LA7) as an activator can improve the cleaning performance very much while maintaining film formation. Surprisingly, only LA7 or LA9 did not significantly degrade film formability or improved cleaning performance when other surfactants with good cleaning performance were mixed in the polyvinyl alcohol polymer / copolymer and laurylsulfate salt system.

Accordingly, the present invention also preferably provides only the lauryl sulfate salt (most preferably sodium salt) and LA7 / LA9 (preferably LA7), which are the main surfactants, as surfactants in the laundry sheet of the present invention. It provides a laundry sheet produced using.

Also preferably, the present invention provides a laundry sheet, characterized in that the mixing ratio (a: b) of (a) and (b) is 90:10 to 60:40, and more preferably, (a) The mixing ratio (a: b) of (b) is provided with a laundry sheet, characterized in that 80:20 to 70:30.

If too much of the auxiliary surfactant LA7 or LA9 is mixed with the sheet, the properties of the sheet may be worsened and the handling may be difficult. If too little is mixed, the improvement of cleaning performance is not significant.

As a result, the present invention provides the above polyvinyl alcohol or polyvinyl alcohol copolymer; Alkali metal salts of lauryl sulfate as the main surfactant; And an auxiliary surfactant LA7, LA9 or a mixture thereof, the content of the polyvinyl alcohol or polyvinyl alcohol copolymer is 30 to 50% by weight based on the total weight of the sheet after drying, Wherein the content of the lauryl sulfate salt as the main surfactant is 30 to 60% by weight, and the content of the auxiliary surfactant is 10 to 20% by weight.

The present invention is also based on the surprising finding that in formulations such as the present invention, it is desirable to substantially avoid the use of starch as the formulation agent (film forming substrate). As the starch was mixed with the formulation agent, that is, the starch was included as a sheet component, the surfactant floated after drying (poor compatibility), and as the starch content increased, the strength of the sheet also decreased. Furthermore, as the starch content increased, solubility also decreased.

Substantially not used in the present invention means no more than 5% by weight, preferably no more than 3% by weight, more preferably no more than 1% by weight, even more preferably no weight at all relative to the dry weight of the sheet.

Washing sheet according to the present invention, in order to improve the cleaning performance or film forming ability within the range that does not inhibit the film forming, storage stability, ease of manufacture, etc. of the sheet, fluorescent brightener; Enzymes (eg, cellulases, proteases, etc.); Alkali builders (e.g. sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium metasilicate, sodium alkali silicate, neutral sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium borate, zeolite (sodium aluminosilicate), sodium sesquicarbonate) , MEA, TEA); Disintegrants / disintegrant aids (eg, starch, cellulose derivatives, sodium chloride, citric acid, glycerin, propylene glycol); Fibrous softeners (eg, cationic surfactants of quaternary ammonium salts, silicone fibrous flexible components); Bleaches (for example, perborates, percarbonates, superphosphates, diacyl, tetraacyl peroxides); Dispersants / emulsifiers (eg, polyoxy alkylene alkyl phenyl ethers, polyoxy alkylene alkyl ethers, polyoxy ethylene polyoxy propylene block polymers); Bactericidal / disinfectants (eg, sodium hypochlorite, hydrogen peroxide, urea peroxide); Spices; antiseptic; Pigment; Antimicrobial agents, and the like .

The thickness of the washing sheet according to the present invention is preferably 1 µm to 1 cm, more preferably 5 µm to 0.5 cm, and most preferably 50 µm to 1 mm. If the thickness of the dried laundry sheet is less than 1 μm, the loading of the active ingredient is insufficient, the strength of the film is weak, the desired performance is hard to be obtained, and if the thickness of the dried laundry sheet is more than 1 cm, the dissolution is slowed down and the washing performance is reduced. This may fall.

More preferably, the present invention provides 20-50% by weight of PVA (preferably 30-50% by weight), 30-50% by weight of SLS, 10-20% by weight of LA7 / 9, optionally fluorescence, relative to the total weight of the sheet after drying. A sheet water-soluble laundry detergent comprising 1 to 5 wt% of a bleach, and optionally 1 to 5 wt% of an enzyme is provided. The sheet-type laundry detergent of the present invention is completely dissolved when used together with clothes in a laundry container and does not require a removal process.

The washing sheet according to the present invention also comprises the above-mentioned polyvinyl alcohol or polyvinyl alcohol-based copolymers; Alkali metal salts of lauryl sulfate as the main surfactant (most preferably sodium salt); And other cosurfactants within a small amount which does not interfere with the object of the present invention, in addition to the cosurfactant. Examples of such an auxiliary surfactant include a surfactant having no ethylene oxide group in its structure and a nonaromatic surfactant (for example, an alkali metal salt of an alkylsulfate having 8 to 20 carbon atoms other than a laurylsulfate salt, an alpha -olefin sulfonate, an alkanesulfonate alkali metal salt , Fatty acid methyl ester sulfonate alkali metal salts, fatty acids, alkyl glycosides, etc.); Surfactants with ethylene oxide groups in the surfactant structure (preferred examples are sodium laureth sulfate); Aromatic surfactants (alkylbenzenesulfonates being preferred, alkylbenzenesulfonates wherein alkyl is linear alkyl having 8 to 18 carbon atoms, more preferably), and the like, but the present invention is not limited thereto.

The laundry sheet of the present invention may be used in a state in which two or more layers are integrated by stacking sheets of other layers in addition to the sheet of one layer according to the present invention.

The laundry sheet according to the present invention is prepared by dissolving a polyvinyl alcohol or a polyvinyl alcohol-based copolymer in an appropriate amount of water to prepare a polyvinyl alcohol polymer / copolymer solution, and then mixing other components such as surfactants well, and a predetermined thickness thereof. It can be prepared by drying the sheet of the product. In addition, the washing sheet of the present invention is not limited to the above-described manufacturing method, such that other components such as a surfactant may be dissolved first before the polyvinyl alcohol or polyvinyl alcohol-based copolymer is dissolved in water.

The present invention is also based on the fact that it is preferable to further include a bubbling process during the manufacturing process to improve the water solubility of the sheet of the present invention, and through such a bubbling process, When the specific gravity is adjusted to 0.6 to 0.9, various advantages for washing such as water solubility and dissolution rate of the sheet may be further highlighted. Therefore, the present invention comprises the steps of preparing a solution containing a polyvinyl alcohol or polyvinyl alcohol-based copolymer and a surfactant; Bubbling; And it provides a method for producing a laundry sheet comprising the step of drying.

Therefore, the present invention also has the above-mentioned technical characteristics, and also provides a laundry sheet to which a specific gravity of 0.6 to 0.9 is added.

The present invention provides a laundry sheet which is completely dissolved in water and does not need to be removed after washing, has excellent washing performance, is easy to use, secures storage stability, and is not inconvenient at the time of use.

1 is an experimental result showing the change in sheet tensile strength according to the PVA molecular weight, PVA content and water content compared to the solid content. The first number in the X-axis value "03-40-170" in FIG. 1 means the degree of polymerization / 100 (ie, 03 means the degree of polymerization 300), the second number means the content of PVA , And the third number means the water content (wt%) with respect to the solids content. PVA molecular weight is approximately 50 times the degree of polymerization. Y-axis means tensile strength and the unit is kgf / cm ² .
Figure 2 is a result showing the change in tensile strength caused by replacing part of the PVA used as a formulation agent with starch. The Y-axis values in the graph refer to the tensile strength and the unit is kgf / cm ² . The red line in FIG. ² is the boundary line showing 5 kgf / cm ² , which is the minimum tensile strength required (in case of less than it is easily torn or broken) in terms of sheet usability.
3 is a graph showing the viscosity that changes as the molecular weight of PVA increases under specific content conditions. At this time, the water content of each formulation is 240% of solids.

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> Selection of a polymer suitable for a laundry sheet

The film forming, solubility, storage stability, and the like of the polymer were evaluated while preparing the laundry sheet using the various polymers according to Table 1 below. The results are shown in Table 1 below.

100 g of the polymer was dissolved or suspended in an appropriate amount of distilled water or ethanol (about 400 g) to obtain a polymer solution or suspension. The polymer solution or suspension was placed on a release film, and then manufactured to a predetermined thickness using a film applicator manufactured by Elcometer, and then dried for 10 minutes in a 115 ℃ drying oven to prepare a washing sheet (thickness: 0.01 cm). The film formulation was evaluated in three stages: good, normal and poor, using the sheet formation process and the sheets formed after preparation.

Solubility was evaluated as follows. The prepared film sheet was cut into 5 cm x 5 cm and charged into a 500 ml beaker at about 300 ml of 15 ° C. purified water, followed by stirring at a constant speed. The time taken for the film to disintegrate completely and dissolve was measured and evaluated in three stages: good (within 3 minutes), normal (3 minutes-5 minutes) and poor (greater than 10 minutes).

Film forming Solubility Other ratings Polyvinyl alcohol Great Great Good water solubility Polyacrylic acid usually Great Dissolves well in water at high pH and neutrality, but the formed film is brittle. Polyethylene glycol Bad usually - Polyacrylamide Bad Great - Polyvinylpyrrolidone Great Great Soluble in ethanol and organic solvents Poly ATC Great Great Very hygroscopic POLY DMAEMA Great usually Solubility is achieved at low pH POLY HEA Great usually - Cellulose (HEC) usually usually - Cellulose (HPMC) usually usually -

In Table 1, ATC means [2- (Acryloyloxy) ethyl] trimethylammonium chloride, DMAEMA means Dimethyl aminoehtyl methacrylate, HEA means hydroxy ethyl acrylate, HEC means hydroxyethylcellulose, and HPMC means hydroxypropylmethylcellulose. it means.

As shown in Table 1, polyvinyl alcohol was most preferred as a polymer for preparing a laundry sheet in terms of film forming, a solubility of the manufactured sheet, ease of manufacture, storage stability, and the like for manufacturing the laundry sheet. .

&Lt; Example 2 > Evaluation of influence of PVA content and molecular weight

Furthermore, polyvinyl alcohol having various molecular weights and degree of saponification was used to evaluate film forming, solubility, ease of manufacture, storage stability, washing performance, and process (viscosity of the compounding liquid) More preferably a polymer having a molecular weight of 20,000 to 50,000 is used and still more preferably a polymer having a molecular weight of 20,000 to 50,000 is used for the purpose of the present invention in consideration of the relationship with the content of the polyvinyl alcohol or polyvinyl alcohol copolymer, PVA or a copolymer thereof is preferably 30,000. In addition, when alkali builders were not mixed in the saponification degree, the polymer had a saponification degree of 80-90%, and the saponification degree was 60-90% when the PVA copolymer was used and the alkali builders were mixed. Particular preference is given to using polymers, preferably 70-85%, even more preferably 70-82%). The water solubility was lowered when the saponification degree was lower than the saponification degree, and the gelling phenomenon was a problem when the polymer having the saponification degree higher than the saponification degree was used.

Specific experimental results showing the above contents are shown in Tables 3 and 4. Preparation and evaluation of the sheets were performed similarly to Example 1. At this time, the casting condition was 1100 ㎛ (mixing solution coating thickness), the drying condition was 115 ℃, 15 minutes. ("Post-drying surface"), including burying scale, and the like. For example, one point is a case where there is no abnormality in the film, but is buried on the surface, and three points mean a case where phase separation occurs on the surface of the film and is buried on the surface. Evaluation criteria of solubility and tensile strength were as shown in Table 2 below.

Evaluation results Very good Great usually Bad Solubility ◎
(Within 3 minutes) ○
(Within 5 minutes) △
(Within 10 minutes) ×
(More than 10 minutes) The tensile strength
(kgf / cm ² ) ◎
More than 15 ○
over 10 △
5 or more ×
5 or less

When the content of the polymer is changed, the total solids (PVA, SLS, LA7, etc.) content is adjusted to 100% by supplementing or reducing the surfactants (SLS, LA7) and other components (fluorescent brightener, enzyme, fragrance, etc.) The content was fixed at 5% by weight. The basic formulation used 40 wt% PVA, 45 wt% SLS, 10 wt% LA7 and 5 wt% other ingredients (prescription number 1). In the following table, PVA content refers to the weight percentage of PVA in the total solids excluding water, and the content of water means the weight% of water relative to the total weight of solids when preparing the blend. That is, in the formula 1, the PVA content of 40% means that PVA is contained in 40% by weight of the total solids, and the water content of 63% means that the solids content is 37% Therefore, when the solid content is taken as 100, it means that the water content is about 170.

* For the 13th prescription, 2 minutes of drying time was added.

As shown in Tables 3 and 4, when the PVA number average molecular weight was about 15,000 or less, a phenomenon in which the sheet strength was poor and the surface surfactant floated after drying occurred (poor compatibility). In order to solve this, it is possible to secure the sheet forming and strength by increasing the PVA content in the sheet, but the lower the effective content content has resulted in a lower washing performance.

On the other hand, as the molecular weight increased, the sheet surface became more stable (compatibility improvement), and the sheet strength increased. Therefore, the higher the molecular weight, it is advantageous to secure the sheet formulation at a lower PVA content, but the viscosity of the formulation is too high, it is difficult to secure a fairness substantially suitable for mass production. On the other hand, to improve this, that is, to increase the water content in order to lower the viscosity can be produced, but the problem that the productivity is greatly reduced.

 Therefore, as a result, the number average molecular weight of the PVA or copolymer thereof used in view of sheet strength and compatibility with the laundry active ingredient is preferably 20,000 or more. In addition, the number average molecular weight of the PVA or its copolymer is preferably 50,000 or less, and preferably 30,000 or less, in terms of the manufacturing process, since 5,000 cps or less is appropriate in a certain PVA content (about 30%) and water content (240 wt% based on the solid content). It was more preferable that it was the following.

In this regard, the molecular weight of the PVA is increased when 30 wt% PVA, 52 wt% SLS, 13 wt% LA7 and 5 wt% of other components are used and water is used at 240 parts by weight relative to 100 wt% sheet solids. While measuring the viscosity of the polymer solution changes while the results are shown in FIG. In the case of the polymer solution to be used during the manufacturing process is not preferable if the viscosity is too high or too low, the polymer solution having a component of the same type of the present invention was found to increase the viscosity rapidly from about 50,000 molecular weight.

For reference, the measurement results of changes in sheet tensile strength according to molecular weight, PVA content, and water content relative to solid content are shown in FIG. 1. In terms of sheet usability, it is required to be at least 5 kgf / cm ² (easily torn or broken when it is less than 5 kgf / cm ² ), and it is considered to be a good level when it is 10 kgf / cm ^{2 or} more. In terms of tensile strength, Prescription, 10-40-170 prescription, 15-30-200 prescription, 10-40-200 prescription, 15-40-240 prescription, 10-30-200 prescription, 10-35-200 prescription were desirable.

Example 3 Evaluation of Main Surfactant

According to the ingredients and contents shown in Table 5 below, a sheet for washing was prepared, and the film forming and washing performance of the prepared sheet were compared and evaluated.

number ingredient Content (unit%) One Polyvinyl Alcohol (PVA) 40% 2 Surfactants of Table 3 below 55% 3 Fluorescent brightener 2 % 4 enzyme 1.5% 5 Incense and more 1.5%

Specifically, 145 g of PVA (blackness: 86.5%, average degree of polymerization: 500) were added to 630 g of distilled water, and then dissolved at 80 ° C. for 2 hours to prepare a PVA solution. The remaining components of Table 2 were added to the prepared PVA solution, followed by mixing using a mechanical stirrer. The mixed solution was placed on a release film, and then prepared to a predetermined thickness using an Elcometer film applicator, followed by drying for 10 minutes in a 115 ℃ drying oven to prepare a PVA sheet containing a surfactant as a washing component.

Evaluation results of film forming, washing performance, etc. according to the type of surfactant are shown in Table 6 below. Film formulation was evaluated in three steps of good, normal and poor as in Example 1 above. The cleaning performance was evaluated by the method given below, and the cleaning power was judged to be excellent when the cleaning power was 60% or more, 50-59% is normal, and less than 50% was poor.

Specifically, the washing power was evaluated by using a washing machine under the same conditions, and at this time, general tap water was used as the washing water. In addition, the temperature of the washing was cold water was the same as the conditions used in normal households, and the emulsified cloth used for the evaluation of cleaning power was used as the artificial wet cloth and protein contaminant EMPA 116 manufactured by the Japan Laundry Science Association. In addition, the soil cloth was evaluated by attaching to the actual cotton t-shirt. In addition, 16 contaminated cloths of 5 cm × 5 cm size were used for comparative evaluation. At this time, the W _B value which is the value which shows the whiteness of a contaminated cloth was measured using the color difference meter before and after washing. The laundry sheet prepared in the above example was cut to a size of 20 cm × 15 cm, and two pieces of the detergent thus cut were used. In the initial stage of washing, the laundry sheets prepared in the examples were put together with the contaminated cloth, and the washing conditions were performed at a medium water level in a standard course of the washing machine (20 minutes of washing and two rinsing cycles). It was dried for 1 day at 25 ℃, 20% RH), and ironed to measure the WB value by the same colorimeter. The obtained result was substituted into the Kubelka Munch equation represented by Equation 2 to calculate the washing power, and the results are shown in Table 6 below.

In Equation 1, Rs represents the surface reflectance of the contaminated cloth, Rc represents the surface reflectivity of the contaminated cloth after the washing process, and Ro represents the surface reflectance of the white cotton cloth.

Kinds designation Film forming Washing performance Remarks Nonionic surfactant Pentaoxyethylated lauryl alcohol (LA5)
(Polyoxyethylene Lauryl Ether) Bad usually Liquid LA7 (heptaoxyethylated lauryl alcohol) Bad Great Liquid LA9 (nonaoxyethylated lauryl alcohol) Bad Great Liquid LC-7 (Laureth-7-citrate) Bad usually Liquid CA7 (Polyoxyethylene cetyl ether) Bad usually Semisolid CA9 Bad usually Semisolid CA15 usually usually Semisolid SA14 (Polyoxyethylene stearyl ether) usually usually Semisolid OA14 (Polyoxyethylene oleyl ether) usually usually Semisolid AG200 (Alkyl glucoside) usually usually 50% solution Coconut Acid Monoethanol Amide (C-MEA) usually Bad elegance Anionic surfactant SLES 2 (sodium laureth sulfate) Bad Great 70% solution SLES 3 Bad Great 70% solution SLS (sodium lauryl sulfate) Great Great elegance SAS (Sodium alkanesulfonate) Bad usually 25% solution Ammonium Lauryl Sulfate (ALS) Bad usually 26% solution AOS (Alpha Olefin sulfonate) Bad Great 35% solution ALES 3mol (Ammonium Laureth Sulfate) Bad Great 30% solution Linear alkylbenze sulphonate (LAS) -mono ethanol amine (MEA) Bad usually Semisolid LAS-Na (Soduim linear alkylbenze sulphonate) Bad usually Semisolid Lauric acid-K (Potassium Laurate) Bad Bad elegance Myristic acid-K (Potassium Myristrate) Bad usually elegance MES (methyl ester sulfonate) Bad usually elegance Amphoteric surfactant Amine-oxide Bad Bad 30% solution Cocamidopropyl Betaine usually Bad elegance

As shown in Table 6, when using polyvinyl alcohol as a polymer substrate, only sodium lauryl sulfate (SLS) was excellent in film formability, and various other cleaning surfactants had moderate or poor film formability. It was. For example, surfactants such as LAS, SLES, and MEA did not have good compatibility with PVA due to phase separation in the manufacturing process, and poor storage stability and ease of handling such as sticky or broken sheets. .

&Lt; Example 4 > Selection evaluation of cosurfactant

Sodium lauryl sulfate was used as the main surfactant, and various nonionic surfactants were used as auxiliary surfactants to prepare and evaluate various laundry sheets according to the formulation of Table 7 below. Laundry sheets were prepared in a similar manner to Example 3.

Item Example a b c d e f g h i j k Polymer
matrix PVA ⁽¹⁾ 40 40 40 40 40 40 40 40 40 40 40 Nonion
Surfactants LA5 15 - - - - - - - - - - LA7 - 15 - - - - - - - - - LA9 - - 15 - - - - - - - - LC7 - - - 15 - - - - - - - CA7 - - - - 15 - - - - - - CA9 - - - - - 15 - - - - - CA15 - - - - - - 15 - - - - SA14 - - - - - - - 15 - - - OA14 - - - - - - - - 15 - - AG200 - - - - - - - - - 15 - C-MEA - - - - - - - - - - 15 Anion
Surfactants SLS ⁽²⁾ 40 40 40 40 40 40 40 40 40 40 40 additive Fluorescent Dyes ⁽³⁾ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Incense and more 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sum Sum 100 100 100 100 100 100 100 100 100 100 100

In Table 7, PVA ⁽¹⁾ means polyvinyl alcohol having a degree of saponification of 86.5% and an average degree of polymerization of 500, SLS ⁽²⁾ is sodium lauyl sulfate, and fluorescent dye ⁽³⁾ is Tinopal CBS-X (Ciba Specialty). Chemical).

The prepared laundry sheets were tested in the same manner as in Example 1 or 3, and evaluated according to the criteria of Table 8 below, and the results are shown in Table 9 below.

Film tensile strength was evaluated as follows. The test method followed the ISO 527-3 standard test method, using a Zwick 1120 universal tester. Each sample was prepared to be 0.2mm thick and cut into 2 × 10 (cm ² ), and the specimen was held by screw grip. The distance between grips was maintained at 50mm and the tension test was performed at a speed of 20 mm / min. It was. The point at which the film was cut without breaking the force was set as the tensile strength, and was considered based on the numerical values of Table 8 in consideration of ease of use.

Evaluation results Very good Great usually Bad Solubility ◎
(Within 3 minutes) ○
(Within 5 minutes) △
(Within 10 minutes) ×
(More than 10 minutes) The tensile strength
(kgf / cm ² ) ◎
More than 15 ○
over 10 △
5 or more ×
5 or less

Example a b c d e f g h i j k Cleaning power (%)
(Japan Laundry Science Association) 60 71 70 64 58 66 64 67 62 68 58 Cleaning power (%)
(Protein contaminants, EMPA 116) 66 68 67 68 64 66 65 68 60 62 56 Solubility ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ ○ The tensile strength ○ ◎ ◎ ○ ◎ ◎ ◎ ◎ ○ ○ ◎

As shown in Table 9 above, LA7 and LA9 were superior to other nonionic surfactants in terms of washing power and physical properties, and LA7 was somewhat superior to LA9 in terms of washing power.

<Example 5> Evaluation of effect of SLS content, which is a main surfactant, and LA7 content, an auxiliary surfactant

As shown in Table 10, the washing sheet was prepared while varying the contents of the main surfactant SLS and the auxiliary surfactant LA7. The preparation method was the same as in Example 4.

Ingredient / Content (% by weight) Example 5-1 Example
5-2 Example
5-3 Example
5-4 Example
5-5 Example
5-6 Polyvinyl Alcohol (PVA) 40% 40% 40% 40% 40% 40% Sodium lauryl sulfate 55% 50% 45% 40% 35% 30% LA7 0% 5% 10% 15% 20% 25% Fluorescent dyes (Tinopal CBS-X, Ciba chem.) 2% 2% 2% 2% 2% 2% Enzyme (Savinase-16L, Novozyme) 1.5% 1.5% 1.5% 1.5% 1.5% 1.5% Incense and more 1.5% 1.5% 1.5% 1.5% 1.5% 1.5% Sum 100% 100% 100% 100% 100% 100%

The film forming, washing performance and the like of the thus prepared laundry sheet were evaluated in the same manner as in the evaluation method of Example 4, and are shown in Table 11 below.

Sample Film forming Cleaning performance (%) Japanese pollution gun EMPA116 Example 5-1 Great 65 55 Example 5-2 Great 67 58 Example 5-3 Great 69 62 Examples 5-4 Great 71 68 Example 5-5 usually 72 66 Example 5-6 Bad 68 60

As shown in Table 11, considering the film formulation and washing performance, the content of SLS is 40 to 50% by weight relative to the total weight of the sheet, and 5 to 15% by weight of LA7, which is a nonionic surfactant, is preferable.

<Example 6> Comprehensive evaluation

To prepare a water-soluble sheet in the formulation and content of Table 12 below to evaluate various aspects. The preparation method was the same as in Example 4.

Item Example Comparative Example a b c d e f g h i j k l a b c Polymer
matrix PVA 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Nonion
Surfactants LA7 0 5 10 15 20 25 15 15 15 15 - - 55 - - Anion
Surfactants SLS 55 50 45 40 35 30 30 20 10 0 57 56.5 - - - SLES - - - - - - 10 20 30 40 - - - 55 - AOS - - - - - - - - - - - - - - 55 additive Fluorescent dyes 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 0 2.0 2.0 2.0 2.0 enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 0 1.5 1.5 1.5 Incense and more 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sum Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

In Table 12, PVA having a saponification degree of 86.5% and an average degree of polymerization of 500 was used as PVA, and LA7, which is a polyoxyethylene alkyl ether, was used as a nonionic surfactant, and AOS means α-olefin sulfonate, and a fluorescent dye. Tinopal CBS-X (Ciba Specialty Chemical) was used as the furnace.

Sheet Formation  evaluation

Formulation properties of the water-soluble sheet detergent prepared in Comparative Examples and Examples were evaluated according to the following criteria through visual observation, and the results are shown in Table 13 below.

◎: Sheet formulation is flexible and excellent without any bleeding phenomenon

○: The sheet formulation is flexible, but the liquid component is slightly buried.

(Triangle | delta): The sheet | seat flexibility lacks and the phenomenon which a little burrs occurs.

X: Sheet formulation was not carried out and a lot of liquid components were buried.

Example Comparative Example a b c d e f g h i j k l a b c Sheet forming ◎ ◎ ◎ ◎ ○ △ ○ ○ △ △ ◎ ◎ × △ ×

As shown in Table 13, the sheet formulation of Examples a, b, c, d, k and l was excellent, and it was confirmed that the film formulation was significantly degraded when the nonionic surfactant and the SLES content were increased.

Solubility and The tensile strength  evaluation

The laundry sheets prepared in Examples and Comparative Examples were tested in the same manner as in Example 4 to evaluate solubility and tensile strength. The writing results are shown in Table 14 below.

Example Comparative Example a b c d e f g h i j k l a b c Solubility ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ - ○ - The tensile strength ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ △ ◎ ◎ - △ -

In Comparative Examples a and c, the sheet formulation was not formed, so it was impossible to measure solubility and tensile strength.

As shown in Table 14, in Examples a, b, c, d, k and l, both solubility and tensile strength were very excellent.

Detergency evaluation

The cleaning power of the laundry sheets prepared in Examples and Comparative Examples which can be manufactured as a laundry sheet was evaluated by the following method (Comparative Examples a and c were evaluated by the same amount of the active ingredient formulation instead of the water-soluble detergent sheet).

Specifically, the washing power was evaluated by using a washing machine under the same conditions, and at this time, general tap water was used as the washing water. In addition, the temperature of the washing was cold water was the same as the conditions used in normal households, and the emulsified cloth used for the evaluation of cleaning power was used as the artificial wet cloth and protein contaminant EMPA 116 manufactured by the Japan Laundry Science Association. In addition, the soil cloth was evaluated by attaching to the actual cotton t-shirt. In addition, 16 contaminated cloths of 5 cm × 5 cm size were used for comparative evaluation. At this time, the WB value which is the value which shows the whiteness of the contaminated cloth was measured using the color difference meter before and after washing. The laundry sheet prepared in the above example was cut to a size of 20 cm × 15 cm, and two pieces of the detergent thus cut were used. In the initial stage of washing, the washing sheet and detergent were put together with the contaminated cloth, and the washing conditions were performed at the medium water level in the standard course of the washing machine (20 minutes of washing and two rinsing cycles), and the dehydrated contaminated cloth was placed in a constant temperature and humidity room (25 ° C). , 20% RH) was dried for 1 day, and ironed to measure the W _B value using the same colorimeter. The obtained result was substituted into the Kubelka Munch type | mold same as Example 3, and washability was computed. The results are shown in Table 15 below.

Example Comparative Example a b c d k l a b c Cleaning power (%)
(Japan Laundry Science Association) 65 67 69 71 55 58 72 64 60 Cleaning power (%)
(Protein contaminants, EMPA 116) 55 58 62 68 52 50 48 66 62

As shown in Table 15 above, 15% by weight of polyoxyethylene alkyl ether, which is a nonionic surfactant, is contained in Examples a, b, c, d, k, and l having proper sheet forming, solubility and tensile strength. The washing performance of example d was the best.

Example 7 Evaluation of stability (hygroscopicity)

The stability of the laundry sheet prepared in Example d of Example 6 was evaluated, and the results are shown in Table 16 below.

After 1 month Two months later Remarks Dry residue Film status Dry residue Film status Room temperature 96% Good 96.5% Good Moisture in the sheet dries, making the sheet brittle, but there is no significant difference in solubility. 50 degrees 97% Good 97.5% Good Freeze / Thaw
(cycle: -15 ~ 50 ℃) 95.5% Good 96% Good Almost no change from the initial state. 30 degree, 80% humidity 94.5% Good 94% Good It feels a bit damp, but it doesn't get on your hands, is not sticky, and the film is slightly soft. daylight 96% Good 96.5% Good Similar to room temperature

The initial sheet drying residue was 95% by weight, the moisture content was 5% by weight, and the drying residue was measured after drying for 10 minutes at 105 ℃ using a Halogen moisture analyzer.

As shown in Table 16, despite being a water-soluble sheet detergent, it was possible to secure stability as a product under various conditions including hot and humid rainy season conditions.

Example 8 Evaluation of Use of PVA Copolymer

To prepare a laundry sheet in accordance with the prescription of Table 17, the manufacturing method was the same as in Example 4.

Item Example a b c d e f g h i Polymer
matrix PVA ⁽¹⁾ 40 40 - - - - - - - PVA copolymer ⁽²⁾ - - 40 40 40 40 40 40 40 Nonion
Surfactants LA7 15 13.5 15 14.3 13.6 13.0 12.3 11.6 10.9 Anion
Surfactants SLS ⁽³⁾ 40 36.4 40 38.2 36.4 34.5 32.7 30.9 29.1 additive Builders ⁽⁴⁾ - 5 - 2.5 5 7.5 10 12.5 15 Fluorescent Dyes ⁽⁵⁾ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Incense and more 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sum Sum 100 100 100 100 100 100 100 100 100

In Table 17, PVA ⁽¹⁾ means polyvinyl alcohol having a degree of saponification of 86.5% and an average degree of polymerization of 500, and PVA copolymer ⁽²⁾ refers to vinyl alcohol (98 mol%, saponification: about 77 mol%)-methacrylic acid ( 2 mol%) was used as a copolymer having an average degree of polymerization of 500, SLS ⁽³⁾ is sodium lauyl sulfate, sodium carbonate (soda) as builder ⁽⁴⁾ , Tinopal CBS-X as fluorescent dye ⁽⁵⁾ (Ciba Specialty Chemical) was used.

The manufactured laundry sheets were evaluated in the same manner as in Example 4, and the results are shown in Table 18 below.

Example a b c d e f g h i Cleaning power (%)
(Japan Laundry Science Association) 71 64 70 70 72 71 68 66 64 Cleaning power (%)
(Protein contaminants, EMPA 116) 68 60 67 69 72 76 74 72 68 Solubility ◎ X ◎ ◎ ◎ ◎ ◎ ◎ ◎ The tensile strength ◎ △ ◎ ◎ ◎ ○ ○ △ △

As shown in Table 18, when the builder is added to the PVA, the PVA is cured so that the solubility and physical properties are drastically reduced, and the washing performance is also ineffective due to the insoluble component. However, when the PVA-copolymer is used, the addition of the builder does not cause hardening, and thus the washing power is improved by the builder, and above a certain concentration, the effect is offset by the washing power reduction due to the decrease of the relative surfactant amount. In addition, the sheet strength was reduced by the large amount of builders in the film when the amount of builders was 7.5% or more.

&Lt; Example 9 > Evaluation of influence of addition of starch

To prepare a sheet having a prescription as shown in Table 19, using the PVA, starch or a mixture thereof as a formulation agent was evaluated the effect of the addition of starch. The results were evaluated in the same manner as in Example 2, and are shown in Table 20, and the tensile strength of the results in Table 20 is shown in FIG.

Raw material content One Formulation Agent 40% 2 SLS 45% 3 LA7 10% 4 Etc 5% water 170 (seat solid content 100)

Formulation Agent
PVA / starch
(total 40%) Casting after drying
surface Solubility The tensile strength
(kgf / cm ² ) Remarks A 1/0 Good Good ◎ 10.7 (○) B 3/1 Good Floating phenomenon (3 points) X (Hazy) 6 (?) Starch powder sinks 3/1 (starch) Good Floating phenomenon (3 points) ◎ 5.3 (△) C 2/1 Good Floating phenomenon (4 points) X (Hazy) 4.1 (X) Starch powder sinks 2/1 (starch) Good Floating phenomenon (4 points) ◎ 4.1 (X) D 1/1 Good Floating phenomenon (4 points) X (Hazy) 2 (X) Starch powder sinks 1/1 (starch) Good Floating phenomenon (4 points) Δ 2.1 (X) Some residue left

As shown in Table 20 and FIG. 2, as the starch is mixed and used as a formulation agent, that is, as the starch is included as a sheet constituent, a phenomenon in which the surfactant floats after drying (poor compatibility) is increased, and the starch content is increased. The strength of the sheet also decreased with the increase. Furthermore, as the starch content increased, solubility also decreased. Therefore, it was understood that it is preferable not to use starch while manufacturing the laundry sheet as in the present invention. In order to overcome the compatibility and tensile strength problems, there is a problem in that the content of the formulation agent in the sheet (50% or more) increases, and in order to improve solubility, starch must first be gelatinized.

Claims (23)

A laundry sheet produced by using a polyvinyl alcohol or polyvinyl alcohol copolymer as a polymer and containing a surfactant,
The surfactant is a laundry sheet, characterized in that containing an alkyl sulfate alkali metal salt of 8-18 carbon atoms. The laundry sheet according to claim 1, wherein the alkali metal salt of the alkyl sulfate is sodium lauryl sulfate. The washing sheet according to claim 1, wherein the alkyl sulfate alkali metal salt having 8 to 18 carbon atoms is a main surfactant contained at least 50% by weight based on the total content of the surfactant. The laundry sheet according to claim 3, wherein the main surfactant is contained in an amount of 60 wt% or more based on the total content of the surfactant. According to claim 1, wherein the total content of the surfactant is 40 to 70% by weight based on the total weight of the sheet, the total content of polyvinyl alcohol or polyvinyl alcohol-based copolymer is 30 to 50% by weight relative to the total weight of the sheet. Washing sheet. The washing sheet according to claim 1, wherein the polyvinyl alcohol or polyvinyl alcohol copolymer has a number average molecular weight of 20,000-50,000. 7. The laundry sheet according to claim 6, wherein the polyvinyl alcohol or polyvinyl alcohol copolymer has a number average molecular weight of 20,000-30,000. The laundry sheet according to claim 1, wherein the polymer is polyvinyl alcohol and the degree of saponification of the polyvinyl alcohol is 80-90%. According to claim 5, wherein the total content of the polyvinyl alcohol or polyvinyl alcohol-based copolymer in the sheet is 30 to 50% by weight based on the total weight of the sheet after drying, the content of the lauryl sulfate alkali metal salt of the main surfactant is 30 to 60 wt%, and the total content of the auxiliary surfactant is 10 to 20 wt%. The laundry sheet according to any one of claims 1 to 9, wherein the laundry sheet includes bubbles to improve water solubility. The laundry sheet according to any one of claims 1 to 9, wherein the specific gravity of the laundry sheet is 0.6 to 0.9. A laundry sheet comprising a polymer, a surfactant and an alkali builder,
Wherein the polymer is a polyvinyl alcohol-based copolymer including a monomer unit having a carboxyl group,
The surfactant is a laundry sheet, characterized in that containing an alkyl sulfate alkali metal salt of 8-18 carbon atoms. 13. The method according to claim 12, wherein the copolymer comprises a vinyl alcohol unit and an anionic monomer unit of the following general 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 laundry sheet according to claim 12, wherein the alkali metal salt of the alkyl sulfate is sodium lauryl sulfate. The laundry sheet according to claim 12, wherein the alkyl sulfate alkali metal salt is a main surfactant containing 60 wt% or more based on the total content of the surfactant. The method of claim 12, wherein the total content of the surfactant is 40 to 70% by weight based on the total weight of the sheet, the total content of the polyvinyl alcohol-based copolymer is 30 to 50% by weight relative to the total weight of the sheet Sheet. The laundry sheet according to claim 12, wherein the polyvinyl alcohol-based copolymer has a number average molecular weight of 20,000-50,000. 13. The laundry sheet according to claim 12, wherein the saponification degree of the polyvinyl alcohol copolymer is 60-85%. 19. The laundry sheet according to any one of claims 12 to 18, wherein the laundry sheet includes bubbles to improve water solubility. 19. The laundry sheet according to any one of claims 12 to 18, wherein the specific gravity of the laundry sheet is 0.6 to 0.9. 19. A laundry sheet according to any one of claims 1 to 9 and 12 to 18, wherein said sheet is substantially free of starch. Preparing a solution containing a polyvinyl alcohol or polyvinyl alcohol-based copolymer and a surfactant; Bubbling; And drying the laundry sheet. 23. The method of claim 22, wherein the surfactant comprises an alkyl sulfate alkali metal salt having 8-18 carbon atoms.

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