KR20180059643A - poly(vinyl alcohol)/poly(methyl methacrylate) blend films prepared by the heterogeneous surface saponification of poly(vinyl acetate)/poly(methyl methacrylate) blend films and a preparing method thereof - Google Patents

Abstract

The present invention relates to a novel method for manufacturing polyvinyl alcohol/polymethylmethacrylate blend film and a polyvinyl alcohol/polymethylmethacrylate blend film manufactured thereby. More particularly, the present invention relates to a method for manufacturing a polyvinyl alcohol/polymethylmethacrylate blend film comprising a step of impregnating the polyvinyl acetate/polymethylmethacrylate blend film with a first solvent capable of maintaining a film form, and heterogeneously saponifying the polyvinyl acetate/ polymethylmethacrylate blend film to manufacture a polyvinyl alcohol/polymethylmethacrylate blend film.

Description

[0001] The present invention relates to a polyvinyl alcohol / polymethylmethacrylate blend film produced by heterogeneous saponification of a polyvinyl acetate / polymethylmethacrylate blend film, and a process for producing the blend film of poly (vinyl alcohol) / poly (methyl methacrylate) the heterogeneous surface saponification of poly (vinyl acetate) / poly (methyl methacrylate) blend films and a preparing method thereof}

The present invention relates to a novel process for producing a polyvinyl alcohol / polymethylmethacrylate blend film and a polyvinyl alcohol / polymethylmethacrylate blend film produced thereby.

A method of producing a film with an organic polymer includes a solution casting method in which a high viscosity polymer solution obtained by dissolving a polymer in a solvent is developed on a wide and smooth surface free from adherence to volatilize the solvent and obtain a film, A melt processing method in which a polymer material is heated to a melting temperature or a softening temperature or higher and applied to obtain a film. The melt processing method is disadvantageous in that it is not suitable for a high-quality film such as an optically functional film because the film thickness is not adjusted very precisely and fine lines (so-called dy line) are formed on the film. On the other hand, the solution casting method has a better optical isotropy and thickness uniformity than the melt processing method and can produce a film having a small amount of foreign substances. In addition, since the method of use and installation equipments are experimentally simple, the content of inorganic materials It is possible to easily produce a film exhibiting excellent characteristics according to the present invention.

On the other hand, polyvinyl alcohol, which is a hydrophilic polymer, has a relatively low viscosity as compared with other polymers, and is nontoxic and has unique properties such as biodegradability. In addition, it has excellent miscibility when blended with other polymers and is used for various purposes such as medical materials, packaging materials, release films, and water-soluble films.

In addition, the hydrophobic polymer, polymethyl methacrylate, is excellent in transparency and weatherability, and has excellent hardness, chemical resistance, surface gloss and adhesion, and is used as a substitute for glass. However, There is a disadvantage in that the thickness is increased and the use thereof is limited.

Polymethylmethacrylate also has many excellent properties in itself, but due to these drawbacks, a polymer blend is widely used to overcome the disadvantages. The polymer blend is a mixture of two or more kinds of polymers, and it is advantageous in that the cost is much lower than that of the modification by the modification copolymerization method of polymer properties by blending. Also, in the case of a compatible polymer blend, the physical and chemical performance of the polymer blend may be superior to that of the polymer blend due to the synergistic effect of the physical and chemical performance among the polymer blend. However, if there is no strong intermolecular attraction between the constituent polymers, most of the polymer blends are incompatible, resulting in a heterogeneous mixture. The low interfacial adhesion between the constituent polymers is a major cause of the low mechanical performance of the heterogeneous polymer blend.

Polyvinyl alcohol as a hydrophilic polymer and polymethyl methacrylate as a hydrophobic polymer are incompatible with each other, so it is difficult to find a single solvent capable of dissolving the two polymers, making the blend difficult. Thus, a compatibilizer that increases the compatibility of a blend using a graft or block copolymer may be used, or a blend of two or more solvents may be used.

The present inventors have made efforts to develop a technique for producing a polyvinyl alcohol as a hydrophilic polymer and a poly (methyl methacrylate) blend film as a hydrophobic polymer. As a result, it has been found that polyvinyl alcohol, which is a precursor of polyvinyl alcohol, Vinyl acetate / polymethyl methacrylate blend film was prepared by blending methacrylate with solution casting method, and then -OCOCH ₃ in a polyvinyl acetate / polymethyl methacrylate blend film was subjected to a heterogeneous saponification process -OH, it is possible to produce a polyvinyl alcohol / polymethylmethacrylate blend film, and thus the present invention has been completed.

Japanese Patent Application Laid-Open No. 2002-28938

An object of the present invention is to provide a method for producing a film comprising a hydrophobic polymer, polymethylmethacrylate, and a hydrophilic polymer, a polyvinyl alcohol blend.

Another object of the present invention is to provide a polyvinyl alcohol / polymethylmethacrylate blend film having nano-sized curvature in which wrinkles are formed on the surface to improve the specific surface area.

A first aspect of the present invention is a method for producing a polyvinyl acetate / polymethylmethacrylate blend film by impregnating a polyvinyl acetate / polymethylmethacrylate blend film with a first solvent capable of maintaining a film form, Polyvinyl alcohol / polymethylmethacrylate blend film having a nano-sized bend, which comprises saponifying the polyvinyl alcohol / polymethylmethacrylate blend film and converting it into a polyvinyl alcohol / polymethylmethacrylate blend film.

A second aspect of the present invention provides a polyvinyl alcohol / polymethylmethacrylate blend film produced by the first aspect and having nano-sized curvature.

Hereinafter, the present invention will be described in detail.

The production method of the present invention does not directly saponify the polyvinyl acetate / polymethylmethacrylate blend in a solvent but dissolves the solution obtained by dissolving saponified polyvinyl alcohol in a solvent and polymethylmethacrylate in a solvent Is not blended. A polyvinyl alcohol / polymethylmethacrylate blend film is prepared and then saponified while maintaining the film form to prepare a polyvinyl alcohol / polymethylmethacrylate blend film. Therefore, it is important to select and use a solvent that allows the polyvinyl acetate / polymethylmethacrylate blend film to maintain the film shape during saponification.

In the present invention, polyvinyl acetate and polymethyl methacrylate can be used by bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization. In particular, bulk polymerization is advantageous in that relatively high molecular weight polyvinyl acetate and polymethylmethacrylate can be obtained because the probability of chain transfer is lower than in other polymerization methods due to the presence of only monomers in the polymerization system.

The polyvinyl acetate / polymethyl methacrylate blend film can be produced by molding a polymer solution dissolved in a second solvent capable of dissolving polyvinyl acetate and polymethyl methacrylate, followed by drying . Specifically, a high-viscosity polymer solution obtained by dissolving polyvinyl acetate and polymethyl methacrylate in a second solvent is developed on a large smooth surface free from adhesion, followed by solution casting Method (solvent casting method).

The second solvent for dissolving the polyvinyl acetate and polymethyl methacrylate is not limited as long as it is a solvent capable of dissolving both polyvinyl acetate and polymethyl methacrylate, but is preferably a solvent such as benzene, toluene, methanol, ethanol, o- But are not limited to, xylene, xylene, m-xylene, trichloromethane, trichlorethylene, 1,4-dioxane, cyclohexanone, butanol, methyl ethyl ketone, pentyl acetate, ethyl acetate, chloroform, acetone, acetophenone, Dimethyl sulfoxide (DMSO) or a mixture thereof may be used as a solvent.

The polyvinyl acetate / polymethyl methacrylate blend may be from 1 wt.% To 50 wt.%, More preferably from 5 wt.% To 20 wt.%, Based on the total polymer solution. When the concentration is less than 1 wt.%, The solution is too thin to form a film, and when it exceeds 50 wt.%, It is difficult to form a film due to a high viscosity.

The blend ratio of the polyvinyl acetate and polymethyl methacrylate may be 0.5: 99.5 to 99.5: 0.5 (w / w), more preferably 90:10 to 30:70 (w / w) , Uniform blending in the above range is possible.

Further, in order to stabilize the polymer solution, the solution may be left to stand at a temperature of 20 ° C to 35 ° C, for example, for 0.5 to 5 hours to dry. Preferably at a temperature of about < RTI ID = 0.0 > 20 C. < / RTI >

Thereafter, the polymer solution is developed on the surface of a smooth substrate having no adhesiveness, and then the solvent is volatilized to produce a film. A vacuum dryer can be used to volatilize the solvent and a polyvinyl acetate / polymethyl methacrylate blend film placed on a flat surface by volatilizing the solvent at a temperature of about 30 ° C to 50 ° C, for example 24 hours to 60 hours Can be obtained.

The polyvinyl acetate / polymethyl methacrylate blend film prepared above was impregnated with a first solvent capable of maintaining the film form, and the polyvinyl acetate / polymethyl methacrylate blend film was nonuniformly saponified to prepare -OCOCH ₃ is converted to -OH, a polyvinyl alcohol / polymethylmethacrylate blend film can be produced.

Specifically, the polyvinyl acetate / polymethyl methacrylate blend film is impregnated with an acid solution or an alkaline solution (first solvent) containing a dispersant and a swelling agent to form a polyvinyl acetate / polymethyl methacrylate A polyvinyl alcohol / polymethyl methacrylate blend film can be prepared by converting -OCOCH3 of the blend film to -OH.

The acid in the acid solution for saponification may be hydrochloric acid, nitric acid, or a mixture thereof, and the alkali in the alkali solution for saponification may be sodium chloride, sodium hydroxide, potassium hydroxide, or a mixture thereof, but is not limited thereto.

The dispersing agent may be sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate or a mixture thereof.

The swelling agent may be methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), benzene, acetone or a mixture thereof. Preferably, methanol can be used which is easy to obtain, low in cost, low in boiling point, and easy to handle.

In one embodiment, the acid solution is hydrochloric acid, nitric acid or a mixture thereof; A dispersing agent selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate or a mixture thereof; Any one of swelling agents selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), benzene, acetone or mixtures thereof; And a first solvent in which water, preferably distilled water, is mixed and dissolved may be used, but the present invention is not limited thereto.

In another embodiment, the alkali solution is selected from the group consisting of sodium chloride, sodium hydroxide, potassium hydroxide, or mixtures thereof; A dispersing agent selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate or a mixture thereof; Any one of swelling agents selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), benzene, acetone or mixtures thereof; And a first solvent in which water, preferably distilled water, is mixed and dissolved may be used, but the present invention is not limited thereto.

More specifically, sodium chloride; Sodium sulfate; Methanol; And a first solvent in which water, preferably distilled water, is mixed and dissolved can be used.

In the present invention, the saponification of the polyvinyl acetate / polymethyl methacrylate blend film can be carried out at a temperature of 10 to 70 DEG C for 10 to 300 hours. In one embodiment, it may be saponified at a temperature of 40 to 55 占 폚 for 20 to 180 hours, and in another embodiment may be saponified at a temperature of 45 to 55 占 폚 for 60 to 100 hours. The saponification can be carried out at a temperature ranging from 10 to 70 캜 in order to maximize the activation of the swelling agent serving as a catalyst. The time conditions for saponification may vary depending on the temperature conditions.

The saponification degree of the polyvinyl acetate / polymethyl methacrylate blend film produced by the present invention is preferably 60 to 99.99%. Here, the " degree of saponification " indicates the proportion of units actually saponified as vinyl alcohol units among the units obtained by conversion to vinyl alcohol units by saponification. Specifically, it can be expressed as a ratio of the number of moles of the compound converted to -OH to the number of moles of the compound having -OCOCH ₃ .

In another aspect, the present invention provides a polyvinyl alcohol / polymethyl methacrylate blend film having a curvature formed on the surface of the film.

The depth of bending of the polyvinyl alcohol / polymethyl methacrylate blend film may be 10 nm to 10 탆.

The polyvinyl alcohol / polymethyl methacrylate blend film of the present invention can be produced by the production method according to the present invention. The polyvinyl alcohol / polymethylmethacrylate blend film produced by the present invention is a new technology that has not yet been reported.

According to the production method of the present invention, a novel polyvinyl alcohol / polymethyl methacrylate blend film can produce a novel film having not only surface curvature but also hydrophobic and hydrophilic properties.

The process for producing a polyvinyl alcohol / polymethyl methacrylate blend film can be carried out by using a film of poly (methyl methacrylate), a hydrophobic polymer, and a polyvinyl alcohol blend, which is a hydrophilic polymer. Such a film can be used as an implantable material, Coatings, adhesives, polarizing films, and the like.

1 is an optical microscope photograph of a polyvinyl acetate / polymethyl methacrylate blend film.
2 is an optical microscope photograph of a heterogeneous saponified polyvinyl alcohol / polymethyl methacrylate blend film.
3 is a FT-IR analysis result of a non-uniform saponified polyvinyl alcohol / polymethyl methacrylate (blend ratio = 5: 5 weight ratio) blend film.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples. Aldrich reagent was used as the starting material and reaction reagent in the compounds used below. All solvents were pure and used without drying or purification.

In the following Production Examples 1 to 4, experiments were conducted to produce a polyvinyl acetate / polymethyl methacrylate blend film. Various blend ratio polyvinyl acetate / polymethyl methacrylate blend films were prepared by controlling the blend ratios of polyvinyl acetate and polymethyl methacrylate solutions dissolved in chloroform.

Manufacturing example  1: Solution casting method Polyvinyl acetate / Polymethyl methacrylate  Preparation of blend film (blend ratio = 9: 1) (w / w)

The polyvinyl acetate solution and the polyvinyl acetate solution of poly (methyl methacrylate) (9: 1) (w / w) were added to the chloroform solvent at 40 ° C for 30 minutes, Lt; / RTI > The remaining experimental conditions were the same as in Production Example 1.

Manufacturing example  2: Solution casting method Polyvinyl acetate / Polymethyl methacrylate  Preparation of blend film (blend ratio = 7: 3) (w / w)

The polyvinyl acetate and polymethyl methacrylate 10 wt.% (7: 3) (w / w) were added to the chloroform solvent and stirred at 40 ° C for 30 minutes. The polyvinyl acetate solution thus prepared was stirred at room temperature for one hour Lt; / RTI > The remaining experimental conditions were the same as in Production Example 1.

Manufacturing example  3: Solution casting method Polyvinyl acetate / Polymethyl methacrylate  Preparation of blend film (blend ratio = 5: 5) (w / w)

The polyvinyl acetate and polymethyl methacrylate 10 wt.% (5: 5) (w / w) were added to the chloroform solvent and stirred at 40 ° C for 30 minutes. Then, the polyvinyl acetate solution was stirred at room temperature for one hour Lt; / RTI > The remaining experimental conditions were the same as in Production Example 1.

Manufacturing example  4: Solution casting method Polyvinyl acetate / Polymethyl methacrylate  Preparation of blend film (blend ratio = 3: 7) (w / w)

The polyvinyl acetate and polymethyl methacrylate 10 wt.% (3: 7) (w / w) were added to the chloroform solvent and stirred at 40 ° C for 30 minutes. The polyvinyl acetate solution was stirred at room temperature for one hour Lt; / RTI > The remaining experimental conditions were the same as in Production Example 1.

division Blend ratio (w / w) Polymer concentration Temperature (℃) Vapor pressure Film creation PVAc PMMA Production Example 1 9 One 10 wt.% ≪ 40 40 cmHg ○ Production Example 2 7 3 10 wt.% ≪ 40 40 cmHg ○ Production Example 3 5 5 10 wt.% ≪ 40 40 cmHg ○ Production Example 4 3 7 10 wt.% ≪ 40 40 cmHg ○

In the following Examples 1 to 12, experiments were conducted to produce a polyvinyl alcohol film by saponifying the polyvinyl acetate film prepared in Production Example. The polyvinyl acetate film prepared in Production Example was saponified by using an alkali solution, and the film was put in distilled water and stirred again, and then dried at room temperature to prepare a polyvinyl alcohol film.

Example  One: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

Distilled water (100 mL), NaOH (10 g) and Na ₂ SO ₄ (10 g) were added to the polyvinyl acetate / polymethyl methacrylate blend film (9: 1) of Production Example 1 prepared by solution casting Gently stirred. Polyvinyl acetate / polymethyl methacrylate blend film (1 g) was added to the prepared alkali solution, and the saponification reaction was carried out at 50 ° C for 24 hours. After the saponification reaction, the film was washed several times with distilled water, and the washed film was dried at room temperature for 12 hours to prepare a polyvinyl alcohol / polymethyl methacrylate blend film.

In the following Examples 2 to 12, polyvinyl alcohol / polymethylmethacrylate blend films were prepared by varying the saponification conditions according to Table 2.

Example  2: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (9: 1) of Preparation Example 1 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 48 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  3: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (9: 1) of Preparation Example 1 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 72 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  4: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

A polyvinyl acetate / polymethyl methacrylate blend film (7: 3) of Preparation Example 2 (7: 3) was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 24 hours, To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  5: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (7: 3) of Preparation Example 2 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 48 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  6: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

A polyvinyl acetate / polymethyl methacrylate blend film (7: 3) of Preparation Example 2 (7: 3) was added to the prepared alkali solution, and the saponification reaction was carried out at 50 ° C for 72 hours. To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  7: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (5: 5) of Preparation Example 3 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 24 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  8: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (5: 5) of Production Example 3 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 48 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  9: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (5: 5) of Preparation Example 3 was added to the alkali solution and the saponification reaction was carried out at 50 ° C for 72 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  10: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (3: 7) of Production Example 4 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 24 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  11: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (3: 7) of Preparation Example 4 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 48 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

Example  12: Polyvinylacetic acid / Polymethyl methacrylate Blend  Film Heterogeneous system Saponification  Polyvinyl alcohol / Polymethyl methacrylate Blend  Production of film

The procedure of Example 1 was repeated except that the polyvinyl acetate / polymethyl methacrylate blend film (3: 7) of Preparation Example 4 was added to the prepared alkali solution and the saponification reaction was carried out at 50 ° C for 72 hours To prepare a saponified polyvinyl alcohol / polymethyl methacrylate blend film.

The experimental conditions and the results of the above-described Examples 1 to 12 are summarized in Table 2 below.

division Saponification reaction time Blend ratio (w / w) Temperature (℃) Saponification solution (weight ratio)
_{(NaOH: Na 2 SO 4:} MeOH: H 2 O) PVAc PMMA Example 1 24 hours 9 One 50 10: 10: 10: 100 Example 2 48 hours 9 One 50 10: 10: 10: 100 Example 3 72 hours 9 One 50 10: 10: 10: 100 Example 4 24 hours 7 3 50 10: 10: 10: 100 Example 5 48 hours 7 3 50 10: 10: 10: 100 Example 6 72 hours 7 3 50 10: 10: 10: 100 Example 7 24 hours 5 5 50 10: 10: 10: 100 Example 8 48 hours 5 5 50 10: 10: 10: 100 Example 9 72 hours 5 5 50 10: 10: 10: 100 Example 10 24 hours 3 7 50 10: 10: 10: 100 Example 11 48 hours 3 7 50 10: 10: 10: 100 Example 12 72 hours 3 7 50 10: 10: 10: 100

Claims (12)

Polyvinyl acetate / polymethyl methacrylate blend film was impregnated with a first solvent capable of maintaining the film form, and the polyvinyl acetate / polymethyl methacrylate blend film was nonuniformly saponified to prepare a polyvinyl alcohol / polymethyl Polyvinyl alcohol / polymethylmethacrylate blend film having nano-sized bending, comprising the step of converting the polyvinyl alcohol / polymethylmethacrylate blend film into a methacrylate blend film.
The method according to claim 1, wherein the polyvinyl acetate / polymethyl methacrylate blend film is produced by molding a polymer solution dissolved in a second solvent capable of dissolving polyvinyl acetate and polymethyl methacrylate, followed by drying Wherein the polyvinyl alcohol / polymethylmethacrylate blend film comprises a polyvinyl alcohol / polymethylmethacrylate blend film.
The polyvinyl alcohol / polymethylmethacrylate blend film according to claim 2, wherein the polyvinyl acetate / polymethylmethacrylate blend is 1 wt.% To 50 wt.% Based on the total polymer solution. ≪ / RTI >
The non-uniform saponification according to claim 1, wherein the heterogeneous saponification comprises impregnating a first solvent, which is an alkaline solution containing a dispersant and a swelling agent, with a polyvinyl acetate / polymethylmethacrylate blend film to perform nonuniform saponification, A process for producing an alcohol / polymethyl methacrylate blend film.
The polyvinyl alcohol / polymethyl methacrylate blend film according to claim 2, wherein the blend ratio of the polyvinyl acetate and polymethyl methacrylate is 0.5: 99.5 to 99.5: 0.5 (w / w) Gt;
The method of claim 2, wherein the second solvent is selected from the group consisting of benzene, toluene, methanol, ethanol, o-xylene, m-xylene, trichloromethane, trichlorethylene, 1,4-dioxane, cyclohexanone, A process for producing a polyvinyl alcohol / polymethyl methacrylate blend film, which is ethyl ketone, pentyl acetate, ethyl acetate, chloroform, acetone, acetophenone, dimethylformamide, dimethylsulfoxide (DMSO) or mixtures thereof.
The method of claim 4, wherein the dispersing agent is sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or a mixture thereof.
5. The composition of claim 4, wherein the swelling agent is selected from the group consisting of poly (methyl methacrylate), ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), benzene, acetone, Vinyl alcohol / polymethyl methacrylate blend film.
The process for producing a polyvinyl alcohol / polymethyl methacrylate blend film according to claim 1, wherein the saponification is performed at a temperature ranging from 10 ° C to 70 ° C for 10 hours to 300 hours.
The method of claim 1, wherein the first solvent is selected from the group consisting of sodium chloride; Sodium sulfate; Methanol; And distilled water are mixed and dissolved. The method for producing a polyvinyl alcohol / polymethylmethacrylate blend film according to claim 1,
A polyvinyl alcohol / polymethyl methacrylate blend film having nano-sized curvature, produced by the method of any one of claims 1 to 10.
12. The polyvinyl alcohol / polymethyl methacrylate blend film according to claim 11, wherein the nano-sized bending has a depth of 10 nm to 10 mu m.

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