TWI782618B - Gas barrier film preparation method and gas barrier film - Google Patents

Abstract

A method for preparing a gas barrier film, comprising sequentially performing film-forming treatment and annealing treatment on a component comprising an amorphous polymer material whose crystallinity ranges from greater than 0% to less than 20%, wherein the amorphous polymer material It is selected from polyether imide, polyether imide, polymethyl methacrylate, or any combination of the above, and the temperature range of the annealing treatment is above the glass transition temperature of the non-crystalline polymer material. The invention also provides a gas barrier film prepared by the preparation method, and the gas barrier film has gas barrier properties.

Description

Preparation method of gas barrier film and gas barrier film

The invention relates to a method for preparing a film and the film, in particular to a method for preparing a gas-barrier film and the film.

The Republic of China Patent Publication No. 201824613A discloses a porous membrane, which is composed of semi-crystalline polymers with a crystallinity ranging from 20% to 80% and mineral fillers, which are sequentially subjected to film-forming treatment, annealing treatment and stretching. Formed by stretching treatment, wherein the semi-crystalline polymer is polyolefins, fluorocarbons, polyamides, polyesters, polyacetals (or polyoxymethylenes), polysulfides, polyvinyl alcohols, The above-mentioned copolymers or any combination of the above-mentioned. By controlling the temperature of the annealing treatment within the range of (melting temperature-80°C) to (melting temperature-10°C), and performing stretching treatment by stretching, the porous membrane has holes, and can For air, water vapor and other gases to pass through, so that it can be used in air filtration and other fields.

From the above, it can be seen that the porous film of this patent does not have gas barrier ability, so it cannot be applied in food packaging or encapsulation industry.

Therefore, an object of the present invention is to provide a method for preparing a gas barrier film capable of producing a gas barrier film with gas barrier properties.

Therefore, the preparation method of the gas barrier film of the present invention includes: performing film-forming and annealing treatment on the component comprising an amorphous polymer material whose crystallinity ranges from more than 0% to less than 20%, wherein the amorphous high The molecular material is selected from polyether imide, polyether imide, polymethyl methacrylate, or any combination of the above, and the temperature range of the annealing treatment is above the glass transition temperature of the non-crystalline polymer material.

Another object of the present invention is to provide a gas barrier film with gas barrier properties.

The gas barrier film of the present invention is produced by the above-mentioned preparation method of the gas barrier film.

The effect of the present invention is that: through the annealing treatment, the method for preparing the gas barrier film of the present invention can make the gas barrier film formed by the components containing the non-crystalline polymer material whose crystallinity range is greater than 0% and less than 20% It has gas barrier properties.

Other features and effects of the present invention will be clearly presented in the implementation manner with reference to the drawings, wherein: Fig. 1 is a graph illustrating the effect of the gas barrier film of Example 1 on oxygen, hydrogen and nitrogen at different times Gas-barrier effect; Fig. 2 is a graph, illustrates the gas-barrier film of embodiment 2 to oxygen, gas at different times The gas barrier effect of hydrogen and nitrogen; Fig. 3 is a graph, illustrates the gas barrier effect of the gas barrier film of embodiment 3 to oxygen, hydrogen and nitrogen at different times; Fig. 4 is a graph, illustrates comparative example 1 The gas barrier effect of the hollow fiber membrane on oxygen, hydrogen and nitrogen at different times; and FIG. 5 is a graph illustrating the gas barrier effect of the gas barrier membrane of Comparative Example 2 on oxygen, hydrogen and nitrogen at different times.

The present invention will be described in detail below.

<Manufacturing method of gas barrier film>

The preparation method of the gas barrier film comprises performing film-forming and annealing treatment on the component comprising the non-crystalline polymer material whose crystallinity ranges from more than 0% to less than 20%, wherein the non-crystalline polymer material is selected from Polyether imide, polyether imide, polymethyl methacrylate, or any combination of the above, and the temperature range of the annealing treatment is above the glass transition temperature (Glass transition temperature) of the non-crystalline polymer material.

In some embodiments of the present invention, the amorphous polymer material is polyetherimide with a crystallinity of 18% or less.

The film-forming treatment is not particularly limited, and is adjusted according to the desired film configuration, For example, a coating method, a spinning method, or the like is used. The configuration of the membrane is, for example, a flat plate membrane, a hollow fiber membrane, or the like. The spinning method is, for example, a dry spinning method, a wet spinning method, or a dry-wet spinning method. In the preparation method of the gas barrier membrane of the present invention, a coating method can be used for film formation to obtain a flat membrane, or a spinning method can be used for membrane formation to obtain a hollow fiber membrane. In some embodiments of the present invention, the film-forming treatment is performed by a dry-wet spinning method.

In some embodiments of the present invention, when the amorphous polymer material is polyetherimide with a crystallinity of 18% or less, the temperature range of the annealing treatment is between 220°C and 240°C, and the annealing The processing time was 1 hour.

In order to make the gas barrier film have better hardness and gas barrier properties, preferably, in the preparation method of the gas barrier film, the component further includes an inorganic material. Based on 100wt% of the total amount of the components, the total amount of the inorganic material ranges from 10wt% to 30wt%. The inorganic material can be used alone or in combination, and the inorganic material is for example but not limited to layered silicate, graphene, carbon nanotubes or inorganic particles below the micron level. The inorganic particles below the micron level can be used alone or in combination, and the inorganic particles below the micron level are for example but not limited to alumina particles, silicon dioxide particles, or titanium dioxide particles. In some embodiments of the present invention, the inorganic material is silica microparticles.

In the production method of the gas barrier film of the present invention, the component further contains a solvent. The solvent can be used alone or in combination, and the solvent is for example but not limited to N- Methyl-2-pyrrolidone (N-methyl-2-pyrrolidone).

<Gas barrier film>

The gas barrier film is prepared by the above-mentioned preparation method of the gas barrier film. The preparation method of the gas barrier film is as described above, so it will not be repeated here. The configuration of the gas barrier membrane is, for example, a flat membrane, a tubular membrane, or a hollow fiber membrane. In some embodiments of the present invention, the gas barrier membrane is a hollow fiber membrane. The gas barrier film of the present invention can effectively block the passage of hydrogen, oxygen, or nitrogen.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limitations on the implementation of the present invention.

Example 1 Gas barrier film

25 grams of polyetherimide (brand: Sigma-Aldrich; model: 700193; molecular weight: 38770 Dalton; crystallinity: 18%; glass transition temperature: 217 ° C) and 75 grams of N-methyl-2- The pyrrolidones were mixed and stirred at a speed of 60 rpm for 24 hours at a temperature of 80° C. to form a uniform mixed solution. Next, the mixed solution was left to stand for 24 hours at a temperature of 28° C.±2° C., so as to dissipate the air bubbles in the mixed solution to form a settled mixed solution. Then, use the spinning equipment and adopt the dry-wet spinning method to perform membrane-forming treatment on the static mixed solution to obtain a hollow fiber membrane with a thickness of 750 μm, wherein the spinning equipment includes inner and outer diameters respectively Spinning nozzles of 2.0mm and 3.5mm, stainless steel tank (accommodating the static mixed solution), injection pump (brand: Teledyne Isco Inc., model: D-Series) and The core liquid (as a coagulant; component: secondary water) has a pressure of 1.2 atm, a flow rate of the static mixed solution of 25.7 mL/min, and an air gap of 20 cm. Then, place the hollow fiber membrane in a tubular furnace (brand name: Changhua Electric Heating Co., Ltd.) and perform annealing treatment to obtain a gas barrier membrane, and the annealing treatment is carried out at a temperature of 220° C. for 1 hour in a vacuum environment. Heat treatment, followed by natural cooling to room temperature.

Example 2

The preparation steps of Example 2 are roughly the same as those of Example 1, the difference mainly lies in: the temperature of the annealing treatment is different. In this Example 2, the temperature of the annealing treatment was 240°C.

Example 3 Gas barrier film

20 grams of silica microparticles with a particle size of 1.03 μm and 25 grams of polyetherimide (brand: Sigma-Aldrich; model: 700193; molecular weight: 38770 Daltons; crystallinity: 18%; glass transition temperature: 217° C.) was mixed with 75 grams of N-methyl-2-pyrrolidone, and stirred at a speed of 60 rpm for 24 hours at a temperature of 80° C. to form a uniform mixed solution. Next, the mixed solution was left to stand for 24 hours at a temperature of 28° C.±2° C., so as to dissipate the air bubbles in the mixed solution to form a settled mixed solution. Then, a hollow fiber membrane with a thickness of 750 μm is obtained by using a spinning device and a dry-wet spinning method, wherein the spinning device includes a nozzle with an inner diameter and an outer diameter of 2.0 mm and 3.5 mm, respectively. , stainless steel tank (accommodating the static mixed solution), injection pump (brand: Teledyne Isco Inc., type No.: D-Series) and core fluid (as a coagulant; component: secondary water), the pressure is 1.2atm, the flow rate of the mixed solution is 25.7mL/min, and the air distance is 20 cm. Then, place the hollow fiber membrane in a tubular furnace (brand name: Changhua Electric Heating Co., Ltd.) for annealing treatment to obtain a gas barrier membrane, and the annealing treatment is a heat treatment at a temperature of 220°C for 1 hour in a vacuum environment , and then naturally cooled to room temperature.

Comparative example 1

The preparation steps of Comparative Example 1 are roughly the same as those of Example 1, the main difference being that in Comparative Example 1, no annealing treatment was performed.

Comparative example 2

The preparation steps of Comparative Example 2 are roughly the same as those of Example 1, the difference mainly lies in: the temperature of the annealing treatment is different. In the comparative example 2, the temperature of the annealing treatment is 200° C., which is lower than the glass transition temperature of the polyetherimide.

[evaluation items]

Measurement of oxygen permeate side pressure and oxygen permeation flux: In order to clearly understand the measurement process, the gas barrier film of Example 1 is used for illustration below, while the rest of the examples and comparative examples are carried out in the same manner. Coating epoxy resin to a first end portion of the gas barrier film of Example 1, and curing the epoxy resin, in order to avoid the gas in the gas barrier film passing through the first end in the gas permeation test Then, the gas barrier film enters through the first opening of a stainless steel tube, and is installed in an accommodating space of the stainless steel tube, and then, the epoxy resin is passed through the stainless steel tube opposite to the first opening a second opening of an opening enters and is applied to a second end of the gas barrier film opposite to the first end, and curing the epoxy resin at room temperature for 24 hours to seal the second opening and the gap between the second end. Next, use a vacuum pump to control the pressure in the hollow cavity of the accommodating space and the gas barrier film at -1kg/cm ² , then turn off the vacuum pump, and then introduce oxygen at a pressure of 2kg/cm ² In the hollow cavity of the gas-barrier membrane, a computer is used to record the pressure value of the permeate side displayed by the pressure sensor at the gas outlet of the stainless steel tube connected to the accommodating space, and at the same time, draw the permeate side A graph of pressure and time, and then calculate the slope value of the permeate side pressure steadily rising with time (Pseudo steady state), and substitute it into a formula to calculate the permeation flux, the formula is as follows:

Among them, Pg is the permeate flux, dp/dt is the slope value of the permeate side pressure rising steadily with time (unit: cmHg/sec), V is the volume of gas flowing into the pressure sensor (unit: cm ³ ), T ₀ is 273K, L is the thickness of the gas barrier film (unit: cm), A is the inner surface area of the gas barrier film (unit: cm ² ), △p is the pressure difference between the first opening and the second opening (unit: : cmHg), P ₀ is 76cmHg, and T is the gas temperature (unit: K).

Measurement of hydrogen permeate side pressure and hydrogen permeate flux: The method of measuring the hydrogen permeate side pressure is roughly the same as the oxygen permeate side pressure measurement method, the difference mainly lies in the replacement of oxygen with hydrogen.

Nitrogen permeate side pressure (permeate side pressure) measurement: the The pressure measurement method of the nitrogen permeation side is roughly the same as that of the oxygen permeation side, the difference mainly lies in the replacement of oxygen with nitrogen.

From the experimental data of permeation flux in Table 1, it can be seen that compared with the hollow fiber membrane of Comparative Example 1 without annealing treatment and the gas barrier membrane of Comparative Example 2 whose annealing temperature is lower than the glass transition temperature of the amorphous polymer material, Membrane, the gas barrier film prepared by the method for preparing the gas barrier film of the present invention has a lower permeation flux, which means that the method for preparing the gas barrier film of the present invention can indeed prepare a gas barrier film with gas barrier properties.

Furthermore, from the experimental data of the permeation side pressure of the gas barrier membranes of Examples 1 to 3 in Figure 1 to Figure 3 and the hollow fiber membrane of Comparative Example 1 in Figure 4, The gas barrier film can still block the passage of hydrogen with a kinetic diameter of 2.89 Å, nitrogen with a kinetic diameter of 3.64 Å, or oxygen with a kinetic diameter of 3.46 Å for a long time. The gas barrier of the gas film to oxygen and nitrogen is the best, and even if the time is extended to the fifth day, the permeation side pressure of oxygen and nitrogen is still close to -1kg/cm ² , which means that Example 3 can completely block Oxygen and nitrogen permeation, showing the best gas barrier properties.

To sum up, through the annealing treatment, the method for preparing the gas barrier film of the present invention can indeed make the gas barrier film formed by the component comprising the amorphous polymer material with a crystallinity ranging from more than 0% to less than 20% It has gas barrier properties, so it can really achieve the purpose of the present invention.

But the above-mentioned ones are only embodiments of the present invention, and should not limit the scope of the present invention. All simple equivalent changes and modifications made according to the patent scope of the present invention and the content of the patent specification are still within the scope of the present invention. Within the scope covered by the patent of the present invention.

Claims (5)

A method for preparing a gas barrier film, comprising: sequentially performing film-forming and annealing treatment on a component comprising an amorphous polymer material whose crystallinity ranges from greater than 0% to less than 20%, wherein the amorphous polymer The material is selected from polyether imide, polyether imide, polymethyl methacrylate, or any combination of the above, and the temperature range of the annealing treatment is above the glass transition temperature of the non-crystalline polymer material; the group The component also includes an inorganic material, the inorganic material is selected from layered silicate, graphene, carbon nanotubes, inorganic particles below the micron level, or any combination of the above, and the inorganic particles below the micron level are selected from two Silicon oxide, aluminum oxide, titanium oxide or any combination of the above. The method for preparing a gas barrier film according to Claim 1, wherein the non-crystalline polymer material is polyetherimide. The method for preparing a gas barrier film according to claim 2, wherein the temperature range of the annealing treatment is between 220°C and 240°C. The method for preparing a gas barrier film according to claim 1, wherein the film forming process is performed by a dry-wet spinning method. A gas barrier film produced by the method for preparing a gas barrier film according to any one of Claims 1 to 4.

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