KR101341133B1 - Functional fluorinated polymer film and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a functional fluorine-based polymer film improved surface hydrophobicity by introducing silane into the polymer film in a liquid phase reaction, followed by introducing fluorine into a gas phase reaction, and a method of manufacturing the same. In the method for producing a functional fluorine-based polymer film according to the present invention, a step of preparing a silane mixed solution by mixing a silane (silane), alcohol and a silane polymerization catalyst, by supporting the polymer film in the silane mixture solution silane on the surface of the polymer film Applying a silane to the surface of the polymer film by irradiating microwaves to the polymer film coated with the silane, and introducing a fluorine element into the polymer film into which the silane is introduced by the vapor phase fluorination method. . According to the present invention, a polymer film having a hydrophobic surface can be prepared by introducing silane into the polymer film to have a surface roughness suitable for showing surface hydrophobicity, and introducing fluorine to introduce a hydrophobic functional group on the surface.

Description

Functional fluorinated polymer film and method for manufacturing the same

The present invention relates to a functional fluorine-based polymer film and a method of manufacturing the same, and more particularly, to introduce a silane into a liquid phase reaction in a polymer film, and then to introduce a fluorine in a gas phase reaction to improve the surface hydrophobicity and a functional fluorine-based polymer film and its preparation It is about a method.

Recently, various digital devices such as smartphones, digital TVs, tablet PCs, laptops, PMPs, and navigation devices have been released, and the demand for flat panel display panels and touch screens is increasing.

Flat panel display panels include LCD, PDP, OLED, etc., and are widely used as display devices of various digital devices due to features such as light weight, thin film, low power drive, full color, and high resolution. The touch screen is an input device installed on the display surface of various flat panel display devices and used to allow a user to select desired information while viewing the display device.

The display panel or the touch screen is exposed to the outside of the front surface is easily contaminated by moisture or pollutants containing moisture. And if it is left standing for a long time in a contaminated state, it is difficult to clean the contaminants. Moreover, the display panel or touch screen needs to be protected from moisture because moisture may adversely affect the function of the product.

Recently, various methods for protecting a display panel or a touch screen from contamination by moisture have been proposed, and a protective film covering and protecting the display panel or the touch screen has been applied to various products. The protective film is simply attached to the surface of the display panel or the surface of the touch screen to easily protect the display panel or the touch screen from moisture or contaminants containing moisture.

As a conventional method of manufacturing a protective film, a method of manufacturing a thin film coated with a fluorine-based polymer on a polymer film by spraying or the like and a method of impregnating the fluorine-based polymer in a film to hydrophobize the film itself are mainly used. For example, Korean Patent Laid-Open Publication No. 2008-0073061 (2008. 08. 08 publication) discloses a technology for preventing contamination of a terminal by coating a desiccant made of a fluorine composition on a substrate of the terminal.

However, the conventional method of manufacturing a protective film in which a fluorine-based polymer is coated on a polymer film by spraying or impregnating a fluorine-based polymer in the film to make the film hydrophobic is up to 50 times higher than that of a general polymer film. There is a very high problem.

The present invention has been devised in view of this point, and an object of the present invention is to introduce a silane into a liquid phase reaction into a polymer film and then introduce fluorine into a gas phase reaction to improve surface hydrophobicity of the polymer film, thereby protecting the surface from moisture. An object of the present invention is to provide a functional fluorine-based polymer film and a method for producing the same.

Method for producing a functional fluorine-based polymer film according to the present invention for achieving the above object, (a) mixing the silane (silane), alcohol and silane polymerization catalyst, (b) the silane obtained through the step (a) Applying a silane to the surface of the polymer film by supporting the polymer film in a mixed solution, (c) irradiating microwaves to the polymer film to which the silane is applied through the step (b) to produce a silane on the surface of the polymer film. (D) introducing a fluorine element into the polymer film in which silane is introduced to the surface through step (c).

In the step (a), the silane is hexadecyltrimethoxysilane (Hexadecyltrimethoxysilane), trimethoxymethylsilane (Trimethoxymethylsilane), trimethoxy (propyl) silane (Trimethoxy (propyl) silane), trimethoxyhexylsilane (Trimethoxyhexylsilane ) And two or more thereof may be selected from the group consisting of mixed mixtures.

In the step (a), the alcohol is ethyl alcohol (CH ₃ CH ₂ OH), isopropyl alcohol ((CH ₃ ) ₂ CHOH), isoamyl alcohol ((CH ₃ ) ₂ CHCH ₂ CH ₂ OH), isobutyl alcohol ((CH ₃ ) ₂ CHCH ₂ OH), butyl alcohol (CH ₃ (CH ₂ ) ₃ OH), benzyl alcohol (C ₆ H ₅ CH ₂ OH) and selected from the group consisting of a mixture of two or more thereof Can be.

In the step (a), the silane polymerization catalyst is preferably a basic material having a weak basicity, and the basic material is ammonia (NH ₄ OH), cupric hydroxide (Cu (OH) ₂ ), and aniline (C). ₆ H ₅ NH ₂ ), alanine (CH ₃ CH (NH ₂ ) COOH), methylamine (CH ₃ NH ₂ ), pyridine (C ₅ H ₅ N), acetylacetone (C ₅ H ₈ O ₂ ) and among these Two or more may be selected from the group consisting of mixed mixtures.

The silane mixture solution prepared in step (a) preferably contains 5 to 10 parts by weight of the silane based on 100 parts by weight of the silane mixture solution.

The silane mixture solution prepared in step (a) preferably contains 0.5 to 1 parts by weight of the silane polymerization catalyst based on 100 parts by weight of the silane mixture solution.

In step (b), the supporting time of the polymer film is preferably 20 minutes to 40 minutes.

In the step (c), the microwave irradiation time for the polymer film is preferably 5 minutes to 30 minutes.

In the step (c), the microwave output is preferably 100W to 1000W.

In the step (d), the gas phase fluorination reaction temperature is preferably 25 ° C. to 70 ° C.

In step (d), fluorine gas may be supplied at a pressure of 0.05 to 1 bar to introduce fluorine element into the polymer film.

In the step (d), the gas phase fluorination reaction time is preferably 1 minute to 60 minutes.

The functional fluorine-based polymer film according to the present invention has a surface roughness suitable for showing surface hydrophobicity by introduction of silane and has a hydrophobic characteristic by introducing hydrophobic functional groups on the surface by introduction of fluorine, thereby exhibiting a protective function against moisture and the like. However, even dirt and contaminants that contain moisture can be easily removed.

In addition, the functional fluorine-based polymer film according to the present invention can be produced at a lower cost than the conventional hydrophobic polymer film by introducing silane through the liquid phase reaction and microwave irradiation, fluorine is introduced through the gas phase fluorination reaction.

In the conventional functional polymer film manufacturing method, a fluorine-based polymer is prepared and impregnated into a polymer to form a film, or a method of applying to the surface of the polymer film is mainly made, and the manufacturing cost thereof is high. However, the silane used in the present invention not only has a low cost of materials but also a gas phase fluorination reaction, which proceeds at room temperature or below room temperature as a dry process, and does not require additives or special catalysts. This can produce a polymer film having a similar level of function at a lower cost than the prior art.

1 is a process flow diagram showing a process for producing a functional fluorine-based polymer film according to the present invention.
Figure 2 shows the SEM image (a) of the PET film according to Example 1 of the present invention and the SEM image (a) of the PET film according to Comparative Example 1.

Hereinafter, with reference to the accompanying drawings, a functional fluorine-based polymer film according to the present invention and a manufacturing method thereof will be described in detail.

In describing the present invention, the sizes and shapes of the components shown in the drawings may be exaggerated or simplified for clarity and convenience of explanation. In addition, terms that are specifically defined in consideration of the configuration and operation of the present invention may vary depending on the intention or custom of the user or operator. These terms are to be construed in accordance with the meaning and concept consistent with the technical idea of the present invention based on the contents throughout the present specification.

The functional fluorine-based polymer film according to the present invention is prepared by introducing silane into a polymer film in a liquid phase reaction and then fluorinating the polymer film in a gas phase reaction. When silane is introduced into the polymer film, the surface roughness may be changed to be suitable for showing surface hydrophobicity. When fluorinated the polymer film, hydrophobic functional groups may be introduced to the surface of the polymer film to form a hydrophobic surface. Such a functional fluorine-based polymer film according to the present invention can be produced through the same process flow diagram shown in FIG.

Referring to the process flow diagram shown in Figure 1, the method for producing a functional fluorine-based polymer film according to the present invention comprises the steps of preparing a silane mixture solution (S10), coating the silane on the polymer film (S20), the silane is coated Microwave treatment (S30) of the polymer film, and fluorine treatment (Fluorination) of the polymer film into which the silane is introduced (S40).

The silane mixed solution is composed of silane, alcohol and silane polymerization catalyst. Silane is to change the roughness of the surface so that the polymer film is suitable for showing surface hydrophobicity, various organic compounds including a silane functional group may be used. For example, silanes include hexadecyltrimethoxysilane, trimethoxymethylsilane, trimethoxy (propyl) silane, trimethoxyhexylsilane, and among them. Two or more may be selected from the group consisting of mixed mixtures. Of course, the silane is not limited to this kind and various known ones can be used.

Alcohol is used as a solvent to dissolve the silane in the constituent materials of the silane mixture solution. As alcohol, various kinds of alcohols may be used, and ethyl alcohol (CH ₃ CH ₂ OH), isopropyl alcohol ((CH ₃ ) ₂ CHOH), isoamyl alcohol ((CH ₃ ) ₂ CHCH ₂ CH ₂ OH), isobutyl alcohol ((CH ₃ ) ₂ CHCH ₂ OH), butyl alcohol (CH ₃ (CH ₂ ) ₃ OH), benzyl alcohol (C ₆ H ₅ CH ₂ OH) and two or more of them are mixed It may be selected from the group consisting of a mixture. Of course, alcohol may be used in a variety of known other than these.

Of the constituent materials constituting the silane mixed solution, the silane polymerization catalyst plays a role in assisting the polymerization of the silane. As the silane polymerization catalyst, various kinds of basic materials having a weak base may be used. For example, ammonia (NH ₄ OH), cupric hydroxide (Cu (OH) ₂ ), and aniline (C ₆ H ₅ NH ₂ ), alanine (CH ₃ CH (NH ₂ ) COOH), methylamine (CH ₃ NH ₂ ), pyridine (C ₅ H ₅ N), acetylacetone (C ₅ H ₈ O ₂ ) and two or more of them It may be selected from the group consisting of a mixed mixture. In this invention, the kind of silane polymerization catalyst is not limited to what was mentioned above.

Looking at the specific constituent ratio of the silane mixture solution, the silane is preferably contained 5 to 10 parts by weight based on 100 parts by weight of the silane mixture solution. In the case of silane, when the content is less than 5 parts by weight, it is difficult to sufficiently coat the silane on the polymer film. When the content is more than 10 parts by weight, an excessive amount of silane is coated on the polymer film to reduce the transparency of the polymer film, and the coating thickness is not constant. Not preferred.

The silane polymerization catalyst is preferably contained 0.5 to 1 parts by weight based on 100 parts by weight of the silane mixture solution. In the case of the silane polymerization catalyst, if the content is less than 0.5 part by weight, the functionality as a catalyst is poor, and it does not help the polymerization reaction. If the content exceeds 1 part by weight, the upper limit, there is no profit. That is, when the silane polymerization catalyst is contained in an upper limit of 1 part by weight or more than that, the functionality as a catalyst is not significantly different.

Coating the silane on the polymer film (S20) may be performed through a process of supporting the polymer film in the silane mixture solution. The time for supporting the polymer film in the silane mixed solution is preferably 20 minutes to 40 minutes. When the supporting time is less than 20 minutes, the silane in the silane mixed solution does not sufficiently adhere to the surface of the polymer film, and when the upper limit exceeds 40 minutes, there is no profit. That is, the case where the polymer film is supported in the silane mixed solution for 40 minutes, which is the upper limit of the supporting time, or when the polymer film is supported for longer time or the coating amount of the silane is not significantly different.

Microwave treatment (S30) of the silane-coated polymer film (S30) may be performed through a process of irradiating the microwave (microwave) to the polymer film. Microwaves irradiated on the silane-coated polymer film radicalizes the surface of the polymer film to help polymerization of the silane.

The output of the microwave is preferably 100W to 1000W. When the output of the microwave is lower than the lower limit of 100W, the time required for reaching the radical reaction is increased, and the reaction does not occur sufficiently. When the output of the microwave exceeds the upper limit of 1000W, the polymer film may be damaged beyond the limit energy that the polymer film can withstand, which is not preferable.

In addition, the time for irradiating the microwave to the polymer film is preferably 5 minutes to 30 minutes. When the reaction time by microwave irradiation is less than 5 minutes which is a lower limit, silane will not fully introduce into the surface of a polymer film. In addition, if the reaction time exceeds the upper limit of 30 minutes, the polymer film may be exposed to high energy for a long time, and thus the polymer film may be damaged.

Fluorination of the polymer film into which the silane is introduced (S40) is performed by introducing a fluorine element into the polymer film through a vapor phase fluorination method. As is well known, the gas phase fluorination method is a method of introducing fluorine to the surface of an object by supplying fluorine gas into a reactor containing the object.

In the fluorine treatment step, the reaction temperature is preferably 25 ° C to 70 ° C. If the reaction temperature is lower than the lower limit of 25 ℃ fluorine is less reactive, fluorine is not sufficiently doped. When the reaction temperature exceeds 70 ° C, which is the upper limit, the reaction between the polymer film and fluorine occurs violently, which may damage the polymer film.

In addition, the gas injected into the reactor in the fluorine treatment step may be a fluorine gas or a mixed gas of fluorine gas and inert gas. The fluorine gas may be any gas that contains fluorine, and examples thereof include fluorine (F ₂ ), nitrogen trifluoride (NF ₃ ), carbon tetrafluoride (CF ₄ ), and carbon trifluoride (CHF _3). ), Trifluorofluorocarbons (C ₃ F ₈ ), tetrafluorocarbons (C ₄ F ₈ ) and mixtures thereof, but is not necessarily limited thereto.

When fluorine gas is used alone, the fluorine gas is preferably in a pressure range of 0.05 to 1 bar, and when a mixed gas of fluorine gas and inert gas is used, the partial pressure of fluorine gas is preferably in the range of 0.05 to 1 bar.

If the pressure of the fluorine gas or the partial pressure of the fluorine gas is less than the lower limit, the reactivity is poor and the fluorine is not sufficiently doped. If the pressure or the partial pressure of the fluorine gas exceeds the upper limit, the reaction between the polymer film and the fluorine occurs violently. This is undesirable because it can be damaged.

In addition, the reaction time in the fluorine treatment step is preferably 1 minute to 60 minutes. When reaction time is less than 1 minute which is a lower limit, fluorine will not fully be introduced. When the reaction time exceeds the upper limit of 60 minutes, the reaction between the polymer film and fluorine occurs violently, which may damage the polymer film.

In the following, the present invention will be described based on Examples.

The following examples are merely illustrative of the present invention, the present invention is not limited to the examples.

Example  1: Preparation of functional fluorine-based polymer film 1

Polyethylene terephthalate (hereinafter referred to as 'PET') as a polymer film, trimethoxy (propyl) silane as silane, methanol (CH ₃ OH) as solvent, ammonia (NH ₄ as catalyst) OH), fluorine (F ₂ ) and nitrogen (N ₂ ) were selected as gases.

First, a 5 wt% trimethoxy (propyl) silane solution was prepared using methanol as a solvent, and 0.5 g of ammonia was added to prepare a silane mixed solution. Next, the PET film was supported for 30 minutes in the prepared silane mixture solution. Next, the supported PET film was irradiated with microwave at 700 W for 10 minutes to introduce silane into the PET film surface. Next, a fluorine element was introduced into the PET film using a fluorination reactor with a total pressure of 0.5 bar and a nitrogen to fluorine pressure ratio of 7: 3. At this time, the reaction temperature was maintained at 25 ℃, the reaction time was 30 minutes. Through this process, the PET film finally introduced with silane and fluorine was prepared.

Example  2: Preparation of functional fluorine-based polymer film 2

The same process as in Example 1 was performed, but finally, a silane and fluorine-introduced PET film was prepared using a pressure ratio of nitrogen to fluorine of 9: 1 in the fluorine treatment process.

Example 3 Preparation of Functional Fluoropolymer Film 3

The same process as in Example 1 was carried out, but the final silane and fluorine-introduced PET film was prepared using a silane content of 1wt%.

Comparative Example  One

A comparative example was selected for comparison with the above examples. Comparative Example 1 was selected as a PET film not treated.

Surface Chemical Composition Analysis

In order to confirm the surface chemical composition of the PET film according to Example 1 and Comparative Example 1, each of them was analyzed using an X-ray photoelectron spectroscopy (XPS). Surface composition results of the PET film according to Example 1 and Comparative Example 1 are as shown in Table 1 below.

Elemental composition of Table 1 shows the element ratio of the measured sample surface. Comparative Example 1 is the surface chemical composition ratio of the PET film not treated at all, and Example 1 shows the surface chemical composition ratio changed by silane introduction using a liquid phase reaction and fluorine introduction using a gas phase reaction in the PET film. The surface chemical composition ratio of Example 1 was smaller than that of Comparative Example 1, and the ratio of fluorine was increased. This analysis confirms the introduction of fluorine functional groups that impart hydrophobic properties to the PET film surface.

Contact angle  Measurement analysis

In order to compare the surface contact angle of the PET film according to the above examples and comparative examples, a drop of distilled water was applied to the PET film and the contact angle with the PET film was measured. Specifically, the contact angle measurement was applied on the film so that the diameter of the distilled water drops to 1mm using a microsyringe on a PET film of 2cm × 2cm size. As soon as the droplets of distilled water were applied to the PET film surface and reached equilibrium, an image system captured the contact angle image of the enlarged PET film surface and the droplets applied thereto. The contact angle in the captured image was calculated by the measurement program and measured so that the error between left and right angles was less than 1.5 (degree).

Measurement results for the surface contact angle is shown in Table 2 below.

Looking at Table 1, the average surface contact angle of the PET film (Comparative Example 1) in which no surface treatment was performed in the case of PET film (Examples 1 to 4) to which the present invention was applied was 52.72 ° to 87.97 °. It can be seen that it is larger than 47.47 °. The smaller the surface contact angle is, the higher the hydrophilic property is, and the larger the surface contact angle is, the higher the hydrophobic property is. Thus, the PET film to which the present invention is applied can be confirmed that the hydrophobic property is higher than that of the conventional PET film.

SEM ( Scanning Electron Microscopy ) analysis

2 (a) is an SEM image of the PET film according to Example 1 of the present invention, Figure 2 (b) is an SEM image of the PET film according to Comparative Example 1. Looking at Figure 2, in Comparative Example 1, a relatively smooth surface can be seen with the naked eye. However, in the case of Example 1 it can be seen that the surface is not smooth and agglomerated material is spread widely over the surface. As a result, it can be visually confirmed that the process of introducing silane using the liquid phase reaction and microwave irradiation on the PET film surface according to Example 1 was successful. This indicates that a film surface suitable for exhibiting surface hydrophobicity was formed by introducing silane to roughen the smooth surface.

As described above, the functional fluorine-based polymer film according to the present invention has excellent hydrophobicity and can be manufactured at low cost, compared to a conventional polymer film, and can be manufactured in various types of flat panel display panels, touch screens, or other devices that must avoid moisture. It can be used as a protective film.

The embodiments of the present invention described above and shown in the drawings should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters described in the claims, and those skilled in the art can improve and modify the technical idea of the present invention in various forms. Accordingly, these modifications and variations are intended to fall within the scope of the present invention as long as it is obvious to those skilled in the art.

Claims (14)

(a) mixing silane, alcohol and silane polymerization catalyst;
(b) applying a silane to the surface of the polymer film by supporting the polymer film in the silane mixed solution obtained through the step (a);
(c) irradiating microwaves to the polymer film to which the silane is applied through step (b) to introduce silane to the surface of the polymer film; And
(d) introducing a fluorine element into the polymer film into which the silane is introduced into the surface through step (c) by a gas phase fluorination method.
The method of claim 1,
In the step (a), the silane is hexadecyltrimethoxysilane (Hexadecyltrimethoxysilane), trimethoxymethylsilane (Trimethoxymethylsilane), trimethoxy (propyl) silane (Trimethoxy (propyl) silane), trimethoxyhexylsilane (Trimethoxyhexylsilane ) And a method of producing a functional fluorine-based polymer film, characterized in that selected from the group consisting of a mixture of two or more thereof.
The method of claim 1,
In the step (a), the alcohol is ethyl alcohol (CH ₃ CH ₂ OH), isopropyl alcohol ((CH ₃ ) ₂ CHOH), isoamyl alcohol ((CH ₃ ) ₂ CHCH ₂ CH ₂ OH), isobutyl alcohol ((CH ₃ ) ₂ CHCH ₂ OH), butyl alcohol (CH ₃ (CH ₂ ) ₃ OH), benzyl alcohol (C ₆ H ₅ CH ₂ OH) and selected from the group consisting of a mixture of two or more thereof Method for producing a functional fluorine-based polymer film, characterized in that.
The method of claim 1,
In the step (a), the silane polymerization catalyst is ammonia (NH ₄ OH), cupric hydroxide (Cu (OH) ₂ ), aniline (C ₆ H ₅ NH ₂ ), alanine (CH ₃ CH (NH ₂₎ ) COOH), methylamine (CH ₃ NH ₂ ), pyridine (C ₅ H ₅ N), acetylacetone (C ₅ H ₈ O ₂ ) and selected from the group consisting of a mixture of two or more thereof Method for producing a functional fluorine-based polymer film.
delete The method of claim 1,
Method for producing a functional fluorine-based polymer film, characterized in that the silane mixture solution prepared in step (a) contains 5 to 10 parts by weight of the silane based on 100 parts by weight of the silane mixture solution.
7. The method according to claim 1 or 6,
Method for producing a functional fluorine-based polymer film, characterized in that the silane mixture solution prepared in step (a) contains 0.5 to 1 parts by weight of the silane polymerization catalyst based on 100 parts by weight of the silane mixture solution.
The method of claim 1,
In step (b), the supporting time of the polymer film is a manufacturing method of the functional fluorine-based polymer film, characterized in that 20 to 40 minutes.
The method of claim 1,
The microwave irradiation time for the polymer film in the step (c) is a method for producing a functional fluorine-based polymer film, characterized in that 5 minutes to 30 minutes.
The method of claim 1,
Microwave output in the step (c) is a method for producing a functional fluorine-based polymer film, characterized in that 100W to 1000W.
The method of claim 1,
The vapor phase fluorination reaction temperature in the step (d) is a method for producing a functional fluorine-based polymer film, characterized in that 25 ℃ to 70 ℃.
The method of claim 1,
Gas phase fluorination in the step (d) is a method of producing a functional fluorine-based polymer film, characterized in that the pressure of the fluorine gas is made in the range of 0.05 to 1 bar.
The method of claim 1,
Gas phase fluorination reaction time in the step (d) is a method for producing a functional fluorine-based polymer film, characterized in that 1 to 60 minutes.
delete

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