JPH101553A - Preparation of stainproof plastic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a coating film having functions such as water repellency and stainproofness on the surface of a plastic film in high productivity by continuously vapor-depositing a specified reactive organic compound on the film by the high-frequency plasma CVD method. SOLUTION: A reactive organic perfluoro compound is vapor-deposited by reaction on a continuously running plastic film at a power of high-frequency of 10-50w in a high-frequency plasma CVD continuous processing apparatus. The above apparatus consists of (a) vacuum system (a vacuum pump 2 and a vacuum container 1), (b) a film carrying system (a film delivery roll system 3, a film running zone in which CVD vapor deposition on the surface of the running film delivered, and a take-up roll system 4 around which the vapor- deposited film is wound); (c) a plasma deposition system (a plasma generator 6 and a plasma generating zone adjoining to a film running zone b); and a material feeding system (a heatable container 7 for the reactive organic compound, and a pipe for introducing a vapor of the compound from the container 7 into the plasma generating zone c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of continuously forming a film of an organic compound having a specific function such as water repellency and antifouling property on the surface of a plastic film by a CVD (chemical vapor deposit) method. And a method for producing an antifouling plastic film. The present invention relates to a method for continuously forming a film of an organic compound having a specific function such as water repellency and antifouling property on a surface of an antireflection processed plastic film using a thin film.

[0002]

2. Description of the Related Art In an optical element having an anti-reflection process comprising a single-layer or multi-layer thin film, reflection interference occurs due to whitening (drainage) caused by contact with water containing impurities and oily dirt. There is a disadvantage that a color change occurs.

On the other hand, JP-A-6-122776 and JP-A-6-222776
In 122778, a low surface energy substance is vaporized, introduced into a decompression processing chamber containing an object to be processed with an antireflection layer such as glasses or lenses, and brought into contact with the surface of the object to be processed under a plasma atmosphere. A surface treatment method for forming a low surface energy film on the surface of an object to be treated and an apparatus therefor have been proposed.

[0004]

However, in this example, the object to be processed is a molded article such as a lens, and the productivity is low because it is applied in a batch system.

An object of the present invention is to solve the above-mentioned conventional problems. A film of an organic compound having a specific function, particularly water repellency, is formed by a high-frequency plasma CVD method.
A method for forming an antifouling layer of a plastic film, preferably an antireflection plastic film, which has high productivity by continuously applying a functional film such as antifouling property to the film surface and has high quality. It is about.

[0006]

According to the present inventors' earnest studies, the above object of the present invention has been industrially advantageously achieved by the present invention having the following constitution.

[1] A high-frequency plasma CVD (chemical vapor deposit) continuous processing apparatus comprising the following apparatus components as components, and a high-frequency output of 10 to
A method for producing an antifouling plastic film, wherein a reactive organic compound containing a perfluoro group is reactively vapor-deposited on a continuously running plastic film at 50 w to form an organic compound film continuously.

(A) Vacuum system (vacuum pump and vacuum vessel) (b) Film transport system (film running area in which CVD deposition can be performed on a film surface that runs out from a film feeding roll system and a continuous feeding roll system) (C) Plasma deposition system (high-frequency plasma generator and plasma generation region adjacent to film traveling region (b)) (d) Material supply system ( A heatable container filled with a reactive organic compound containing a perfluoro group capable of forming an organic compound film by plasma polymerization, and vaporization of the reactive organic compound from the container to generate plasma inside a vacuum system (a) (Piping device to be introduced into region (c)) [2] The traveling speed of the plastic film is 1 to 50 m
/ Min, the method for producing an antifouling plastic film according to the above [1].

[3] The above-mentioned [1], wherein the introduction direction of the reactive organic compound containing a perfluoro group is at an angle of 0 ° to 45 ° from the running direction of the film.
Alternatively, the method for producing an antifouling plastic film according to the above [2].

[4] The above-mentioned [1] to [3], wherein an anti-reflection process using a multilayer thin film is performed, and an organic compound film is continuously formed on the surface on which the anti-reflection process is performed. The method for producing an antifouling plastic film according to any one of the above.

[5] An organic compound film is continuously formed on a surface on which antireflection processing has been performed on a single-layer or multilayer antireflection processing plastic film made of a thin film made of silicon oxide. The method for producing an antifouling plastic film according to the above [4], which is characterized in that:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.

An object of the present invention is to produce a thin film having anti-fouling properties such as water repellency and oil repellency. If the contact angle of water is 90 ° or more, the thin film is effective for this purpose. Also, when wiping 24 hours after applying oily magic,
If it can be wiped with 0 stroke or less, it can be said that it has good oil repellency.

The plastic film used in the present invention is not particularly limited as long as it is made of an organic polymer. However, a plastic film having transparency, shape retention and durability is desirable. Ether resin, polymethacrylic acid resin, polyester resin, unsaturated polyester resin, polycarbonate resin, polysulfone resin, polyamide resin, polyimide resin, maleimide resin, polysulfide resin, epoxy resin, melamine resin Examples of the film include a resin, a phenol resin, a diallyl phthalate resin, a polyphosphazene resin, a cellulose resin, and a polyurethane resin. A polyester resin film, particularly a polyethylene terephthalate film or a polycarbonate resin film, is preferably used in terms of cost and performance. In addition, a uniaxially stretched film, for example, a triacetyl cellulose film is preferable in that there is no optical anisotropy.

The equipment required to realize the process will be described with reference to FIG.

The vacuum system comprises a vacuum vessel 1 and a vacuum pump system 2 for adjusting the pressure to a required reduced pressure. The vacuum pump system is constituted by a vacuum pump such as a rotary pump, a mechanical booster pump, a diffusion pump, and a cryopump in order to create and maintain a required reduced pressure state. At this time, it is desirable to use a plurality of pumps having different decompression abilities in appropriate combination in series and in parallel in order to improve the pumping speed and maintain a good decompression state.

Further, the vacuum vessel has a processing pressure of 6-1.
A range of 0 × 10 ⁻⁴ Torr is suitable for obtaining antifouling properties, and a range of 7 to 9 × 10 ⁻⁴ Torr is more preferable. 6x
At a pressure of less than 10 ^-4 Torr, the glow discharge plasma discharge becomes unstable, and the contact angle of water is reduced or unevenness occurs. If the pressure exceeds 10 × 10 ⁻⁴ Torr, the contact angle of water and the wiping property are reduced, and it is not preferable because sufficient antifouling performance cannot be expected. .

The film transport system includes a film feeding roll system 3, a film running region where CVD deposition can be continuously performed on the film surface, and a CVD system in the film running region.
It is constituted by a take-up roll system 4 of a deposited film. The film to be subjected to the surface processing is set in a feeding roll system while being wound on a roll. The film continuously fed from this is guided to a film running area, is CVD-deposited on one side facing the plasma deposition system adjacent thereto, and is continuously wound by a take-up roll system. The winding direction is preferably such that the deposition surface is on the outside because curling can be reduced and handling properties in the subsequent process and product yield can be improved.

The running speed of the film is 1 to 50 m / mi.
The range of n is preferable from the viewpoint of achieving both productivity and antifouling performance. When this is converted into the time actually deposited by the deposition system (the time required to pass through the deposition system), 45.6 to
0.9 seconds. 2-30 m / min, 2
More preferably, it is set to 2.8 to 1.52 seconds. 50 m
If it exceeds / min, the glow discharge plasma becomes unstable and the antifouling property is lowered, which is not preferable. Also, 1 m
If it is less than / min, high productivity cannot be expected, which is not preferable.

Further, in order to prevent the organic compound serving as the material of the coating from going to the back of the film, the unwinding / winding system and the film forming region (the region consisting of the film traveling system and the plasma deposition system) are provided with barriers. It is preferable that the chamber is substantially divided into two chambers, an upper chamber and a lower chamber. Further, it is more preferable that the barrier 9 is provided in two stages to exhaust each gas to prevent the gas from flowing around.

The plasma deposition system includes a high-frequency plasma generator 6 and a plasma generation region adjacent to the film running region. Further, in order to stabilize the glow discharge plasma, it is preferable to use the glow discharge plasma gas concentration box 8. Here, an organic compound simple substance serving as a material of the coating is supplied from a material supply system, and activated by plasma to form an organic compound coating.

The high frequency output of the plasma generator is 10 to 5
An output range as low as 0 w is suitable for achieving both productivity and antifouling property. Further, the range of 25 to 35 w is more preferable. If it is less than 10 w, the glow discharge plasma becomes unstable and the film cannot be formed uniformly, and if it exceeds 50 w, the contact angle of water and the wiping performance are reduced, so that it is not preferable because sufficient antifouling performance cannot be expected.

As a power source for generating plasma, high frequency (0.1 MHz to 1 G) is used in terms of uniformity and stability of glow discharge.
Hz) is preferred. Further, 13.56 MHz is most preferable in consideration of compatibility with film damage.
It is preferable to use a rectangular electrode rather than a round plasma electrode because the uniformity of the antifouling performance in the width direction is good.
Further, at the time of vapor deposition, it is preferable to maintain the temperature of the film serving as the substrate for film formation at 30 ° C. or higher, since the contact angle of water is improved and high antifouling performance is obtained.

The material supply system is composed of a heatable container 7 filled with an organic compound, and a piping device for vaporizing the organic compound from the container and introducing it to the plasma generation region.
After filling the organic compound, it is vaporized by decompression and heating, and is led to a plasma deposition system through a pipe that can be heated and kept warm.

When introduced into the plasma deposition system, the direction of gas flow is 0 deg (parallel) from the film transport direction.
If the angle is set to 45 ° from the angle, the uniformity is improved. More preferably, the temperature is set to 0 deg.

The film to be deposited is a continuous long plastic film, and preferably has at least one surface subjected to antireflection processing using a single-layer or multilayer thin film. Here, the antireflection film is a film in which an antireflection layer is formed by a method such as vacuum evaporation, sputtering, or ion plating on a plastic film to which a hard coat layer has been previously provided. Here, the method of applying is not limited to the above method as long as it is a dry process. In the present invention, a dry process without degassing in a vacuum is suitable in terms of processing stability. The outermost layer is made of a metal, a metal compound, or an oxide. In particular, when silicon oxide is used, a reaction occurs with an organic compound used for film formation, and adhesion strength and stability after formation of the antifouling layer are improved, which is preferable in terms of mechanical properties. Further, a protective film is preferably provided on the back surface in order to prevent the organic compound alone from turning around and blocking.

The organic compound has a vapor pressure sufficient to vaporize and evaporate under reduced pressure and form a polymer film which is activated in a glow discharge atmosphere and reacts with the substrate being transported to increase the density. It is a compound that can be formed, and as such a compound, a compound group having various reactive groups such as an epoxy group, an amino group, a vinyl group, and an alkoxyl group, and a group of compounds referred to as an alkylsilane or a fluoroalkylsilane-based silane coupling agent is preferable. Used. Such compounds include heptadecafluoro-1,1,2,2-
Tetrahydrodecyltrimethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrotrichlorosilane, octafluorocyclobutane, perfluoromethylcyclohexane, perfluoro-n-hexane, perfluoro-n-heptane, tetradecafluoro -2-
Methylpentane, perfluorododecane, perfluoroeicosane, perfluorodecanoic acid, perfluorooctanoic acid, 3,3,4,4,5,5,5-heptafluoro-2-pentanol, heptadecafluoro-1, 1,
2,2-tetrahydrodecylamine and the like.

The thickness of the coating depends on the heating temperature of the supply system,
It is controlled by the flow rate and film transport speed.
At this time, it is preferable to control the film thickness to several tens angstroms, since the optical characteristics of the antireflection film of the substrate are not hindered.

[0029]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, each characteristic value in a specification, an Example, and a comparative example was measured according to the following method.

The contact angle of water is determined by F of Kyowa Interface Science Co., Ltd.
It was determined by a droplet method using an ACE contact angle meter.

For the magic wiping property, a hydraulic felt pen (black, red) manufactured by Pentel Co., Ltd. is used. This was applied to the antifouling layer, and after 24 hours, the applied layer was wiped off with an emergency cotton manufactured by White Cross Co., Ltd., and the number of times until it was wiped off was determined.

Example 1 thickness 188 μm, width 50c
A hard coat layer having a thickness of 4 μm was provided on one side of a PET film having a length of 100 m and a length of 100 m, and a film was further prepared on which an antireflection film having the following configuration was formed.

First layer: ITO, second layer: SiO ₂ , third layer:
ITO, fourth layer: SiO ₂ The thickness of each layer consists of an optical thickness designed and calculated optically. Also, in the wavelength range of visible light, it has high antireflection performance with an average reflectance of 1% or less. The contact angle of water on the antireflection surface before the antifouling treatment is 30 deg, the number of strokes until the magic is wiped off is 50 times or more, and the antifouling performance is extremely low.

Using the high-frequency plasma CVD (chemical vapor deposition) continuous processing apparatus shown in FIG. 1, a film made of a perfluoroalkylsilane condensate having a thickness of about 15 angstroms was formed on the antireflection surface under the following conditions. .

Organic compound: (Heptadecafluoro-1,1,2,2
-Tetrahydrodecyl) -1-1-trimethoxysilane Processing pressure: An organic compound is introduced after the vacuum vessel has reached 4 × 10 ⁻⁵ Torr, and 7 × 10 ^{−4 in a} steady state during high-frequency CVD film formation. Maintain Torr High frequency power frequency: 13.56 MHz High frequency output: 30 w Film running speed: 6 m / min Heating temperature of heatable container filled with organic compound: 95
° C Organic compound gas inflow direction: 0 deg (parallel) At this time, the formed polymer film exhibited the following good antifouling performance.

Water contact angle: 106 deg. Number of strokes until magic is wiped off: 3 times (average of N number 10) Area that can be formed in one batch: 50 m ² Also, before and after film formation, the reflectance and the No difference was found in the spectral characteristics.

Comparative Example 1 A film was formed under the same conditions as in Example 1 except that only the high-frequency output was 60 watts, which was larger than the range of the present invention. The polymer film formed at this time had a low contact angle as described below, and the magic was difficult to wipe off. Water contact angle: 103 deg Number of strokes until magic is wiped: 13 times (N
Average of number 10)

[0038]

According to the method of the present invention, an antifouling plastic film having the following performance can be obtained with high productivity.

(1) The contact angle is 100 deg or more. (2) The number of times of magic wiping is 10 or less. (3) The reflectance of the antireflection film as the substrate is not affected.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing an example of a high-frequency plasma CVD (chemical vapor deposit) continuous processing apparatus used in the present invention.

[Explanation of symbols]

 1: Vacuum container 2: Vacuum pump system 3: Feed-out roll system 4: Take-up roll system 5: Carrier roll 6: High-frequency plasma generator 7: Heatable container filled with organic compounds 8: Glow discharge plasma densely packed box 9: barrier

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shunroku Toyama 33-1, Nagafushi, Mishima-shi, Shizuoka Toyo Metallizing Co., Ltd. Mishima Plant

Claims (5)

[Claims] 1. A high-frequency plasma CVD (chemical vapor deposition) continuous processing apparatus comprising the following apparatus components as components, and a high-frequency output of 10 to 50:
w as a plastic film running continuously,
A method for producing an antifouling plastic film, comprising continuously forming an organic compound film by reactive vapor deposition of a reactive organic compound containing a perfluoro group. (a) Vacuum system (vacuum pump and vacuum vessel) (b) Film transport system (film feeding area, film running area where CVD deposition can be performed on the film surface that is continuously fed from the feeding roll system, and film) (C) Plasma deposition system (high-frequency plasma generator and plasma generation region adjacent to film traveling region (b)) (d) Material supply system (by plasma polymerization) A heatable container filled with a reactive organic compound containing a perfluoro group capable of forming an organic compound film, and the reactive organic compound is vaporized from the container to form a plasma generation region (c) inside a vacuum system (a). ) Piping equipment to be introduced) 2. The traveling speed of the plastic film is 1 to 5
2. The method for producing an antifouling plastic film according to claim 1, wherein the rate is 0 m / min. 3. The direction of introduction of the reactive organic compound containing a perfluoro group is from 0 ° to 45 ° from the running direction of the film.
3. The method for producing an antifouling plastic film according to claim 1, wherein the angle is deg. 4. A continuously running plastic film having at least one surface subjected to anti-reflection processing by a single-layer or multi-layer thin film, and continuously forming an organic compound film on the surface subjected to the anti-reflection processing. The method for producing an antifouling plastic film according to any one of claims 1 to 3, wherein: 5. An organic compound film is continuously formed on an antireflection-treated surface of a plastic film which has been subjected to a single-layer or multi-layer antireflection treatment with a thin film whose outermost layer is made of silicon oxide. 5. The method according to claim 4, wherein
The method for producing the antifouling plastic film described in the above.