JP2622316B2 - Water / oil repellent film and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water- and oil-repellent film,
It relates to the manufacturing method . More specifically, a water- and oil-repellent film in which a fluorocarbon-based water- and oil-repellent monomolecular film is formed on an irregularly roughened surface using a sandblasting method, a mold contact method, and an etching method, and a method for producing the same <br/>

[0002]

2. Description of the Related Art Water-repellent and oil-repellent films are useful for attaching to glass windows of high-rise buildings and vehicles, and for covering films on surfaces of electric appliances, automobiles, industrial equipment and the like.

Conventionally, a method of manufacturing a coating film which has been widely used for the purpose of water and oil repellency is generally based on Al.
(Aluminum) Roughen the surface of the substrate etc. with a wire brush or chemical etching, apply a primer, etc., apply a paint in which fine particles of fluorocarbon such as polytetrafluoroethylene are suspended in ethanol, etc., and dry , About 4
A method has been used in which a heat treatment is performed at about 00 ° C. for about one hour and a fluorocarbon-based polymer is baked on the substrate surface.

[0004]

However, although the above-mentioned prior art is easy to manufacture, the polymer and the substrate are merely bonded by the anchor effect only, so that the adhesion to the substrate is limited, Further, the surface of the coating film was subjected to a high-temperature heat treatment at about 400 ° C., so that the surface was flattened, and a good water- and oil-repellent surface could not be obtained. Also, coating on a plastic film or the like was impossible. Therefore, it is insufficient as a method for manufacturing a device that requires a water-repellent and oil-repellent coating film such as an electric appliance, an automobile, and an industrial device, which is attached to a glass window of a high-rise building or a vehicle. As another method, there is a means of applying a fluorocarbon polymer coating material, but there is a limit in the adhesion to the substrate because the polymer and the substrate are simply bonded only by the anchor effect.

In order to solve the above-mentioned problems of the prior art, the present invention provides a film with good adhesion and no pinholes.
A water- and oil-repellent film having a coating film that is excellent in water- and oil-repellency, heat resistance, weather resistance, and abrasion resistance, and the same.
It is intended to provide a manufacturing method .

[0006]

In order to achieve the above object, a water- and oil-repellent film of the present invention has a roughened surface.
On the surface of the film that has been treated and contains OH groups on the surface.
Is a residue of the OH group.
Is fixed by a siloxane bond via O.

In the above structure, it is preferable that the roughness of the roughened surface of the film is not more than 0.3 μm. Further, in the above configuration, it is preferable that the material of the film is a polyethylene terephthalate resin or a polyethylene trifluoride chloride resin.

Further, in the above structure, it is preferable that an adhesive is applied to the back surface of the film. Next, the first method for producing a water- and oil-repellent film of the present invention comprises the steps of: applying a chlorosilyl group at one end to the surface of a film whose surface is roughened to have irregularities on the order of submicron to micron order and having an OH group on the surface; By contacting a chlorosilane compound having a fluorocarbon group at the other end with a dehydrochlorination reaction, a water- and oil-repellent chemically adsorbed monomolecular film fixed via a siloxane bond on the surface of the film is formed. It is characterized by forming. Next, the second method for producing a water- and oil-repellent film of the present invention is characterized in that a plurality of chloro groups are added to the surface of the film whose surface is roughened to have irregularities of the order of submicron to micron and which contains OH groups on the surface. A silanol compound is contacted to form a chemically adsorbed film containing a silanol group on the surface of the film, followed by a chlorosilane having a chlorosilyl group at one end and a fluorocarbon group at the other end. It is characterized in that a water- and oil-repellent chemically adsorbed monomolecular film fixed via a siloxane bond on the surface of a silanol group-containing chemically adsorbed film is formed by contacting a system compound to cause a dehydrochlorination reaction.

[0009]

According to the structure of the present invention, the surface of the film is roughened to have a rough surface, and a chemically adsorbed monomolecular film containing fluorine is formed on the surface of the film through siloxane bonds. A water- and oil-repellent film with a coating film that has excellent adhesion and no pinholes, has excellent water and oil repellency, and is also excellent in heat resistance, weather resistance, and abrasion resistance despite being a fluorine-based coating film. it can.

According to the preferred structure of the present invention, in which the roughness of the surface of the roughened film is 0.3 μm or less, the film has excellent light transmittance and light transmittance in the visible light region of the film. It does not hinder the properties.

Further, according to the preferred structure of the present invention in which the material of the film is polyethylene terephthalate resin or polyethylene trifluoride chloride resin, preferable quality characteristics as a cover film or a protective film can be exhibited.

Further, according to the preferred structure of the present invention in which an adhesive is applied to the back surface of the film, the film can be easily attached to the substrate to be attached. Further, according to the first and second manufacturing methods of the present invention, the water / oil repellent film of the present invention can be efficiently and rationally manufactured.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The water- and oil-repellent film of the present invention can be applied to a substrate such as a window glass, a windshield, an eyeglass lens, a building window glass, a sanitary ware, a tableware, a vase, an aquarium. And ceramic products, such as sashes, metal products such as outer walls of door buildings, and films for furniture and covers. In addition, as a film material,
Examples include a fluororesin film such as trifluorinated polyethylene, a polyester film such as polyethylene terephthalate, a polyimide film, a polyamide film such as nylon, a polyethylene film and a polypropylene film.

An example of a fluorocarbon surfactant which can be used in the present invention is CF ₃ (CF ₂ ).
₇ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ (CH
₂ ) ₂ SiCl ₃ , CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiC
l ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₁₅ SiCl ₃ , F (CF ₂ ) ₄ (CH ₂ ) ₂ Si (CH
₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ , F (CF ₂ ) ₈ (CH
₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ , CF
₃ COO (CH ₂ ) ₁₅ SiCl _{3 and the} like. If a vinylene group or an ethynylene group is added to or incorporated in an alkyl chain portion, it can be cross-linked by electron beam irradiation of about 5 megarads after forming a monomolecular film, so that the hardness is further increased. Can also be improved.

[0015] In the present invention, advance the film surface or etched uneven in the sub-micron to micron order, the steps of roughened by sandblasting and types rely method, one end Kurorushi lil group (SiCl _n X _3-n Group, n =
1, 2, 3, and X are functional groups), and a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end is chemically adsorbed on the film surface to form a monomolecular adsorption film. Thus, a fluorocarbon-based chemically adsorbed monomolecular film having an extremely high water / oil repellency on the surface can be produced.

Further, following the step of roughening the surface of the film by etching or roughening the surface of the film in the order of sub-micron to micron , a plurality of chloro groups are formed.
A step of depositing said material on the surface of the film in contact with a non-aqueous solvent mixed with silyl compound number comprising reacting the chlorosilyl group of a hydroxyl group and the silyl compound of the film surface, the use of a non-aqueous organic solvent after remaining the excess silyl compounds were washed away on the film, inserting the step of reacting with water, forming a monomolecular film made of material containing a plurality of silanol groups on the film surface, Kurorushi drill at one end Group (SiCl _n X _3-n group, n =
(1, 2, 3, and X are functional groups) and a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end is chemically adsorbed on the film surface to accumulate a monomolecular adsorption film. Thus, a fluorocarbon-based chemisorption monomolecular film having a higher molecular adsorption density can be produced.

The rough surface roughness of the film surface is preferably on the order of submicron to micron, that is, 0.3 micron or less. In this case, the film has excellent light transmittance and the light transmittance in the visible light region of the film is improved. There is no hindrance. If the roughness of the film surface is more than 0.3 micron, the water and oil repellency is not affected and the optical properties are slightly lowered, but there is no problem depending on the application. For example, when providing characteristics such as a light-shielding film or frosted glass, it is preferable that the rough surface is considerably rough.

If an adhesive is applied to the back surface of the film, it can be easily attached to the substrate to be attached without affecting the optical characteristics. Note that a release sheet may be present on the surface of the adhesive.

A specific embodiment will be described below. In the following examples, what is simply indicated as% is wt%.
Means Example 1 As shown in FIG. 1, a fluorinated polyethylene film 1 having a thickness of 100 to 200 μm (μm) was prepared, and kept at 10 ^{−1 to} 10 ⁻² Pa in a vacuum chamber. Sputter etching is performed in a plasma atmosphere by an RF glow discharge containing oxygen, for example, treatment is performed at a discharge power density of 0.15 W / cm ₂ for 1 to 10 minutes to form irregularities on the surface. At this time, the surface roughness was about 0.1
There was no devitrification in the film (about 1 micron) (FIG. 1 (a)). (Actually, if it is 0.3 micron or less, it is sufficiently smaller than the wavelength of visible light, so that it does not devitrify. Conditions can be selected as appropriate). Next, a nonaqueous mixed with material containing fluorocarbon groups and Kuroroshi Lil group solvent, for example, using the following (Formula 1), Afurudo dissolved at a concentration of about 5% (by Asahi Glass fluorine-based solvent) solution It was adjusted.

[0020]

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When the roughened film is immersed in a conditioning solution for about 1 hour, the film is etched by oxygen plasma, and a hydroxyl group (OH) is formed on the surface. The following bond (Formula 2) was formed on the surface, and the monomolecular film 2 containing fluorine was formed along the irregularities in a state of being chemically bonded.

[0022]

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The monomolecular film did not peel at all even when the cross test was performed. Here, FIG.
FIG. 2 is an enlarged schematic view of a portion A in FIG. In this case, since the fluorocarbon group was formed on the surface in an oriented state, the surface energy was extremely low, and the wetting angle to water was 135 to 145 degrees.

Example 2 For example, a polyethylene terephthalate film 11 is prepared and kept at 10 ^{-1 to} 10 ^-2 Pa in a vacuum chamber, and its surface is sputter-etched in a plasma atmosphere by RF glow discharge containing oxygen in advance. For example, a treatment is performed at a discharge power density of 0.1 W / cm ² for 1 to 5 minutes to form irregularities on the surface. At this time, the surface roughness was about 0.1
It was on the order of microns and the film did not devitrify. Actually, if the thickness is 0.3 μm or less, no devitrification occurs, so that the etching conditions may be appropriately selected. In the case of a film that does not require transparency, a rough surface processing of about several tens of microns was sufficiently effective.

Next, a reagent that contains a large number of Kuroroshi Lil group,
For example, SiCl ₄ (SiHCl ₃ , SiH ₂ Cl ₂ ,
_{Cl- (SiCl 2 O) n -SiCl} 3 (n is an integer))
(Asahi glass-based fluorine-based solvent) solution prepared by dissolving the solution at a concentration of about 5%, and immersing the roughened film for about 1 hour, the film is etched by oxygen plasma. As shown in a), since the surface contains hydroxyl groups (OH) 12, a dehydrochlorination reaction occurs on the surface, and the molecule has a -SiO- bond on the film surface as shown in the following (Chem. 3) and (Chem. 4). Fixed to the surface via

[0026]

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[0027]

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After that, when the film is washed with a non-aqueous solvent such as Aflude (a fluorine-based solvent made by Asahi Glass) and further washed with water, SiCl ₄ molecules that have not reacted with the film are removed. As shown, a siloxane monomolecular film 13 of the following (Chemical Formula 5) or (Chemical Formula 6) is obtained on the surface in a state of being chemically bonded.

[0029]

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[0030]

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[0031] Therefore, then the solvent of the nonaqueous mixed with material containing fluorocarbon groups and chloro <br/> silyl group, for example, using the following (Formula 7), Afurudo (Asahi dissolved at a concentration of about 3% A glass fluorine-based solvent) solution was prepared.

[0032]

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When the film on which the monomolecular film is formed is immersed in an adjusting solution for about 1 hour, a dehydrochlorination reaction occurs on the surface of the film since the film surface contains a large number of hydroxyl groups (OH). 8) was generated, and as shown in FIG. 2 (c), the monomolecular film 14 containing fluorine could be formed unevenly in a state of being chemically bonded. This film could be formed at a higher density than in Example 1.

[0034]

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The monomolecular film did not peel at all even when the cross test was performed. In this case, since the fluorocarbon group was formed on the surface in an oriented state, the surface energy was extremely low, and the wetting angle to water was 140 to 150 degrees.

Further, an adhesive was applied to the back surface of the water-repellent and oil-repellent film thus obtained, and the film was stretched on glass. A transparent glass having extremely high water and oil repellency was obtained. Further, dirt was hardly attached, and even if it was attached, it could be easily removed, and the practicality was extremely high.

[0037] As the above embodiments, or etched uneven advance the film surface in the sub-micron to micron order, a rough surface-treated film surface by sandblasting and types rely method, one end Kurorushi lil group (SiCl _n X
A chlorosilane-based surfactant having a _3-n group, n = 1, 2, 3, and X is a functional group) and having a linear fluorocarbon group at the other end is chemically adsorbed via a siloxane bond, and fluorinated. Since a carbon-based monomolecular adsorption film is formed, it does not peel off with a high water / oil repellency. The surface roughness of the film surface is on the order of sub-micron to micron, and the thickness of the monomolecular film is on the order of nanometers. It can be excellent.

[0038]

As described above, according to the present invention, a transparent film having an extremely high water / oil repellent effect on its surface can be prepared, and this film is fixed to the film surface by a chemical bond (covalent bond). Therefore, it is possible to obtain a water- and oil-repellent film having a coating film that is excellent in durability, heat resistance, weather resistance, and abrasion resistance without being damaged or peeled off. In addition, various substrate surfaces can be made water- and oil-repellent very easily by simply attaching a super-water- and oil-repellent film without directly treating the substrate surface.

[Brief description of the drawings]

FIG. 1 (a) is a conceptual cross-sectional view of a polyethylene trifluorochloride film before forming a water / oil repellent film according to a first embodiment of the present invention. FIG. 2B is a conceptual cross-sectional view in which the portion A of the film surface (a) after the formation of the water- and oil-repellent film on the trifluorinated polyethylene film according to the first embodiment of the present invention is enlarged to the molecular level.

FIG. 2 (a) is a conceptual cross-sectional view of a polyethylene terephthalate film according to a second embodiment of the present invention, in which the film surface before forming a water / oil repellent film is enlarged to a molecular level. (B) A conceptual sectional view of a polyethylene terephthalate film according to a second embodiment of the present invention, in which a water- and oil-repellent film is being formed on a polyethylene terephthalate film, and the film surface is enlarged to the molecular level. (C) A conceptual cross-sectional view of a polyethylene terephthalate film according to a second embodiment of the present invention, in which the water- and oil-repellent film is formed on a polyethylene terephthalate film and the film surface is enlarged to the molecular level.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fluorochlorinated polyethylene film 2 Monomolecular film 11 Polyethylene terephthalate film 12 Siloxane monomolecular film 13 Monomolecular film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09K 3/18 104 C09K 3/18 104 (56) References JP-A-2-248480 (JP, A JP-A-60-40254 (JP, A) JP-A-58-147483 (JP, A) JP-A-63-175671 (JP, A) JP-A-1-315431 (JP, A)

Claims (6)

(57) [Claims] 1. The method according to claim 1, wherein the surface is roughened unevenly and O
A film containing a fluorocarbon group on the surface of a film containing an H group
Bioadsorbed monolayer is formed through O of the residue of the OH group.
A water-repellent and oil-repellent film fixed by sun bonding . 2. The water- and oil-repellent film according to claim 1, wherein the roughness of the roughened film surface is 0.3 μm or less. 3. The water / oil repellent film according to claim 1, wherein the material of the film is polyethylene terephthalate resin or polyethylene trifluoride chloride resin. 4. The water / oil repellent film according to claim 1, wherein an adhesive is applied to the back surface of the film. 5. A chlorosilane having a chlorosilyl group at one end and a fluorinated carbon group at the other end on the surface of a film whose surface is roughened to have irregularities on the order of submicron to micron and which has an OH group on the surface. The production of a water- and oil-repellent film characterized by forming a water- and oil-repellent chemically adsorbed monomolecular film fixed via a siloxane bond on the surface of the film by contacting a system compound to cause a dehydrochlorination reaction. Method. 6. A dehydrochlorination reaction in which a silyl compound containing a plurality of chloro groups is brought into contact with the surface of a film whose surface is roughened to irregularities on the order of submicron to micron and which contains OH groups on the surface. Forming a chemisorption film containing a silanol group on the surface of the film, and then contacting a chlorosilane-based compound having a chlorosilyl group at one end and a fluorocarbon group at the other end to cause a dehydrochlorination reaction. A method for producing a water- and oil-repellent film, comprising forming a water- and oil-repellent chemically adsorbed monomolecular film fixed via a siloxane bond on the surface of a chemical adsorption film containing groups.