JPH04255345A - Stainproof optical member and manufacture thereof - Google Patents

Abstract

PURPOSE:To form the optical member with excellent stain resistance, water repellency, oil repellency and durability without spoiling the original optical characteristics of an optical member by forming a thinfilm consisting of a fluorinated monomolecular film on a base material of the optical member through chem. bonding. CONSTITUTION:A monomolecular film is formed on the surface of a base material of an optical member through chem. bonding by using hydroxyl groups on the surface of the base material of the optical member, bringing generally it into contact with a non-aq. solvent mixed with a chlorosilane surface active agent having a chlorosilane group and contg. a linear carbon chain and reacting the hydroxyl groups on the surface of the decorative product with chlorosilyl group of a substance contg. a plurality of the above described chlorosilyl groups.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to an optical member having excellent stain resistance, water and oil repellency, and a method for manufacturing the same. More specifically, our products include display-type touch panel switches, copier face plates, Fresnel plates for overhead projectors, display glass, display optical filters, halogen lamps, mercury lamps, sodium lamps, light bulbs, chandeliers, and various lenses. The present invention relates to a high-performance antifouling optical member that has high water-repellent, oil-repellent, and antifouling effects.

0002

[Prior Art] Conventionally, the glass and plastic surfaces of display-type touch panel switches, copier face plates, OHP Fresnel plates, halogen lamps, mercury lamps, sodium lamps, light bulbs, chandeliers, lenses, etc., have been touched by humans. Then, there was a problem that the device would become dirty with sweat and grime, resulting in a significant deterioration in performance. Another problem with lenses and the like is that when water adheres to the lens and dries, it leaves behind a stain (a phenomenon known as water staining) that is difficult to remove.

In order to solve this problem, oligomers such as γ-glycidoxypropyltrimethoxysilane and/or
Alternatively, a technique is known in which fine particles of silica, antimony, etc. are added to this, applied to the surface of the substrate, and cured to form a thin coating. As another example, it has been proposed to treat the surface of a substrate with a silazane compound.

0004

[Problems to be Solved by the Invention] However, the known techniques for preventing stains on glass surfaces and plastic surfaces are not so excellent in stain resistance, water and oil repellency, and have problems in durability. There was a problem.

[0005] In order to solve the problems of the prior art, the present invention provides a high-performance optical member with a high antifouling effect that does not allow dirt to adhere or is easily removed even if it does, and is durable. To provide an optical member having an excellent coating thin film and a method for manufacturing the same.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the antifouling optical member of the present invention is an optical member in which a thin film is formed on the surface of a base material, the thin film being a chemically adsorbed monomer containing fluorine. It is characterized in that it includes at least a molecular film, and the thin film is formed by chemical bonding with a base material.

[0007] In the above structure, it is preferable that a chemically adsorbed monomolecular film containing fluorine is formed on the surface via at least a siloxane monomolecular film.

Further, in the above structure, the base material of the optical member is made of glass or plastic material, and the optical member is a display type touch panel switch, a face plate of a copying machine, a Fresnel plate for an overhead projector, a display glass, a display glass or a plastic material. Typical examples include optical filters, halogen lamps, mercury lamps, sodium lamps, light bulbs, chandeliers, eyeglass lenses, microscope lenses, telescope lenses, binocular lenses, magnifying glass lenses, and various equipment lenses.

Next, in the first manufacturing method of the present invention, after cleaning the substrate, a chlorosilane group (SiCln
3-n group, n = 1, 2, 3, X is a functional group) and immerses the base material in an organic solvent in which a chlorosilane surfactant having a fluorocarbon group at the other end is dissolved. , comprising the step of forming a chemically adsorbed monomolecular film made of the activator over the entire surface of the substrate.

Next, in the second manufacturing method of the present invention, after the substrate is washed, it is brought into contact with a non-aqueous solvent containing a substance containing a plurality of chlorosilyl groups, so that the hydroxyl groups on the surface of the substrate and the chlorosilyl groups are separated. reacting with the chlorosilyl group of a substance containing a plurality of chlorosilyl groups to precipitate the substance on the surface of the substrate, and washing the excess substance containing a plurality of chlorosilyl groups remaining on the substrate using a non-aqueous organic solvent. After removal, a step of forming a monomolecular film of a substance containing a plurality of silanol groups on the base material by reacting with water, and a step of forming a monomolecular film made of a substance containing a plurality of silanol groups at one end; 3.X
The method is characterized in that it includes a step of chemically adsorbing a chlorosilane surfactant having a functional group) and a linear fluorocarbon group at one end onto a substrate to form a monomolecularly adsorbed film.

In the second production method, SiCl4, SiHCl3, SiH2 Cl2, Cl-(Si
It is preferable to use Cl2O)n-SiCl3 (n is an integer).

In both of the above production methods, CF3 -(CF2
)n -R-SiXp Cl3-p (n is 0 or an integer, R is an alkyl group, ethylene group, acetylene group, S
It is preferable that X represents a substituent such as iO- or an oxygen atom, or may be omitted; X represents a substituent such as H or an alkyl group;

[0013]

[Function] According to the configuration of the present invention, there is provided an optical member in which a thin film is formed on the surface of a base material, wherein the thin film includes at least a chemically adsorbed monomolecular film containing fluorine, and the thin film is chemically bonded to the base material. Since the molecules are formed in a lined-up state due to bonding, it is possible to obtain a high-performance optical member with a high antifouling effect so that dirt does not adhere or is easily removed even if it does adhere. It is also highly durable. Furthermore, since fluorine is present on the outermost surface of the thin film, the slipperiness of the surface of the optical member is improved and scratches are less likely to occur.

Furthermore, in the present invention, since a fluorocarbon monomolecular film having an extremely thin film thickness (thin film) on the nanometer level is formed on the surface of the optical member, the inherent functions of the optical member such as light transmittance are completely impaired. There is no. In addition, since this film is a fluorocarbon monomolecular film, it has excellent water and oil repellency, making it possible to enhance the antifouling effect on the surface. Therefore, it is possible to obtain a high-performance optical member that has a high antifouling effect against human sweat and dirt.

Furthermore, the above-described manufacturing method of the present invention allows the thin film of the present invention to be manufactured rationally and efficiently.

[0016]

[Example] The glass used as an example of the optical member described above is an oxide and therefore contains hydroxyl groups on the surface. Therefore, a chlorosilane group (SiCln
Molecules containing a linear carbon chain having a group (n group, n = 1, 2, 3, hydroxyl groups on the glass surface and chlorosilyl groups of the substance containing a plurality of chlorosilyl groups are reacted to deposit a monomolecular film of the substance on the glass surface, or a non-aqueous mixture containing a substance containing a plurality of chlorosilyl groups. a step of causing the hydroxyl groups on the glass surface to react with the chlorosilyl groups of the substance containing a plurality of the chlorosilyl groups by contacting with a solvent to precipitate the substance on the glass surface;
washing and removing the excess substance containing a plurality of chlorosilyl groups remaining on the glass surface using a non-aqueous organic solvent to form a siloxane monomolecular film made of the substance containing a plurality of chlorosilyl groups on the glass; A process of chemically adsorbing a silane surfactant containing a linear carbon chain with a chlorosilane group at one end onto glass to accumulate a monomolecular adsorbed film forms a fluorocarbon chemically adsorbed monomolecular cumulative film on the glass surface. Can be formed.

In addition, if the base material does not have an oxide film on its surface, such as a plastic base material, the surface may be made hydrophilic, that is, treated in advance at 100 W for about 20 minutes in an oxygen-containing plasma atmosphere. It is sufficient to introduce hydroxyl groups onto the surface.

Optical substrates related to the present invention are listed below as display type touch panel switches, copying machine face plates, OHP Fresnel plates, halogen lamps, mercury lamps, sodium lamps, light bulbs, chandeliers, various lenses, etc. There are high-performance glasses and plastics that have a high fouling effect, but a typical example is cathode tubes (CR).
T) Display touch panel switches and OHP Fresnel plates will be explained one by one. In addition, in the following examples, % means weight % unless otherwise indicated.

Example 1 First, a processed glass CRT for a display type touch panel switch is prepared (the face plate before assembly may be used), and after cleaning with an organic solvent, a substance containing a fluorocarbon group and a chlorosilane group is prepared. A non-aqueous solvent mixed with, for example, CF3 (CF2)7 (CH2)2
80 using SiCl3 dissolved at a concentration of about 1%.
%n-hexadecane (toluene, xylene, or dicyclohexyl may also be used), 12% carbon tetrachloride, and 8% chloroform solution is prepared and the CRT is immersed for about 2 hours.
Since the surface of the CRT contains many hydroxyl groups, the hydroxyl groups react with the SiCl groups of substances containing fluorocarbon groups and chlorosilane groups, resulting in a dehydrochloric acid reaction, which causes CF3 (CF2)7 ( CH2)2Si
(O-)3 bonds were generated, and a monomolecular film 2 containing fluorine was formed with a film thickness of approximately 15 angstroms in a state of chemical bonding with the surface of the CRT (FIG. 1). It should be noted that the monomolecular film had extremely strong chemical bonds, so it did not peel off at all.

[0020] When we tried to use this CRT in actual use, we found that the adhesion of dirt and grime was significantly reduced compared to those that were not treated, and even if dirt did adhere, fingerprints and other oils and fats could be easily removed by rubbing it with a tissue. I was able to remove it. Moreover, at this time, there were no scratches at all.

Example 2 In the case of a reinforced glass that is hydrophilic but contains a small proportion of hydroxyl groups, such as an OHP Fresnel plate, a material containing a plurality of trichlorosilyl groups (such as SiCl4, or SiHCl3, SiH2 Cl2, Cl-( S
iCl2O)n-SiCl3 (n is an integer). In particular, if SiCl4 is used, it has a small molecule and high activity towards hydroxyl groups, so it has a great effect of uniformly making the plate surface hydrophilic. When immersed, hydrophilic OH groups 12 are formed on the plate surface 11.
(FIG. 2), a dehydrochlorination reaction occurs on the surface and a chlorosilane monomolecular film of a substance containing a plurality of trichlorosilyl groups is formed.

For example, if SiCl4 is used as the substance containing a plurality of trichlorosilyl groups, the plate surface 11
Since a small amount of hydrophilic OH groups are exposed, a dehydrochlorination reaction occurs on the surface, and the molecule changes to -Si as shown in [Chemical 1] below.
It is anchored to the surface via O-bonds.

[0023]

[Chemical 1] After that, when washing with a non-aqueous solvent such as chloroform and further washing with water, SiC that has not reacted with the vessel is removed.
The l4 molecules are removed, and a siloxane monomolecular film 13 such as the following [Chemical formula 2] is obtained on the plate surface (FIG. 3).

[0024]

[Image Omitted] Note that the monomolecular film 13 formed at this time is completely bonded to the plate through chemical bonds of -SiO-, and therefore will not peel off at all. Moreover, the obtained monomolecular film has many SiOH bonds on the surface. Approximately three times as many hydroxyl groups as the original hydroxyl groups are generated.

Therefore, a non-aqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group, such as CF
3 (CF2)7 (CH2)2SiCl3 was prepared by preparing a solution of 80% n-hexadecane, 12% carbon tetrachloride, and 8% chloroform dissolved at a concentration of about 10%, and a monomer having many SiOH bonds on the surface was prepared. When the plate on which the molecular film is formed is soaked for about 1 hour, CF3 (CF2)7 (CH2)2 Si is formed on the plate surface.
(O-)3 bonds were generated, and the fluorine-containing monomolecular film 14 was chemically bonded to the underlying siloxane monomolecular film, and a film thickness of about 15 angstroms was formed over the entire surface of the plate (Figure 4). . Note that the monomolecular film did not peel off at all even when a peel test was performed.

Furthermore, in the above examples, CF3 (CF2)7 (CH2
)2 SiCl3 was used, but if an ethylene group or acetylene group is added to or incorporated into the alkyl chain part, the hardness of the monolayer can be further improved because it can be crosslinked by electron beam irradiation of about 5 megarads after the monolayer is formed. It is also possible to do so.

In addition to the above-mentioned fluorocarbon surfactants, CF3 CH2 O(CH2)15S
iCl3, CF3(CH2)2Si(CH3)
2 (CH2)15SiCl3, F(CF2)8
(CH2)2 Si(CH3)2 (CH2)
9 SiCl3, CF3 COO(CH2)15S
iCl3, CF3 (CF2)5 (CH2)2
SiCl3 etc. can be used.

As explained above, according to the embodiments of the present invention, an extremely thin fluorocarbon monomolecular film with a film thickness on the nanometer level is formed on the surface of the substrate, thereby impairing the original optical properties of the optical substrate. Nothing happened at all. Furthermore, this fluorocarbon monomolecular film has excellent water and oil repellency, making it possible to enhance the antifouling effect on the surface. Therefore, it is possible to provide a high-performance optical member that has an extremely high antifouling effect against human sweat and dirt. Furthermore, this has the great effect of significantly reducing the number of times of cleaning.

[0029]

[Effects of the Invention] As described above, according to the present invention, since an extremely thin fluorocarbon monomolecular film with a film thickness on the nanometer level is formed on the surface of an optical substrate, the original optical properties of the optical member are not impaired. This makes it possible to enhance the antifouling effect of the surface. Furthermore, this fluorocarbon monomolecular film has excellent water and oil repellency. Therefore, it is possible to provide a high-performance optical member with an extremely high antifouling effect. Furthermore, this has the great effect of significantly reducing maintenance.

[Brief explanation of the drawing]

FIG. 1 is a conceptual cross-sectional view of the surface of a CRT of the present invention enlarged to the molecular level.

FIG. 2 is a conceptual cross-sectional view of the surface of an OHP Fresnel plate before the processing step, enlarged to the molecular level, in order to explain a second embodiment of the glass of the present invention.

FIG. 3 is a conceptual cross-sectional view of the surface of an OHP Fresnel plate during a processing step enlarged to the molecular level to explain a second embodiment of the glass of the present invention.

FIG. 4 is a conceptual cross-sectional view of the surface of an OHP Fresnel plate after processing, enlarged to the molecular level, in order to explain a second example of the glass of the present invention.

[Explanation of symbols]

1...CRT surface, 11...OHP plate surface, 2,
14... Monomolecular film, 12... Hydroxyl group, 13... Siloxane monomolecular film.

Claims (7)

[Claims] 1. An optical member having a thin film formed on the surface of a base material, wherein the thin film includes at least a chemically adsorbed monomolecular film containing fluorine, and the thin film is formed by chemical bonding with the base material. A stain-resistant optical member characterized by: 2. The antifouling optical member according to claim 1, wherein a chemically adsorbed monomolecular film containing fluorine is formed on the surface via at least a siloxane monomolecular film. 3. The base material of the optical member is made of glass or plastic material, and the optical member is a display type touch panel switch, a face plate of a copying machine, a Fresnel plate for an overhead projector, a glass for a display, an optical filter for a display, a halogen The antifouling optical member according to claim 1 or 2, which is selected from a lamp, a mercury lamp, a sodium lamp, a light bulb, a chandelier, and an optical lens. [Claim 4] After washing the base material, it has a chlorosilane group (SiCln Antifouling optics comprising the step of immersing the base material in an organic solvent in which a chlorosilane surfactant is dissolved to form a chemically adsorbed monomolecular film made of the surfactant over the entire surface of the base material. Method of manufacturing parts. 5. After washing the substrate, it is brought into contact with a non-aqueous solvent containing a substance containing a plurality of chlorosilyl groups, and the hydroxyl groups on the surface of the substrate react with the chlorosilyl groups of the substance containing a plurality of chlorosilyl groups. a step of precipitating the substance on the surface of the substrate, and washing and removing a substance containing a plurality of extra chlorosilyl groups remaining on the substrate using a non-aqueous organic solvent, and then reacting with water, forming a monomolecular film made of a substance containing a plurality of silanol groups on a base material;
Chlorosilane group (SiCln X3-n group, n
= 1, 2, 3, X is a functional group) and a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end is chemically adsorbed onto a substrate to accumulate a monomolecular adsorption film. A method for producing an antifouling optical member, the method comprising: Claim 6: S as a substance containing a plurality of chlorosilyl groups
iCl4, or SiHCl3, SiH2Cl2
, Cl-(SiCl2O)n-SiCl3(n
6. The method for manufacturing an antifouling optical member according to claim 5, wherein the number is an integer. 7. CF3-(CF2)n-R-SiXpCl3 as a chlorosilane surfactant having a chlorosilane group at one end and a linear fluorocarbon group at the other end.
-p (n is 0 or an integer, R represents an alkyl group, ethylene group, acetylene group, SiO-, or a substituent containing an oxygen atom, but may be omitted; X is a substituent such as H or an alkyl group; p is 6. The method for producing an antifouling optical member according to claim 4 or 5, wherein the method uses 0, 1, or 2).