WO2010116714A1 - Face plate for display device, process for producing same, and display device and article both made using these - Google Patents

Abstract

A face plate for display devices which has high durability, can be produced at a low cost, is highly safe for the human body and the environment, and is less apt to suffer adhesion of fingerprints or the like thereto; a process for producing the face plate; and a display device and an article each made using the face plate and the process. The face plate has a thin fluorinated organic film (11) obtained by applying a hydrocarbon-group-containing transparent substance so as to cover at least some of the surface of a face plate (10) which is to be located on the outer side and subjecting the coating to a low-pressure plasma treatment in an atmosphere of a fluorocarbon-group-containing gas to thereby replace some or all of the hydrocarbon groups with fluorocarbon groups and/or fluorine atoms (19).

Description

Display device face plate, manufacturing method thereof, display device using the same, and article

The present invention relates to a face plate for a display device, a manufacturing method thereof, and a display device and an article using the same, and more specifically, has high durability, can be manufactured at low cost, and is highly safe for human bodies and the environment. The present invention relates to a face plate for a display device including an optical lens and a housing with less adhesion of fingerprints, a manufacturing method thereof, a display device and an article using the same.

In recent years, with the improvement of living standards and the enhancement of hygiene awareness, countermeasures against contamination of articles around us have been demanded. For display devices including optical lenses and housings used in various information devices and operation terminals, the adhesion of fingerprints is reduced, visibility is improved, maintenance costs are reduced, especially for public health in touch panels. Improvement of antifouling property is required for reasons such as

There are two methods for preventing contamination of the surface of the member: a method of forming a film having a small surface energy on the surface of the member and a surface treatment method of reducing the surface energy of the surface of the member itself. There is a demand for technology with low load and manufacturing technology with less environmental damage when products are discarded.

For example, Patent Document 1 discloses a glass plate on which a highly durable water / oil repellent / antifouling coating is formed, the water / oil repellent / antifouling coating comprising at least a fluorocarbon group and a hydrocarbon group. A water / oil repellent / antifouling glass characterized in that it comprises at least one composite film containing a substance mainly containing a silyl group (for example, perfluoroalkylalkoxysilane) and a substance mainly containing a siloxane group. A plate and its manufacturing method are disclosed.

Patent Document 2 discloses a technique for antifouling the surface of a member using fluorine gas.

JP 2005-206447 A JP 2005-290118 A

However, the method for producing a water- and oil-repellent and antifouling glass plate described in Patent Document 1 has a drawback that the production cost is high because an expensive fluorocarbon silane compound is used.
On the other hand, the method described in Patent Document 2 does not require a solvent during the antifouling treatment, but has a problem that transparency is deteriorated due to the treatment, and a long time (several hours) is required for the reaction, so that the efficiency is poor. have.

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and a face plate for a display device including an optical lens and a housing that has a low environmental impact at the time of processing or disposal, and that can be manufactured inexpensively and has a low adhesion of fingerprints and the like, and its manufacture. It is an object of the present invention to provide a method and a display device and an article using them.

According to the first aspect of the present invention that meets the above-mentioned object, a transparent functional group having a fluorine-containing functional group in which part or all of the hydrogen atoms in the hydrocarbon group are substituted with either or both of a fluorine atom and a fluorocarbon group. The present invention solves the above-mentioned problems by providing a face plate for a display device, wherein a non-existent substance is present so as to cover at least a part of a transparent substrate exposed on the surface on the outer side. .
In the present invention, the “display device” includes a device operation touch panel and a portable information terminal having both a display function and an operation function. Furthermore, the “article” includes a mobile phone, an electronic computer, a PDA (personal digital assistant), a GPS terminal, a television receiver, a cash dispenser (CD) device, an automatic teller machine (ATM), and the like.

The “face plate” is a transparent member that covers the outermost surface of the display surface of the display device. The touch panel has a display surface protection and input function, a camera lens of a mobile phone that is an information input member, and an input. A touch panel portion of a portable information terminal that also serves as a housing and a housing is also included in the “face plate” in the present invention. The “outside surface” refers to a surface that becomes the outside when the display device is assembled as a face plate, and may be abbreviated as “outside surface” hereinafter.

At least a part of the outer surface of the face plate for a display device including a camera lens and a housing incorporated in a cellular phone has a part or all of the hydrogen atoms in the hydrocarbon group are fluorine atoms and fluorocarbon groups. By covering with a substance having a fluorine-containing functional group substituted with either or both, the surface energy of the substrate can be reduced, and high water and oil repellency can be imparted.

The display device faceplate according to the first aspect of the present invention, wherein the fluorine-containing functional group has a hydrocarbon group present so as to cover at least a part of the outer surface of the substrate. Is preferably obtained by low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group.
In this way, by obtaining a substance containing a fluorine-containing functional group having water / oil / oil repellency / antifouling property, water / oil / oil / oil repellency / antifouling property can be obtained at a lower cost than when an expensive fluorocarbon film compound is used. A face plate for a display device having the above can be manufactured.

In the face plate for a display device according to the first aspect of the present invention, the substance having a fluorine-containing functional group includes a linear film substance having the fluorine-containing functional group, which is the outside of the substrate. An organic thin film chemically bonded to the surface on the side may be formed.
Since the substance having a fluorine-containing functional group present so as to cover at least a part of the surface on the outer side of the base material forms an organic thin film having a nanometer level film thickness, Water and oil repellency can be imparted without impairing optical properties and the like.

In the face plate for a display device according to the first aspect of the present invention, the fluorine-containing functional group is any one of a hydrocarbon group, a hydrocarbon group having an ester group, and a hydrocarbon group having an ether group. Or the functional group by which the several hydrogen atom was substituted by either a fluorine atom or a fluorocarbon group may be sufficient.

In the display device faceplate according to the first aspect of the present invention, the fluorine-containing functional group is any one or more hydrogen atoms in the functional groups represented by the following formulas (I) to (V): It may be a functional group substituted with either a fluorine atom or a fluorocarbon group.

In the formulas (I) to (V), m and n each independently represent an integer of 0 or more and 24 or less, and m ≧ n.

In the face plate for a display device according to the first aspect of the present invention, the fluorine-containing organic thin film may be a monomolecular film of the film substance chemically bonded to the outer surface of the substrate. .
When the fluorine-containing organic thin film is a monomolecular film, the appearance (color tone, gloss, etc.) and optical properties of the base material are not impaired, and it can be suitably applied to optical materials and housings of various devices. Moreover, since the fluorine-containing organic thin film is chemically bonded to the surface on the outer side of the base material, it is excellent in durability and can exhibit water / oil / oil repellency / antifouling properties over a long period of time.

In the display device faceplate according to the first aspect of the present invention, the fluorine-containing organic thin film may contain polysiloxane molecules formed of alkoxysilane and / or alkoxypolysiloxane.
Further, in this case, the film substance having the fluorine-containing hydrocarbon group is bonded to the outside of the base material through a film of the polysiloxane molecule bonded and fixed to the surface on the outside side of the base material. It may be bonded and fixed to the surface on the other side.

Alternatively, in this case, the polysiloxane molecule coating is formed on the base material via a bond formed by a reaction between an alkoxysilyl group and a surface functional group present on the outer surface of the base material. A part of the film substance having the fluorine-containing hydrocarbon group fixed to the outer surface is directly bonded to the outer surface of the substrate, and the rest is coated with the polysiloxane molecule. It may be bonded and fixed to the outer surface of the substrate.
By forming a film of polysiloxane molecules, the density of the film material on the outermost surface can be improved, and durability and water / oil repellent / antifouling properties can be improved. Note that the polysiloxane molecule coating film has a nanometer-level film thickness, so that the thermal conductivity is not impaired. Therefore, it can be suitably applied to a heat radiating member.

In the face plate for a display device according to the first aspect of the present invention, in which the fluorine-containing organic thin film contains a polysiloxane molecule, the polysiloxane molecule is an alkoxysilane and / or a formula (VII) represented by the following formula (VI): It may be formed by a condensation reaction of an alkoxypolysiloxane represented by:
SiH _x (OA) _4-x (VI)
(AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (VII)
In the formulas (VI) and (VII),
x is 0, 1, or 2;
A represents an alkyl group,
n is 0, 1, or 2.

In the display device faceplate according to the first aspect of the present invention, the substance having a fluorine-containing functional group may be a fluorine-containing organic polymer having the fluorine-containing functional group.
Since the fluorine-containing organic polymer is present so as to cover at least a part of the surface on the outer side of the substrate, it has both water and oil repellency and can prevent the adhesion of dirt to the outer surface.

In the face plate for a display device according to the first aspect of the present invention, it is preferable that a surface roughness of the outer side surface is 10 nm or more and 400 nm or less.
If the surface roughness of the outer surface of the face plate for a display device is 400 nm or less, which is the shortest wavelength of visible light, the transparency and optical characteristics of the face plate for a display device are obtained even when a transparent substrate is used. High water and oil repellency and antifouling properties can be imparted without impairing water.

According to a second aspect of the present invention, there is provided a surface on the outer side of a transparent base material present so that the transparent substance having a hydrocarbon group covers at least a part of the surface on the outer side of the face plate. The present invention solves the above problems by providing a method for manufacturing a face plate for a display device, comprising a step A of performing low-pressure plasma treatment in a gas atmosphere containing a fluorocarbon group.

In step A, in a gas atmosphere of a compound containing a fluorocarbon group, the surface of the substance having a hydrocarbon group on the surface of the substrate is subjected to low-pressure plasma treatment so that a part or all of the hydrogen atoms in the hydrocarbon group are fluorine. By substituting with one or both of an atom and a fluorocarbon group, water and oil repellency is imparted. Therefore, it is possible to manufacture a face plate for a display device having water repellency, oil repellency and antifouling properties at a lower cost than when an expensive fluorocarbon film compound is used.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, in the step A, the side that is outside the substrate in the mixed atmosphere of the compound gas containing the fluorocarbon group and the oxygen gas. The surface of the substance having the hydrocarbon group on the surface may be subjected to low-pressure plasma treatment.
If the substrate is subjected to low-pressure plasma treatment in a mixed atmosphere of a compound gas containing a fluorocarbon group and oxygen gas, a water- and oil-repellent and antifouling member having higher efficiency and higher durability can be provided.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, the unevenness having a surface roughness of 10 nm or more and 400 μm or less is formed on the outer surface of the substrate before the step A. You may further have the process B to form.
In this case, the apparent surface energy of the surface of the water / oil repellent transparent member can be significantly reduced as compared with the case of a flat surface, and high water / oil repellent / antifouling properties can be imparted. Further, since the surface roughness of the water / oil repellent transparent member is 400 nm or less which is the shortest wavelength of visible light, even when used for a transparent lens or face plate, the transparency of the lens or face plate is impaired. High water and oil repellency and antifouling properties can be imparted.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, the coating of the substance containing a hydrocarbon group covering at least a part of the outer surface of the substrate is formed on the substrate. You may further have the process C formed in the surface of the side used as the said outer side.
By using the inorganic base material which does not have a hydrocarbon group on the surface on the outer side by including the step C of forming a coating of a substance containing a hydrocarbon group on the surface on the outer side of the base material, for a display device A face plate can be manufactured.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, in the step C, a treatment liquid containing a film compound having a hydrocarbon group is brought into contact with the surface on the outer side of the substrate. An organic thin film containing a hydrocarbon group may be formed by a reaction between the film compound and a surface functional group on the surface on the outer side of the substrate.
In Step C, the coating of the substance having a hydrocarbon group formed on the surface on the outer side of the substrate is an organic thin film having a film thickness of nanometer level, so that the optical characteristics and the like of the substrate are impaired. Water and oil repellency can be imparted without any problem.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, the film compound includes any one of a hydrocarbon group, a hydrocarbon group having an ester group, and a hydrocarbon group having an ether group. May be.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, the film compound may be a film compound represented by the following formula (X).
Z-SiX _p Y _3-p (X)
In the formula (X), Z represents a substituent containing any one of an alkyl group having 25 or less carbon atoms, an aryl group, a vinyl group, and a silicone group,
X represents a hydrogen atom or a substituent containing any one of an alkyl group having less carbon atoms than Z, an aryl group, a vinyl group, and a silicone group;
Y represents a halogen atom or an alkoxyl group,
p represents 0, 1 or 2.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, the film compound containing a hydrocarbon group is a film compound represented by any of the following formulas (XI) to (XV): May be.
_{CH 3 (CH 2) n Si} (OA) 3 (XI)
[CH ₃ (CH ₂ ) _n ] ₂ Si (OA) ₂ (XII)
[CH ₃ (CH ₂ ) _n ] ₃ Si (OA) (XIII)
CH ₃ (CH ₂ ) _m —COO— (CH ₂ ) _n Si (OA) ₃ (XIV)
CH ₃ (CH ₂ ) _m —O— (CH ₂ ) _n Si (OA) ₃ (XV)
In the formulas (XI) to (XV), m and n each independently represent an integer of 0 or more and 24 or less, and A represents an alkyl group.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, the treatment liquid is an alkoxysilane represented by the following formula (VI) and / or an alkoxypolysiloxane represented by the formula (VII): May be included.
SiH _x (OA) _4-x (VI)
(AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (VII)
In the formulas (VI) and (VII),
x is 0, 1, or 2;
A represents an alkyl group,
n is 0, 1, or 2.

Alternatively, in the method for manufacturing a face plate for a display device according to the second aspect of the present invention, in the step C, a solution containing the alkoxysilane and / or the alkoxypolysiloxane is used on the outer side of the substrate. A surface is treated to form a polysiloxane molecule film on the surface, and then the substrate on which the polysiloxane molecule film is formed is treated with the treatment liquid, and the organic layer is formed on the polysiloxane molecule film. A thin film may be formed.
By forming a film of polysiloxane molecules, the density of the film material on the outermost surface can be improved, and durability and water / oil repellent / antifouling properties can be improved.

In the method for manufacturing a face plate for a display device according to the second aspect of the present invention, a film containing an organic polymer may be formed as the substrate in the step C.

A third aspect of the present invention solves the above problem by providing a display device using the face plate for a display device according to the first aspect of the present invention.

A fourth aspect of the present invention solves the above problem by providing an article using the display device according to the third aspect of the present invention.

The article according to the fourth aspect of the present invention is any of a mobile phone, an electronic computer or a display device for an electronic computer, a portable information terminal, a GPS terminal, a television receiver, a cash dispenser device, and an automatic teller machine. May be. Furthermore, the lens used for them and the housing itself may be combined.
All of these articles are used for articles that often come into contact with the human body, and antifouling properties are strongly required from the viewpoint of hygiene, and the present invention can be suitably applied.

According to the present invention, there are provided a face plate for a display device having a face plate that can be manufactured at a low cost at the time of processing and disposal, and a manufacturing method thereof, and a display device and an article using them. Further, according to the method of the present invention, it is possible to impart a water / oil repellent / antifouling function only on the outermost surface of the face plate having a hydrocarbon group on the outer surface at low cost, resource saving, energy saving.

The display device according to the present invention and an article using the display device have high antifouling properties, durability, safety for human bodies and the environment, and can exhibit antifouling properties semipermanently.

It is explanatory drawing of the cross-section of the face plate for display apparatuses which concerns on each embodiment of this invention. FIG. 3 is an explanatory diagram schematically showing an enlarged cross-sectional structure of the face plate for a display device according to the first embodiment of the present invention up to a molecular level. In the manufacturing method of the face plate for display apparatuses, it is explanatory drawing which expanded and expanded the cross-sectional structure of the base material in which the organic thin film was formed to the molecular level typically. It is explanatory drawing which expanded the cross-sectional structure of the faceplate for display apparatuses which concerns on the 2nd Embodiment of this invention to the molecular level, and represented typically. In the manufacturing method of the face plate for display apparatuses, it is explanatory drawing which expanded the cross-sectional structure of the base material in which the organic thin film containing a polysiloxane molecule was expanded to the molecular level, and was represented typically. In the manufacturing method of the face plate for display devices, it is an explanatory view showing the state where the organic thin film containing many silanol groups was formed. It is explanatory drawing which expanded the cross-sectional structure of the faceplate for display apparatuses which concerns on the 3rd Embodiment of this invention to the molecular level, and was represented typically. It is explanatory drawing of the manufacturing method of the water / oil repellent antifouling member which concerns on the 4th Embodiment of this invention, (a) and (b) are each in the gas atmosphere of the compound which has a fluorocarbon group. It is explanatory drawing which expanded to the molecular level and represented typically the outer surface vicinity of the base material before and after low-pressure plasma processing of this.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention.

As shown in FIG. 1, the display device faceplate 1 according to each embodiment of the present invention (hereinafter, the display device faceplates 10, 20, and 30 according to first to fourth embodiments which will be described individually). , 40 generic name), a transparent substance 2 having a fluorine-containing functional group in which some or all of the hydrogen atoms in the hydrocarbon group are substituted with either or both of a fluorine atom and a fluorocarbon group (hereinafter, Surfaces on the outer side of the fluorine-containing organic thin films 11, 21, 31 according to the first to third embodiments and the fluorine-containing organic polymer 41 according to the fourth embodiment, which will be described individually, At least a part of the outer surface of the transparent base material 3 exposed to the surface (hereinafter collectively referred to as base materials 12, 22, 32, and 42 according to first to fourth embodiments which will be described individually) As an example, it exists so as to cover the entire surface of the substrate 3 It is present to cover the are shown.) For engagement.

A face plate for a display device (hereinafter sometimes abbreviated as “face plate”) 1 is a base material 3 (covering at least a part of a surface on the outer side of a substance having a hydrocarbon group. Is manufactured by a method including a step A in which a low-pressure plasma treatment is performed in a gas atmosphere containing a fluorocarbon group (see FIGS. 2, 4, 7, and 8 (b)). In this case, the fluorine-containing functional group is a gas atmosphere of a compound containing a fluorocarbon group on the surface on the outer side of the substrate 3 (substance having a hydrocarbon group present so as to cover at least a part thereof). It is obtained by low-pressure plasma treatment.

First, step A will be described.
When plasma is generated by high frequency discharge in a gas atmosphere of a compound containing a fluorocarbon group, a fluorocarbon radical such as a fluorine radical (· F) or a trifluoromethyl radical (· CF ₃ ) is generated. These radicals replace the hydrogen atom of the hydrocarbon group on the surface on the outside of the substrate 3 with trifluoromethyl groups 19 and 43 (an example of a fluorine atom or a fluorocarbon group) (FIGS. 2, 4, 7, 8 (b)). Alternatively, when a gas containing a compound having an unsaturated bond such as tetrafluoroethylene is used, a perfluoroalkyl group having a large carbon number can also be generated by plasma polymerization.

For the low-pressure plasma treatment, any plasma treatment apparatus that can be used for plasma surface treatment or low-temperature ashing can be used. Specific examples of the form of the chamber include a flow tube type, a bell jar type, etc., and as a form of the electrode for discharge, a parallel plate type, a coaxial cylindrical type, a curved counter plate type such as a cylinder, a sphere, etc. Examples include a hyperboloid opposed flat plate type and a plurality of fine wire opposed flat plate types. The high frequency current can be applied by either a capacitive coupling method or an induction method using an external electrode. The output of the high-frequency power source is appropriately adjusted depending on the material and size of the base material, the type of compound containing a fluorocarbon group used, the type and volume fraction of the added gas, the volume and pressure of the chamber, etc. For example, 10 to 250 W.

Examples of the compound containing a fluorocarbon group that has been confirmed to be usable include CF ₄ , C ₂ F ₆ , C ₂ F ₄ , and CHF ₃ . In principle, even a compound that contains a CF ₃ group and is liquid at normal temperature and pressure can be used as long as it can be gasified under low-pressure plasma processing conditions. At this time, if a trace amount (0.1 to 5% by volume) of Ar, He or the like is mixed, there is an effect of stabilizing the discharge.

In addition, when a small amount of oxygen (0.1 to 15% by volume) is contained, the hydrogen atom of the hydrocarbon group is replaced with a fluorine atom or a fluorocarbon group while oxidizing the surface on the outer side of the substrate 12. Therefore, there is an effect of increasing the processing efficiency. Alternatively, low pressure plasma treatment may be performed in a gas atmosphere of a compound containing a fluorocarbon group after performing low pressure plasma treatment in an oxygen gas atmosphere in advance and performing oxidative etching of the outer surface.

Plasma treatment in an oxygen gas atmosphere has an action of cleaning the outer surface of the substrate 12 and an action of roughening the outer surface. By arbitrarily controlling the power of the high-frequency power source and the treatment time, The thickness can be controlled in the range of several nanometers to several hundred microns.

Although the base material 3 used for manufacturing the face plate 1 for a display device is transparent and needs to be present so as to cover at least a part of the surface on the outer side, the substance having a hydrocarbon group, There is no restriction | limiting in particular about a material, a shape, and a magnitude | size, The thing of arbitrary materials, shapes, and magnitude | sizes can be used. In the case of using the base material 3 made of an inorganic material having no hydrocarbon group on the surface on the outer side, in Step C described later, a coating of a substance containing a hydrocarbon group covering at least a part of the outer surface is formed. It can be formed on the outer surface of the substrate 3.
Specific examples of the material of the substrate 3 include organic materials such as resins and inorganic materials such as glass.

Specific examples of transparent resins are polyurethane, polyester, polyethylene, polyphenylene sulfide, polyethylene terephthalate, polyethylene naphthalate, polyvinylidene chloride, polyvinyl chloride, polyolefin, polycarbonate, polyvinyl acetate, polystyrene, polysulfone, polytrimethylene terephthalate. , Polylactic acid, polyvinyl alcohol, polyvinyl pyrrolidone, polybutylene terephthalate, polybutylene naphthalate, polyvinylidene fluoride, polypropylene, polymer alloy, polymethylpentene, ionomer resin, acrylic resin, acetylcellulose, alkyd resin, AS resin, liquid crystal polymer, Examples include ABS resin, epoxy resin, urea resin, and other engineering plastics.

Specific examples of transparent inorganic materials include soda-lime glass, quartz glass, borosilicate glass, crystal glass, glass ceramics, and other metal oxides such as indium oxide, magnesium oxide, and ITO, sodium chloride, and fluoride. Examples thereof include inorganic salts such as single crystals, diamond, and DLC. The base material 3 does not need to be a bulk material, and may be a thin film material such as a vapor deposition film or a coating, or may be a laminated material or the like. Specific examples of the transparent thin film material include a hard coat film containing silica covering the surface of the transparent resin plate, an ITO film, or a sol-gel film of a transparent metal oxide (silica, alumina, zirconia, etc.). Moreover, these thin film materials may have functions of a surface protective film, a polarizing filter, a transparent conductor layer, and the like. For the formation of the thin film material, any known method such as vapor phase epitaxy (PVD and CVD), coating of a coating agent, formation of a fine particle film using nanoparticles, etc., a sol-gel method can be used.

When the face plate 1 is used as a touch panel, the thickness of the substrate 3 may be reduced so as to have flexibility, and a transparent conductor layer such as ITO may be provided on the back side. Or what adhered these resin on the outer surface of transparent base materials, such as glass, may be used as the base material 3. FIG.

The surface roughness of the outer surface of the face plate 1 for display device or the substrate 3 is 10 nm or more and 400 nm or less, preferably 360 nm or less, more preferably 300 nm or less. The shape of the irregularities on the outer surface of the face plate 1 for a display device is not particularly limited as long as the optical characteristics of the base material 3 are not impaired by diffraction or irregular reflection of incident light. It may be a simple shape. In general, when the surface roughness is within the above range, the surface hydrophobicity of the base material 3 can be further improved without deteriorating the surface characteristics of the base material 3, and the optical properties of visible light such as the transparency of the base material 3 can be improved. There is no loss of properties. The surface roughness can be measured using any known method such as a surface roughness meter or a three-dimensional measuring instrument. Further, the size of the unevenness can be measured by image analysis using a stereoscopic microscope or an electron micrograph.

Next, the display device face plate 10 and the manufacturing method thereof according to the first embodiment of the present invention will be described.
As shown in FIG. 2, in the face plate 10 for a display device according to the first embodiment of the present invention, an decyl group (C ₁₀ H ₂₁ : an alkyl group that is a hydrocarbon group) is formed on the outer surface of the substrate 12. Example) in which a hydrogen atom of a terminal methyl group is substituted with a trifluoromethyl group 19 (a part or all of the hydrogen atoms are substituted with one or both of a fluorine atom and a fluorocarbon group) A fluorine-containing organic thin film 11 including an example of a film substance having a fluorine-containing hydrocarbon group is formed. In the present embodiment, the fluorine-containing organic thin film 11 is a monomolecular film made of a film substance that is covalently bonded (an example of a chemical bond) to the outer surface of the substrate 12.

The face plate 10 for a display device is produced by bringing a treatment liquid containing a film compound having a hydrocarbon group into contact with the outer surface of the substrate 12 and reacting the film compound with the surface functional group of the substrate 12. Step C (see FIG. 3) for forming an organic thin film (an example of a substance having a hydrocarbon group present so as to cover at least a part of the outer surface of the base material 12) 18 containing the obtained film material, and a fluorocarbon group A part or all of the hydrogen atoms in the hydrocarbon groups contained in the organic thin film 18 are fluorine atoms by subjecting the outer surface of the base material 12 on which the organic thin film 18 has been formed in a gas atmosphere of a compound containing And a step A of forming the fluorine-containing organic thin film 11 substituted with one or both of fluorocarbon groups.

In addition, before the process A, you may roughen the outer surface of the base material 12 so that it may have the surface roughness and the magnitude | size of an unevenness | corrugation in the said range (process B). The order in which step B is performed may be before or after step C. That is, the steps A to C include (1) Step B → Step C → Step A (the organic thin film 18 is formed after roughening the outer surface of the substrate 12), and (2) Step C → Step B. → You may carry out in any order of step A (roughening the outer surface of the substrate 12 on which the organic thin film 18 is formed). The order of each step is the same for the manufacturing methods of the display device face plates 20 and 30 according to the second and third embodiments described later.

Next, step B will be described.
As a method for roughening the surface on the outer side of the substrate 12, the surface is roughened in advance using any known method such as sandblasting, mechanical polishing, and chemical treatment with chromic acid mixture, phosphoric acid, alkali, or the like. However, the low pressure plasma treatment can be performed in an atmosphere containing oxygen gas and chlorine gas. Plasma treatment conditions may be adjusted as appropriate so that a surface having a desired surface roughness and unevenness can be obtained. The apparatus and processing conditions used for the low-pressure plasma processing are the same as in the case of step A, and thus detailed description thereof is omitted.

Next, step C will be described.
The treatment liquid used for forming the organic thin film 18 in the step C is prepared by dispersing the film compound in a solvent. Here, “dispersion” means a state in which any one of a uniform solution, a suspension, and an emulsion is formed. Examples of the membrane compound that can be used include any compound that contains a chain-like lipophilic functional group and can form a film made of the membrane substance 2 on the outer surface of the substrate 12. In order to fix to the outer surface of the base material 12 through bonding with the surface functional group of the outer surface of 12, it is preferable to have a surface binding group at the terminal. Preferred surface functional groups include alkoxysilyl groups that react relatively rapidly with hydroxyl groups present on the surface of many materials at room temperature. In order to form a monomolecular film, the lipophilic functional group is preferably a linear long-chain alkyl group having self-organization.

As the film compound, for example, a silane compound represented by the following general formula (X) can be used.
Z-SiX _p Y _3-p (X)
In the formula (X), Z represents a substituent containing any one of an alkyl group having 25 or less carbon atoms, an aryl group, a vinyl group, and a silicone group,
X represents a hydrogen atom or a substituent containing any one of an alkyl group having less carbon atoms than Z, an aryl group, a vinyl group, and a silicone group;
Y represents a halogen atom or an alkoxyl group,
p represents 0, 1 or 2.

A preferred film compound is, for example, an alkoxysilane compound represented by any of the following formulas (XI) to (XV).
_{CH 3 (CH 2) n Si} (OA) 3 (XI)
[CH ₃ (CH ₂ ) _n ] ₂ Si (OA) ₂ (XII)
[CH ₃ (CH ₂ ) _n ] ₃ Si (OA) (XIII)
CH ₃ (CH ₂ ) _m —COO— (CH ₂ ) _n Si (OA) ₃ (XIV)
CH ₃ (CH ₂ ) _m —O— (CH ₂ ) _n Si (OA) ₃ (XV)
In the formulas (XI) to (XV), m and n each independently represent an integer of 0 or more and 24 or less (where m ≧ n), and A is an alkyl group, more preferably a methyl group or an ethyl group. Represents.

Specific examples of the membrane compound include compounds shown in the following (1) to (19).
(1) CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
(2) CH 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Si (OCH 3) 3
_{(3) CH 3 (CH 2} ) 6 Si (CH 3) 2 (CH 2) 9 Si (OCH 3) 3
(4) CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(5) CH ₃ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(6) CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(7) CH ₃ (CH ₂ ) ₇ C ₆ H ₄ SiCH _{3
(8) CH 3 CH 2 O} (CH 2) 15 Si (OC 2 H 5) 3
_{(9) CH 3 (CH 2} ) 2 Si (CH 2) 15 Si (OC 2 H 5) 3
_{(10) CH 3 (CH 2} ) 6 Si (CH 2) 9 Si (OC 2 H 5) 3
(11) CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CH ₃ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(13) CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) _{3
(14) CH 3 (CH 2} ) 7 C 6 H 4 Si (OC 2 H 5) 3
(15) [CH ₃ (CH ₂ ) ₅ ] ₂ Si (OCH ₃ ) ₂
(16) [CH ₃ (CH ₂ ) ₃ 5] ₃ SiOCH ₃
(17) [CH ₃ (CH ₂ ) ₅ ] ₂ Si (OC ₂ H ₅ ) ₂
(18) [CH ₃ (CH ₂ ) ₅ ] ₃ SiOC ₂ H ₅
(19) CH ₃ (CH ₂ ) ₅ SiCH ₃ (OCH ₃ ) ₂

The concentration of the membrane compound contained in the treatment liquid is preferably 0.1 mmol / L to 10 mmol / L. When the concentration of the membrane compound is less than 0.1 mmol / L, it is difficult to form a uniform organic thin film 18, and when the concentration exceeds 10 mmol / L, gelation is likely to occur and storage stability is reduced. To do.

As the solvent, any liquid that can dissolve or stably disperse the membrane compound can be used. Since the membrane compound has high hydrophobicity, an organic solvent is used to dissolve it. However, it is preferable to use water from the viewpoint of reducing the environmental load during the manufacturing of the face plate 10 for a display device. However, it is difficult to dissolve or stably disperse the membrane compound only by using water as it is. Therefore, when water is used as a solvent, the treatment liquid contains a surfactant and / or alcohol in order to solubilize or stably disperse the membrane compound in a solvent mainly composed of water.

Any surfactant can be used, but a tetraalkylammonium salt which is a cationic surfactant, more specifically, a tetraalkylammonium represented by the following formula (VIII): Salt.

In the formula (VIII),
R ¹ represents an alkyl group having 1 to 20 carbon atoms, more preferably 12 to 16 carbon atoms,
R ² , R ³ , and R ⁴ represent a methyl group or an ethyl group, more preferably a methyl group,
X represents a halogen.

A particularly preferred tetraalkylammonium salt is hexadecyltrimethylammonium bromide CH ₃ (CH ₂ ) ₁₅ N (CH ₃ ) ₃ Br.

The concentration of the tetraalkylammonium salt is preferably 0.1 mmol / L to 10 mmol / L, more preferably 0.5 mmol / L to 5 mmol / L. When the concentration is less than 0.1 mmol / L, the membrane compound cannot be sufficiently solubilized, and when it exceeds 10 mmol / L, the pH of the treatment liquid falls outside the optimum range described later or bubbles are generated. There is a fear.

As the alcohol, any alcohol that can uniformly disperse the membrane compound in water can be used. However, ethanol, propanol (1-propanol and 2) that are compatible with water and have high volatility are used. -Propanol), butanol (1-butanol, 2-butanol, 2-methyl-2-propanol) and ethylene glycol are preferred. These alcohols may be used alone, or any two or more kinds may be mixed and used at an arbitrary ratio.

The mixing ratio of water and alcohol is not particularly limited, but the volume ratio of water and alcohol is preferably 80:20 to 95: 5.

An acid or a base may be added to the treatment liquid in order to adjust the pH. A preferred pH range is 5-12. When the pH is less than 5, the organic thin film 18 having a high density is not formed, and the storage stability of the treatment liquid is lowered. Moreover, when pH exceeds 12, there exists a possibility that the formed organic thin film 18 may be destroyed by the alkali hydrolysis of a siloxane bond.

The treatment liquid is prepared by a method having a step of mixing and dispersing a membrane compound and a solvent (preferably water containing a surfactant and / or alcohol). First, those components weighed so as to have a desired composition ratio are mixed. The order of adding each component is not particularly limited. Next, when the mixture is treated using an ultrasonic disperser or a homogenizer, a part of the alkoxysilyl group is converted into a silanol group by hydrolysis, and a uniform and transparent treatment liquid is obtained. The treatment temperature and time are not limited, but when an ultrasonic disperser is used, for example, the treatment is performed at room temperature for 10 minutes.

Formation of the organic thin film 18 using the treatment liquid obtained as described above can be performed using, for example, the following method. First, a treatment liquid is applied to the outer surface of the substrate 12 and left to stand until most of the solvent is volatilized (for example, in the atmosphere at room temperature for 1 hour). The film compound is bonded to the outer surface of the base material 12 through a covalent bond (siloxane bond) formed by a condensation reaction between a hydroxyl group (not shown) on the outer surface of the base material 12 and an alkoxysilyl group. A (monomolecular film) 18 is formed (see FIG. 3).

In this case, depending on the concentration of the treatment liquid, an extra film compound may remain on the outer surface of the substrate 12, but in such a case, it may be removed by washing with a solvent. If there is a small amount of excess membrane compound, there is a problem that even if it is left unwashed, a condensation reaction occurs due to silanol groups generated by hydrolysis of alkoxyl groups by moisture in the air, resulting in the formation of membrane materials. There is no.

In order to accelerate the condensation reaction between the alkoxysilyl group and the hydroxyl group on the outer surface of the substrate 12, a condensation catalyst may be added. As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
A specific example of a titanate chelate is bis (acetylacetonyl) di-propyl titanate.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above metal salts (can be used in a mass ratio of 1: 9 to 9: 1, preferably around 1: 1), the reaction time is further shortened. it can.

For example, as a condensation catalyst, H3 of Japan Epoxy Resin Co., which is a ketimine compound, can be used instead of dibutyltin diacetate.

Alternatively, as a condensation catalyst, a mixture of H3 and dibutyltin diacetate manufactured by Japan Epoxy Resin Co., Ltd. (mixing ratio is 1: 1) may be used.

The ketimine compound that can be used here is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

Moreover, although it does not specifically limit as an organic acid which can be used, For example, a formic acid, an acetic acid, propionic acid, a butyric acid, malonic acid etc. are mentioned.

Alternatively, in the above compounds (1) to (19), a halosilane compound having a halosilyl group (chlorosilyl group or bromosilyl group) instead of the alkoxysilyl group may be used as the film compound. In this case, a silanol condensation catalyst and a co-catalyst are not required, but halosilyl groups react quickly with water (including moisture in the air) and alcohol, so that a solvent containing water or alcohol cannot be used as a solvent. The application of the treatment liquid to the outer surface of the substrate 12 and the reaction must be performed under dry conditions (relative humidity of 45% or less).

Next, a face plate 20 for a display device according to a second embodiment of the present invention will be described. As shown in FIG. 4, in the display device face plate 20, the fluorine-containing organic thin film 21 includes polysiloxane molecules 24 formed from alkoxysilane and / or alkoxypolysiloxane. More specifically, as shown in FIG. 4, the polysiloxane molecule 24 is fixed to the outer surface of the substrate 22 through bonding with hydroxyl groups (an example of surface functional groups) on the outer surface of the substrate 22. , A polysiloxane molecule coating 27 covering the surface in a network, and an decyl group (C ₁₀ H ₂₁ : an alkyl group that is a hydrocarbon group) formed on the outer surface of the substrate 12 and the polysiloxane molecule 13. Example) Film material in which the hydrogen atom of the terminal methyl group is substituted with a trifluoromethyl group (fluorine-containing in which part or all of the hydrogen atoms are substituted with either or both of fluorine atoms and fluorocarbon groups) An example of a film substance having a hydrocarbon group). The membrane material is formed by a reaction between an alkoxysilyl group at the end of the membrane compound (an example of a reactive group) and a hydroxyl group (an example of a surface functional group) on the outer surface of the substrate 22 or a silanol group on the polysiloxane molecule 24. It is fixed to the polysiloxane molecules 24 that coat the outer surface of the base material 22 and the outer surface of the base material 22 in a mesh form through the formed bond (Si—O— bond).

The face plate 20 for a display device is brought into contact with a film compound having a hydrocarbon group on the outer surface of a base material 22 and a treatment liquid in which alkoxysilane and / or alkoxypolysiloxane are mixed and dispersed in a solvent. Step C (see FIG. 5) for forming an organic thin film 18 containing a film substance generated by reaction with the surface functional group 22 and a network-like polysiloxane molecule 24, and in a gas atmosphere of a compound containing a fluorocarbon group By subjecting the outer surface of the base material 22 on which the organic thin film 28 has been formed to low-pressure plasma treatment, some or all of the hydrogen atoms in the hydrocarbon groups contained in the organic thin film 28 are either fluorine atoms or fluorocarbon groups. Step A for forming the fluorine-containing organic thin film 21 substituted with one or both, and, if necessary, the outer surface of the substrate 22 before the step A, the surface roughness within the above range and Produced by the process and a step B of roughened to have a size of convex.
Hereinafter, a method for manufacturing the display device face plate 20 will be described.

Since the material that can be used as the base material 22 is the same as that of the base material 12 that can be used for manufacturing the face plate 10 for a display device according to the first embodiment, detailed description thereof is omitted. To do.

The treatment liquid used in Step C is prepared by mixing and dispersing the film compound and alkoxysilane and / or alkoxypolysiloxane in a solvent. Specific examples of the compound that can be used as the film compound, the solvent and the surfactant that can be used are the same as those in the method of manufacturing the face plate 10 for a display device, and thus detailed description thereof is omitted.

The treatment liquid used for manufacturing the display device face plate 20 contains alkoxysilane and / or alkoxypolysiloxane in order to improve the durability of the obtained display device face plate 20. The alkoxysilane is a compound represented by the formula SiH _x (OA) _4-x (formula (VI)), and the alkoxypolysiloxane is represented by the formula (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA). ₃ It is a compound represented by (Formula (VII)). In these formulas, x is 0, 1, or 2, A represents an alkyl group, preferably a methyl group or an ethyl group, and n is 0, 1, or 2.

Specific examples of the alkoxysilane represented by the above formula (VI) and the alkoxypolysiloxane represented by the above formula (VII) include the following compounds (21) to (28).
(21) Si (OCH ₃ ) ₄
(22) SiH (OCH ₃ ) ₃
(23) SiH ₂ (OCH ₃ ) ₂
(24) (CH ₃ O) ₃ SiOSi (OCH ₃ ) ₃
(25) Si (OC ₂ H ₅ ) ₄
(26) SiH (OC ₂ H ₅ ) ₃
(27) SiH ₂ (OC ₂ H ₅ ) _{2
(28) (H 5 C 2} O) 3 SiOSi (OC 2 H 5) 3

These may be used alone, or any two or more of them may be mixed and used in an arbitrary ratio. In order to obtain a suitable face plate 20 for a display device in which water repellency, oil repellency and antifouling properties are maintained over a long period of time, the composition ratio (ratio of the number of silicon atoms) of the film compound and alkoxysilane and / or alkoxypolysiloxane. Is preferably from 1:10 to 1: 0, more preferably from 1: 3 to 3: 1.

Furthermore, the total concentration of the membrane compound and alkoxysilane and / or alkoxypolysiloxane is preferably 0.1 mmol / L to 50 mmol / L, more preferably 0.1 mmol / L to 10 mmol / L. When the total concentration is less than 0.1 mmol / L, it is difficult to form a uniform lipophilic film 17, and when the total concentration exceeds 50 mmol / L, gelation or the like is likely to occur, and storage stability is improved. descend. In particular, when the total concentration is 10 mmol / L to 0.1 mmol / L, gelation of the treatment liquid can be prevented, and the lifetime can be secured up to about 1 month.

The treatment liquid used for the production of the display device face plate 20 is a mixture comprising a film compound and alkoxysilane and / or alkoxypolysiloxane and a solvent (preferably water containing a surfactant and / or alcohol). Is prepared by a method having a step of mixing and dispersing. First, those components weighed so as to have a desired composition ratio are mixed. The order of adding each component is not particularly limited. Next, when the mixture is treated using an ultrasonic disperser or a homogenizer, a part of the alkoxysilyl group is converted into a silanol group by hydrolysis, and a uniform and transparent treatment liquid is obtained. About processing temperature and time, it is the same as that of the case of the processing liquid used for manufacture of the above-mentioned face plate 10 for display devices. The processing conditions of the base material 22 with the processing liquid thus obtained are the same as in the case of manufacturing the display device face plate 10 according to the first embodiment, but are obtained in this way. As shown in FIG. 6, the film is an organic thin film 26 including a film 27a of polysiloxane molecules (24a) having unreacted silanol groups (25). Although it can be used in the next step B as it is, heat treatment may be performed in order to improve the water / oil repellency / antifouling property and the durability of the finally obtained fluorine-containing organic thin film 21. The heat treatment is preferably performed at 120 ° C. to 300 ° C. for about 15 minutes to 1 hour, for example. By the heat treatment, unreacted silanol groups 25 undergo a dehydration reaction, and an organic thin film 28 including a film substance and network-like polysiloxane molecules 24 is formed (see FIG. 5).

Next, the hydrogen in the hydrocarbon groups contained in the organic thin film 28 is obtained by subjecting the outer surface of the base material 22 on which the organic thin film 28 is formed in the gas atmosphere of the compound containing a fluorocarbon group in the process A to low pressure plasma treatment. A fluorine-containing organic thin film 21 in which some or all of the atoms are substituted with one or both of fluorine atoms and fluorocarbon groups is formed to obtain a face plate 20 for a display device. Since this is the same as the manufacturing method of the face plate 10 for a display device according to the first embodiment, detailed description is omitted. Similarly, detailed description of the process B is also omitted.

The display device face plate 20 thus obtained can be used in the same manner as the display device face plate 10 according to the first embodiment.

Next, a face plate 30 for a display device according to a third embodiment of the present invention will be described with reference to FIG. In the display device face plate 30, the fluorine-containing organic thin film 31 is a polysiloxane molecule (34) fixed on the outer surface of the substrate 32 through bonding with a hydroxyl group (an example of a surface functional group) of the substrate 32. And a film substance in which the hydrogen atom of the terminal methyl group in the decyl group (C ₁₀ H ₂₁ : an example of an alkyl group that is a hydrocarbon group) formed thereon is substituted with a trifluoromethyl group ( A film having a two-layer structure comprising a film of an example of a film substance having a fluorine-containing hydrocarbon group in which part or all of hydrogen atoms are substituted with either or both of a fluorine atom and a fluorocarbon group. The membrane material is composed of a bond (Si—O— bond) formed by a reaction between an alkoxysilyl group (an example of a reactive group) at the end of the membrane compound and a silanol group (Si—OH) (not shown) on the polysiloxane molecule 34. ) To the coating 37 of polysiloxane molecules (34) covering the outer surface of the substrate 32 (see FIG. 7).

In the present embodiment, the display device face plate 30 first contacts a treatment liquid containing alkoxysilane and / or alkoxypolysiloxane with the outer surface of the substrate 32, and coats the outer surface of the substrate 32 with polysiloxane molecules. 37, and then a treatment liquid containing a film compound is brought into contact with the surface of the substrate 32 on which the polysiloxane molecule film 26 is formed on the outer surface to form a film of the film material on the polysiloxane molecule film 37. Then, the step A for obtaining the base material 32 on which the organic thin film 38 is formed and the outer surface of the base material 32 on which the organic thin film 38 is formed in a gas atmosphere of a compound containing a fluorocarbon group are subjected to low-pressure plasma treatment. Fluorine-containing compounds in which some or all of the hydrogen atoms in the hydrocarbon groups contained in the organic thin film 28 are substituted with either or both of fluorine atoms and fluorocarbon groups. Step C for forming the thin film 31 and Step B for roughening the outer surface of the base material 32 so as to have the surface roughness and the size of the irregularities within the above range before the step A as necessary. It can be manufactured by the method of having. Regarding the preparation conditions (solvent, concentration, etc.) of each solution, the coating 37 of the polysiloxane molecules (34) on the outer surface of the substrate 32, and the coating conditions (treatment conditions) of the film substance, the first and second described above. Since it is the same as the manufacturing method of the display device faceplates 10 and 20 according to the embodiment, detailed description is omitted.

Next, a face plate 40 for a display device according to a fourth embodiment of the present invention will be described with reference to FIGS. 8 (a) and 8 (b). In the water / oil repellent / antifouling member 40 according to the fourth embodiment of the present invention, a fluorine-containing organic polymer (of a substance having a fluorine-containing functional group) is formed so as to cover at least a part of the outer surface of the substrate 42. An example) 41 exists.
As shown in FIG. 8A, the base material 42 used for manufacturing the water / oil repellent / antifouling member 40 is covered with a hydrocarbon group 43 on the outer surface. On the outer surface of the water / oil repellent / antifouling member 40 after the low pressure plasma treatment in step A, as shown in FIG. 8B, the hydrocarbon group covering the outer surface of the base material 42 before the low pressure plasma treatment. A part of 43 hydrogen atoms is substituted with a trifluoromethyl group 44 which is an example of a fluorocarbon group.

The water / oil repellent / antifouling member 40 comprises a step A for subjecting the base material 42 to low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group, and an outer side of the base material 42 before the step A if necessary. And a step B of roughening the surface so as to have the surface roughness and the size of the irregularities within the above ranges.
When plasma is generated by high frequency discharge in a gas atmosphere of a compound containing a fluorocarbon group, a fluorocarbon radical such as a fluorine radical (· F) or a trifluoromethyl radical (· CF ₃ ) is generated. These radicals substitute the hydrogen atom of the hydrocarbon group on the outer surface of the acrylic base material 42 with the trifluoromethyl group 43 (FIG. 8B).

About the base material 42 having a hydrocarbon group at least in the vicinity of the outer surface, the surface of the compound containing a fluorocarbon group is directly roughened so as to have a predetermined surface roughness and unevenness by the step B. The display device face plate 40 is obtained by performing low-pressure plasma treatment in a gas atmosphere (step A). The method for manufacturing a display device face plate according to the present embodiment is applied to an article made of an inorganic material or a member thereof. When doing so, the process C is implemented and the film which contains an organic polymer as the base material 42 is formed in the outer surface. There are no particular restrictions on the type and molecular weight of the organic polymer used to form the coating, and it has a hydrocarbon group in the main chain and side chain, and in step A, part or all of the hydrogen atoms are fluorine atoms and Any organic polymer can be used as long as it can be substituted with a fluorocarbon group. The film may be formed by spray coating using a solution containing an organic polymer, spin coating, dip coating, cast method, or the like, and a polymerization reaction is caused on the surface of the inorganic material by plasma polymerization or the like. To produce an organic polymer.

For the roughening method of the outer surface of the base material 42 used in the step B and the order of performing the steps A to C, the face plate 10 for a display device according to the first to third embodiments described above, Since it is the same as the manufacturing method of 20 and 30, detailed description is abbreviate | omitted.

Examples of the display device using the display device faceplate 1 obtained as described above include CRT (cathode ray tube, cathode ray tube), liquid crystal display device, plasma display, organic and inorganic EL display devices, and the like.
Articles using the display device incorporating the face plate 1 include a mobile phone, an electronic desk calculator, an electronic computer or a display for an electronic computer, a PDA (personal digital assistant), a portable game machine, a portable GPS terminal, a car navigation system, Examples include a television receiver, a portable DVD player, a digital camera, a video recording device, a cash dispenser (CD) device, an automatic teller machine (ATM), and an automatic ticket machine.

Next, examples carried out for confirming the effects of the present invention will be described. In the following examples, the molecular composition ratio means a molar ratio unless otherwise specified. Moreover,% means weight%.

Example 1
Octadecyltrimethoxysilane CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ (film compound) and tetramethoxysilane Si (OCH ₃ ) ₄ are weighed to a molar ratio of 3: 1, and 0.1% in ethanol. When mixed at 01 mol / L and treated with a homogenizer for about 10 minutes, a part of each methoxysilyl group (—Si (OCH ₃ )) is hydrolyzed by moisture contained in ethanol, and —Si A treatment liquid containing a substance converted into (OH) ₃ group, = Si (OH) ₂ group, or ≡SiOH group (silanol group) was prepared.

Next, a well-dried glass faceplate substrate is prepared as an inorganic substrate, and the treatment liquid prepared above is applied to the outer surface in the air (relative humidity 57% to 70%), and further in the air. It was left for about 1 hour. During this time, most of the ethanol in the treatment solution evaporates into the air, and the entire surface is chemically bonded to the surface by dehydration reaction with silanol groups (Si-OH) generated by hydrolysis of alkoxysilyl groups. A film composed of network-like polysiloxane molecules fixed via (silanol bond) and octadecylsilyl groups fixed on the surface of the faceplate substrate or on the polysiloxane molecules was formed.

Before the coating is completely cured, the unreacted excess octadecyltrimethoxysilane and tetramethoxysilane are washed away with a water-ethanol mixed solvent (this step is not always necessary if the coating amount and the liquid concentration are properly adjusted). In this case, the polysiloxane molecule having a thickness of about 5 nm and the octadecylsilyl group immobilized on the outer surface of the face plate or on the polysiloxane molecule were obtained. A film consisting of the above can be formed in a state of being chemically bonded to the outer surface of the faceplate substrate (FIG. 6).

Thereafter, heat treatment is performed in air at a temperature of 120 to 300 ° C. for about 30 minutes, and unreacted silanol groups (—SiOH) are completely dehydrated to form an organic thin film having a polysiloxane bond (FIG. 5).

Next, the outer surface of the face plate substrate on which the organic thin film was formed was subjected to plasma treatment in a tetrafluoromethane (CF ₄ ) atmosphere containing oxygen under the conditions shown in Table 1. In Table 1, sccm used as a unit of flow rate is a non-SI unit, and 1 sccm = 1.69 × 10 ⁻⁴ Pa · m ³ / sec.

The water droplet contact angle of the face plate thus obtained was measured. Measurements were made at five different points (IV) on the same sample. The measurement results are as shown in Table 2 below. In Table 2, “CA” means a contact angle, and “Avg.” And “SD” mean an average value and a standard deviation, respectively.

A significant increase in water droplet contact angle was observed for all samples. This is because, as shown in FIG. 2, the hydrocarbon groups in the organic thin film react with the .CF ₃ radicals generated in the plasma, and the hydrogen atoms are replaced with —CF ₃ groups. _This is probably because the water repellency of the surface was improved by the bonding of the _three groups.

In addition to CF ₄ , compounds containing CF ₂ groups or CF ₃ groups such as C ₂ F ₆ , C ₂ F ₄ , and CHF ₃ could be used similarly.

Example 2
A face plate was produced under the same conditions as in Example 1 except that the treatment liquid did not contain tetramethoxysilane. In this case, the fluorine-containing organic thin film formed on the outer surface was a monomolecular film containing no polysiloxane molecules. As for the water droplet contact angle, the same results as in Example 1 were obtained. However, the wear resistance of the fluorine-containing organic thin film was inferior to that obtained in Example 1.

Example 3
First, under the conditions shown in Table 3, the surface of the glass faceplate substrate was subjected to low-pressure plasma treatment, and the surface was roughened.

By this plasma roughening treatment, fine unevenness of several tens to several hundreds of nanometers could be formed on the surface of the faceplate substrate.
Thereafter, under the same conditions as in Example 1, formation of an organic thin film and low-pressure plasma treatment in a tetrafluoromethane gas atmosphere were performed.

Table 4 shows the measurement results of the water droplet contact angle of the face plate thus obtained.

It can be seen that the water droplet contact angle on the obtained face plate is greatly increased by performing the plasma surface roughening treatment. Further, in the face plate obtained in this example, a decrease in light transmittance, generation of interference fringes, haze, and the like were not observed.

Example 4: Production of a water / oil repellent / antifouling member based on a transparent acrylic resin substrate First, after the transparent acrylic resin substrate as a substrate was washed with ethanol, under the conditions shown in Table 5 below, Low-pressure plasma treatment (O ₂ plasma treatment) in an oxygen gas atmosphere was performed. Next, plasma treatment was performed in a tetrafluoromethane (CF ₄ ) atmosphere containing oxygen under the conditions shown in Table 6.

The water droplet contact angle of the water / oil repellent / antifouling member thus obtained was measured. Measurements were made at five different points (IV) on the same sample. The measurement results are as shown in Table 7 below. The water droplet contact angle of the acrylic resin substrate before treatment was 75.0 degrees.

A significant increase in water droplet contact angle was observed for all samples. This is because, as shown in FIG. 2B, the hydrocarbon group on the surface of the acrylic resin substrate reacts with the .CF ₃ radical generated in the plasma, and the hydrogen atom is replaced with the —CF ₃ group. It is thought that the surface water repellency was improved by bonding a large number of CF ₃ groups.

Here, the O ₂ plasma treatment has an action of cleaning the surface of the acrylic resin substrate and an action of roughening the surface of the member, and the surface roughness can be controlled by arbitrarily controlling the power of the high frequency power source and the treatment time. Can be controlled within a range of several nanometers to several hundred microns, and the final water droplet contact angle can be controlled to about 165 to 100 degrees. In particular, if the water droplet contact angle was controlled to be 150 degrees or more, a high-performance oil-repellent and antifouling member with extremely low surface energy could be produced. Further, when the surface roughness was set to be equal to or less than the wavelength of visible light (for example, 400 nm), the transparency of the acrylic resin substrate used as the base material was not impaired.

In addition to CF ₄ , compounds containing CF ₂ groups or CF ₃ groups such as C ₂ F ₆ , C ₂ F ₄ , and CHF ₃ could be used similarly.

The materials that can be used are of any material that contains hydrocarbon groups, and in addition to artificial materials such as synthetic resin, synthetic leather, and synthetic fibers, it also applies to natural materials such as woody materials, paper, and wool. I was able to handle it.

The article to which the present invention can be applied may be in any form as long as it is a display device. Specifically, it can be used for a mobile phone, an electronic computer, a PDA, a GPS, a television receiver, a cash dispenser (CD) device, a display device installed in an ATM device, or a member used for them. . Furthermore, the present invention can be applied to optical lenses and casings used in these devices.

DESCRIPTION OF SYMBOLS 1 Display apparatus face plate 2 Transparent substance which has a fluorine-containing functional group 3 Base material 10, 20, 30 Display apparatus face plate 11 Substance which has a fluorine-containing functional group 11a, 21, 31 Fluorine-containing organic thin films 12, 22, 32, 42 Substrate 13, 23, 33 Film material 24, 34 having a hydrocarbon group Polysiloxane molecule 24a Polysiloxane molecule 25 having a silanol group 25 Silanol group 26 Organic thin film 27 having a silanol group 27, 37 Polysiloxane molecule coating 27a Polysiloxane molecule coatings 18, 28, 38 having silanol groups Organic thin film 19, 44 Trifluoromethyl group 41 Fluorinated organic polymer 43 Hydrocarbon group

Claims (26)

1. A transparent substance having a fluorine-containing functional group in which some or all of the hydrogen atoms in the hydrocarbon group are substituted with either or both of a fluorine atom and a fluorocarbon group is exposed on the outer surface. A face plate for a display device, wherein the face plate is present to cover at least a part of a transparent substrate.
2. A substance having a hydrocarbon group present so that the fluorine-containing functional group covers at least a part of the surface on the outer side of the substrate is subjected to low pressure plasma in a gas atmosphere of a compound containing a fluorocarbon group. The display device faceplate according to claim 1, wherein the display device faceplate is obtained by processing.
3. The substance having a fluorine-containing functional group includes a linear film substance having the fluorine-containing functional group, and forms a fluorine-containing organic thin film chemically bonded to the outer surface of the substrate. The face plate for a display device according to any one of claims 1 and 2.
4. The fluorine-containing functional group is any one of a hydrocarbon group, a hydrocarbon group having an ester group, and a hydrocarbon group having an ether group, and any one or more hydrogen atoms are either a fluorine atom or a fluorocarbon group The face plate for a display device according to claim 3, wherein the functional group is substituted with a functional group.
5. The fluorine-containing functional group is a functional group in which any one or more hydrogen atoms in the functional groups represented by the following formulas (I) to (V) are substituted with either a fluorine atom or a fluorocarbon group The display device face plate according to claim 3, wherein the display device face plate is a display device face plate.
   

   

   In the formulas (I) to (V), m and n each independently represent an integer of 0 or more and 24 or less, and m ≧ n.
6. The display device according to claim 3, wherein the fluorine-containing organic thin film is a monomolecular film of the film substance chemically bonded to a surface on the outer side of the base material. For face plate.
7. 6. The face plate for a display device according to claim 3, wherein the fluorine-containing organic thin film contains polysiloxane molecules formed from alkoxysilane and / or alkoxypolysiloxane.
8. The fluorine-containing organic thin film is bonded and fixed to the outer surface of the base material through the polysiloxane molecule film fixed and bonded to the outer surface of the base material. The face plate for a display device according to claim 7.
9. The surface on the outer side of the substrate through a bond formed by a reaction between the alkoxysilyl group and a surface functional group present on the surface on the outer side of the substrate. A part of the film substance having the fluorine-containing hydrocarbon group is directly bonded to the surface on the outer side of the base material, and the remaining part of the base material is bonded to the base material through the polysiloxane molecule coating. 7. The face plate for a display device according to claim 6, wherein the face plate is bonded and fixed to a surface on the outer side.
10. The polysiloxane molecule is formed by a condensation reaction of an alkoxysilane represented by the following formula (VI) and / or an alkoxypolysiloxane represented by the formula (VII): 10. The face plate for a display device according to any one of 1 to 9.
    SiH _x (OA) _4-x (VI)
    (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (VII)
    In the formulas (VI) and (VII),
    x is 0, 1, or 2;
    A represents an alkyl group,
    n is 0, 1, or 2.
11. 3. The face plate for a display device according to claim 1, wherein the substance having a fluorine-containing functional group is a fluorine-containing organic polymer having the fluorine-containing functional group.
12. The face plate for a display device according to any one of claims 1 to 11, wherein the outer surface has a surface roughness of 10 nm or more and 400 nm or less.
13. A gas atmosphere containing a fluorocarbon group is formed on the surface of the transparent substrate on which the transparent substance having a hydrocarbon group exists so as to cover at least part of the surface of the face plate. A process for producing a face plate for a display device, comprising a step A of low-pressure plasma treatment.
14. 14. The water repellent method according to claim 13, wherein, in the step A, the surface on the outer side of the substrate is subjected to a low pressure plasma treatment in a mixed atmosphere of a compound gas containing a fluorocarbon group and an oxygen gas. Manufacturing method of oil-repellent antifouling member.
15. 15. The method according to claim 13, further comprising a step B of forming irregularities having a surface roughness of 10 nm or more and 400 μm or less on the outer surface before the step A. 15. Of manufacturing a face plate for a display device.
16. Before the step A, in a gas atmosphere of a compound containing a fluorocarbon group, the surface of the substance having a hydrocarbon group on the surface on the outer side of the substrate is subjected to low-pressure plasma treatment. The method for manufacturing a face plate for a display device according to any one of claims 13 to 15.
17. In the step C, a treatment liquid containing a membrane compound having a hydrocarbon group is brought into contact with the surface on the outer side of the substrate, and the surface functionality of the surface on the outer side of the membrane compound and the substrate is measured. 17. The method for producing a face plate for a display device according to claim 16, wherein an organic thin film containing a hydrocarbon group is formed by reaction with a group.
18. 18. The method for manufacturing a face plate for a display device according to claim 17, wherein the film compound includes any one of a hydrocarbon group, a hydrocarbon group having an ester group, and a hydrocarbon group having an ether group.
19. 19. The method for manufacturing a face plate for a display device according to claim 17, wherein the film compound is a film compound represented by the following formula (X).
    Z-SiX _p Y _3-p (X)
    In the formula (X), Z represents a substituent containing any one of an alkyl group having 25 or less carbon atoms, an aryl group, a vinyl group, and a silicone group,
    X represents a hydrogen atom or a substituent containing any one of an alkyl group having less carbon atoms than Z, an aryl group, a vinyl group, and a silicone group;
    Y represents a halogen atom or an alkoxyl group,
    p represents 0, 1 or 2.
20. 20. The face plate for a display device according to claim 17, wherein the film compound is a film compound represented by any of the following formulas (XI) to (XV): Method.
    _{CH 3 (CH 2) n Si} (OA) 3 (XI)
    [CH ₃ (CH ₂ ) _n ] ₂ Si (OA) ₂ (XII)
    [CH ₃ (CH ₂ ) _n ] ₃ Si (OA) (XIII)
    CH ₃ (CH ₂ ) _m —COO— (CH ₂ ) _n Si (OA) ₃ (XIV)
    CH ₃ (CH ₂ ) _m —O— (CH ₂ ) _n Si (OA) ₃ (XV)
    In the formulas (XI) to (XV), m and n each independently represent an integer of 0 to 24, m ≧ n, and A represents an alkyl group.
21. 21. The process according to claim 17, wherein the treatment liquid contains an alkoxysilane represented by the following formula (VI) and / or an alkoxypolysiloxane represented by the formula (VII). The manufacturing method of the face plate for display apparatuses as described.
    SiH _x (OA) _4-x (VI)
    (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (VII)
    In the formulas (VI) and (VII),
    x is 0, 1, or 2;
    A represents an alkyl group,
    n is 0, 1, or 2.
22. In the step C, a surface of the substrate on the outer side is treated with a solution containing the alkoxysilane and / or the alkoxypolysiloxane to form a polysiloxane molecule film on the surface, and then the treatment 21. The organic thin film is formed on the polysiloxane molecule film by treating the base material on which the polysiloxane molecule film is formed with a liquid. Manufacturing method of face plate for display device.
23. 17. The method of manufacturing a face plate for a display device according to claim 16, wherein a film containing an organic polymer is formed as the substrate in the step C.
24. The display apparatus using the face plate for display apparatuses of any one of Claim 1 to 12.
25. An article using the display device according to claim 24.
26. 26. The article is any one of a mobile phone, an electronic computer or a display device for an electronic computer, a portable information terminal, a GPS terminal, a television receiver, a cash dispenser device, and an automatic teller machine. The article described.

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