JP5641498B2 - Water / oil repellent transparent member, method for producing the same, and article using them - Google Patents

Description

The present invention relates to a water- and oil-repellent transparent member, a method for producing the same, and an article using the same. More specifically, the water-repellent and water-repellent material has high durability, can be produced at low cost, and is highly safe for human bodies and the environment. The present invention relates to an oily transparent member, a method for producing the same, and an article using them.

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 transparent members used in buildings, automobiles, ships, airplanes, trains, etc., there is a demand for improved antifouling properties for reasons such as public health requirements.

There are two methods for preventing contamination on the surface of the member: a method of forming a film with 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. Therefore, there is a demand for a technology that reduces the environmental damage when the product is discarded.

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

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

JP 2005-206447 A JP-A-2005-290118

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.

The present invention has been made in view of such circumstances, and an object thereof is to provide a water- and oil-repellent transparent member that has a low environmental impact during processing and disposal and can be manufactured at low cost, a method for manufacturing the same, and an article using the same. And

According to the first aspect of the present invention that meets the above-mentioned object, at least a part of the transparent base material is a polysiloxane molecule formed from alkoxysilane and / or alkoxypolysiloxane, and a hydrocarbon group having 6 to 25 carbon atoms. Fluorine-containing functional groups in which some or all of the hydrogen atoms are substituted with either or both of fluorine atoms and fluorocarbon groups by plasma treatment in a gas atmosphere of a compound containing fluorocarbon groups The polysiloxane molecule is covered with a transparent material including a film material having, and the polysiloxane molecule is bonded to the surface of the base material through a bond formed by a reaction between an alkoxysilyl group and a surface functional group present on the surface of the base material. fixed to form a film, the film material having the fluorinated functional group, and characterized in that through a coating of the polysiloxane molecules are bound and fixed to the surface of the substrate It is intended to solve the above problems by providing a repellency transparent member that.
According to a second aspect of the present invention, a part or all of hydrogen atoms in a polysiloxane molecule formed from alkoxysilane and / or alkoxypolysiloxane and a hydrocarbon group having 6 to 25 carbon atoms are fluorocarbon. The substrate is covered with a transparent substance including a film substance having a fluorine-containing functional group substituted with one or both of a fluorine atom and a fluorocarbon group by plasma treatment in a gas atmosphere of a compound containing a group, The siloxane molecule is fixed on the surface of the substrate through a bond formed by a reaction between an alkoxysilyl group and a surface functional group present on the surface of the substrate, and has a fluorine-containing functional group. A part of the film substance is directly bonded to the surface of the substrate, and the rest is bonded and fixed to the surface of the substrate through the polysiloxane molecule coating. By providing a repellency transparent member it is intended to solve the above problems.

Cover at least part of the surface of the transparent substrate with a substance 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. Thereby, the surface energy of a transparent base material can be reduced and high water and oil repellency can be provided.

In the water- and oil-repellent transparent member according to the first and second aspects 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. In which any one or more hydrogen atoms may be substituted with either a fluorine atom or a fluorocarbon group.

In the water / oil repellent member according to the first and second aspects of the present invention, the fluorine-containing functional group may be any one or more of the functional groups represented by the following formulas (I) to (V): It may be a functional group in which a hydrogen atom is substituted with either a fluorine atom or a fluorocarbon group.

In 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 water and oil repellent transparent member according to the first and second aspects of the present invention, it is preferable that the surface roughness of the base material is 10 nm or more and 400 nm or less.
If the surface roughness of the water / oil repellent transparent member is 400 nm or less, which is the shortest wavelength of visible light, the optical characteristics of the water / oil repellent transparent member, particularly transparent, even when a transparent substrate is used. High water and oil repellency and antifouling properties can be imparted without impairing properties.

A third aspect of the present invention is represented by a film compound having a hydrocarbon group having 6 to 25 carbon atoms, an alkoxysilane represented by the following formula (VI) and / or the following formula (VII): A treatment liquid containing alkoxypolysiloxane is brought into contact with the surface of a transparent substrate, and chemically bonded to the surface of the substrate by a reaction between the film compound and a surface functional group of the substrate, and at least a part of the surface Forming an organic thin film having a hydrocarbon group on the surface of the substrate;
The surface of the base material on which the organic thin film is formed is subjected to low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group, and a part of hydrogen atoms in the hydrocarbon group of the organic thin film Alternatively, the present invention solves the above-mentioned problems by providing a method for producing a water / oil repellent transparent member comprising the step A of replacing all or all of fluorine atoms and fluorocarbon groups with one or both of them. .
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 a fourth aspect of the present invention, the surface of a transparent substrate is treated with a solution containing an alkoxysilane represented by the above formula (VI) and / or an alkoxypolysiloxane represented by the above formula (VII). Forming a polysiloxane molecule film on the surface, and then bringing a treatment liquid containing a film compound having a hydrocarbon group having 6 to 25 carbon atoms into contact with the surface of the polysiloxane molecule film, A step C of forming an organic thin film having a hydrocarbon group by chemically bonding to the surface of the polysiloxane molecule coating by a reaction with a surface functional group of the polysiloxane molecule coating; The surface of the base material formed on the surface is subjected to low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group, and part or all of the hydrogen atoms in the hydrocarbon group of the organic thin film are removed from the fluorine atom and fluorine. It is intended to solve the above problems by providing a method for producing a water and oil repellent transparent member, which comprises a step A of substituted with one or both of the carbon groups.

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, a water / oil repellent transparent member having water / oil repellent / antifouling properties can be produced at a lower cost than when an expensive fluorocarbon film compound is used.

In the method for producing a water / oil repellent transparent member according to the third and fourth aspects of the present invention, in the step A, the substrate is formed in a mixed atmosphere of a compound gas containing a fluorocarbon group and an oxygen gas. Low pressure plasma treatment may be performed.
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 producing a water- and oil-repellent transparent member according to the third and fourth aspects of the present invention, an uneven surface having a surface roughness of 10 nm or more and 400 nm or less is formed on the surface of the substrate before the step A. You may have further the process B.
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, the transparency of the water / oil repellent transparent member is impaired even when a transparent substrate is used. High water and oil repellency and antifouling properties can be imparted.

In the method for producing a water- and oil-repellent transparent member according to the third and fourth aspects of the present invention, the film compound is any one of a hydrocarbon group, a hydrocarbon group having an ester group, and a hydrocarbon group having an ether group. May be included.

In the method for producing a water / oil repellent transparent member according to the third and fourth aspects 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 of an alkyl group having 6 to 25 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 producing a water / oil repellent transparent member according to the third and fourth aspects of the present invention, the film compound containing a hydrocarbon group is represented by any of the following formulas (XI) to (XV): It may be a membrane compound.
_{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 formulas (XI) to (XV), m and n each independently represent an integer of 0 or more and 24 or less, m ≦ n, and A represents an alkyl group.

The fifth aspect of the present invention solves the above problem by providing an article using the water / oil repellent / antifouling transparent member according to the first or second aspect of the present invention.
Further, the article according to the fifth aspect of the present invention is a vehicle, building, energy-utilizing device such as a solar cell, road material, a part used for an electric appliance, for example, a vehicle or a window glass of a building, a face plate such as a solar cell, Any of an inorganic base material, an organic base material, and an organic-inorganic composite base material such as a transparent soundproof wall of a road may be used.

According to the present invention, there are provided a water / oil repellent transparent member that can be produced at low cost and has a low environmental load during processing and disposal, a method for producing the same, 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 a base material made of an arbitrary material at low cost, resource saving, energy saving.

The article using the water / oil repellent transparent member according to the present invention has high antifouling property, durability, safety to human body and environment, and can exhibit antifouling property semipermanently.

It is explanatory drawing of the cross-section of the water / oil repellent transparent member which concerns on each embodiment of this invention. It is explanatory drawing which expanded the cross-section of the water / oil repellent transparent member which concerns on the 1st Embodiment of this invention to the molecular level, and represented typically. It is explanatory drawing which expanded the cross-section of the base material in which the organic thin film was formed in the manufacturing method of the said water / oil repellent transparent member to the molecular level typically. It is explanatory drawing which expanded the cross-sectional structure of the water / oil repellent transparent member which concerns on the 2nd Embodiment of this invention to the molecular level, and represented typically. 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 formed to the molecular level typically in the manufacturing method of the said water / oil repellent transparent member. It is explanatory drawing which shows the state in which the organic thin film containing many silanol groups was formed in the manufacturing method of the water / oil repellent transparent member. It is explanatory drawing which expanded to the molecular level and represented typically the cross-sectional structure of the water- and oil-repellent transparent member which concerns on the 3rd Embodiment of this invention. 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 the surface vicinity of the base material before and after a low-pressure plasma processing of this to the molecular level, and was represented typically.

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 water- and oil-repellent transparent member 1 according to each embodiment of the present invention (the water- and oil-repellent transparent members 10 and 20 according to first to fourth embodiments which will be described individually below). , 30, and 40), a transparent substance 2 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 ( Hereinafter, 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, are transparent substrates. 3 (hereinafter, a collective term for the base materials 12, 22, 32, and 42 according to first to fourth embodiments which will be described separately) at least part of the surface (FIG. 1 shows the entire surface of the base material 3 as an example. Is shown to cover the case.) That.

The water / oil repellent transparent member 1 performs low-pressure plasma treatment on the surface of the substrate 3 on which a substance having a hydrocarbon group covers at least a part of the surface in a gas atmosphere of a compound containing a fluorocarbon group. It is manufactured by a method including step A (see FIGS. 2, 4, 7, and 8 (b)). In this case, the fluorine-containing functional group is obtained by subjecting a substance having a hydrocarbon group present so as to cover at least a part of the surface of the substrate 3 to a low pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group. Is obtained.

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 of the substrate 3 with a trifluoromethyl group 19, 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, and the like, and examples of an electrode for high frequency discharge include a parallel plate type, a coaxial cylindrical type, a curved counter plate type such as a cylinder and a sphere, and a twin type. Examples of the electrode include a curved 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, if a small amount of oxygen (0.1 to 15% by volume) is included, the hydrogen atom of the hydrocarbon group is replaced with a fluorine atom or a fluorocarbon group while oxidizing the surface of the base material 12, 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 surface oxidation etching.

Plasma treatment in an oxygen gas atmosphere has the effect of cleaning the surface of the acrylic resin substrate and the effect of roughening the surface of the member. The surface roughness can be controlled by arbitrarily controlling the power and processing time of the high-frequency power supply. It can be controlled in the range of several nanometers to several hundred microns.

The base material 3 used for the production of the water / oil repellent transparent member 1 is transparent and needs to be present so that the substance having a hydrocarbon group covers at least a part of the surface. There is no restriction | limiting in particular about a magnitude | size, The thing of arbitrary materials, a shape, and a magnitude | size can be used. When using the base material 3 made of an inorganic material having no hydrocarbon group on the surface, a coating of a substance containing a hydrocarbon group covering at least a part of the surface is applied to the surface of the base material 3 in step C described later. Can be formed.
Specific examples of the material of the substrate 3 include organic materials such as resins and inorganic materials such as glass.

Specific examples of the transparent resin include polyurethane, polyester, polyethylene, polyphenylene sulfide, polyethylene terephthalate, polyethylene naphthalate, polyvinylidene chloride, polyvinyl chloride, polyolefin, polycarbonate, polyvinyl acetate, polystyrene, polysulfone, and 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.

The surface roughness of the water / oil repellent transparent member 1 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 surface of the water / oil repellent transparent member 1 is not particularly limited as long as it does not impair the optical properties of the substrate 3 due to diffraction of incident light, irregular reflection, etc. Even if it is a regular shape, it is irregular. It may be a 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 water / oil repellent transparent member 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 water / oil repellent transparent member 10 according to the first embodiment of the present invention, a decyl group (C ₁₀ H ₂₁ : an alkyl group which is a hydrocarbon group) is formed on the 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 to the surface of the substrate 12 (an example of a chemical bond).

The water / oil repellent transparent member 10 contacts a treatment liquid containing a film compound having a hydrocarbon group on the surface of the base 12, and a film substance generated by the reaction between the film compound and the surface functional group of the base 12 is obtained. 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 surface of the substrate 12), and a gas of a compound containing a fluorocarbon group By performing low-pressure plasma treatment on the surface of the substrate 12 on which the organic thin film 18 is formed in an atmosphere, some or all of the hydrogen atoms in the hydrocarbon groups contained in the organic thin film 18 are fluorine atoms and fluorocarbon groups. And the step A of forming the fluorine-containing organic thin film 11 substituted with either one or both.

In addition, before the process A, you may roughen the 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 are (1) Step B → Step C → Step A (the surface of the substrate 12 is roughened and then the organic thin film 18 is formed), and (2) Step C → Step B → You may implement in any order of the process A (The surface of the base material 12 in which the organic thin film 18 was formed is roughened.). About the order of each process, it is the same also about the manufacturing method of the water- and oil-repellent transparent members 20 and 30 which concern on the 2nd and 3rd embodiment mentioned later.

Next, step B will be described.
As a method for roughening the surface of the substrate 12, it may be roughened in advance using any known method such as sandblasting, mechanical polishing, and chemical treatment with chromic acid mixed solution, phosphoric acid, alkali or the like. Although it is good, it can also be performed by performing low-pressure plasma treatment in an atmosphere containing oxygen gas or 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 surface of the substrate 12. In order to fix to the surface of the base material 12 through a bond with a surface functional group on the surface, it is preferable to have a surface bond 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 preferable 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 equation (XI) ~ (XV), m and n are each independently a integer of 0 or more 24 or less, A is an alkyl group, more preferably a methyl group or an ethyl group.

Specific examples of the membrane compound include the compounds shown in the following (1) to (1 6 ). C ₆ H ₄ represents a phenylene group.
(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 COO (CH} 2) 15 Si (OC 2 H 5) 3
(1 0 ) CH ₃ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(1 1 ) CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(1 2 ) CH ₃ (CH ₂ ) ₇ C ₆ H ₄ Si (OC ₂ H ₅ ) ₃
(1 3 ) [CH ₃ (CH ₂ ) ₅ ] ₂ Si (OCH ₃ ) ₂
(1 4 ) [CH ₃ (CH ₂ ) ₅ ] ₂ Si (OC ₂ H ₅ ) ₂
(1 5 ) [CH ₃ (CH ₂ ) ₅ ] ₃ SiOC ₂ H ₅
(1 6 ) 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, the use of water is preferable from the viewpoint of reducing the environmental load during the production of the water / oil repellent transparent member 10. 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) having compatibility with water and high volatility can be 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 surface of the substrate 12 and left to stand until most of the solvent is volatilized (for example, in the air at room temperature for 1 hour). The membrane compound is bonded to the surface of the substrate 12 through a covalent bond (siloxane bond) formed by a condensation reaction between a hydroxyl group (not shown) on the surface of the substrate 12 and an alkoxysilyl group, and an organic thin film (single layer) A molecular 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 surface of the substrate 12, but in such a case, it may be washed away 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 promote the condensation reaction between the alkoxysilyl group and the hydroxyl group on the 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, and 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, and 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.
Specific examples of titanate chelate include bis (acetylacetonyl) di-propyl titanate.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, 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, and examples thereof include 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. Application of the treatment liquid to the surface of the substrate 12 and reaction must be performed under dry conditions (relative humidity of 45% or less).

Next, the water / oil repellent transparent member 20 according to the second embodiment of the present invention will be described. As shown in FIG. 4, in the water- and oil-repellent transparent member 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 surface of the base material 22 through a bond with a hydroxyl group (an example of a surface functional group) on the surface of the base material 22. a coating 27 of a polysiloxane molecules covering the surface in a mesh shape, are formed on the surface and polysiloxane molecules 13 of the substrate 12, a decyl group (C _{10 H 21:} an example of alkyl groups is a hydrocarbon group) in Membrane material in which the hydrogen atom of the methyl group at the end of is substituted with a trifluoromethyl group (a fluorine-containing hydrocarbon group in which some or all of the hydrogen atoms are substituted with either or both of a fluorine atom and a fluorocarbon group) An example of a film substance having The film substance is formed by a reaction between an alkoxysilyl group (an example of a reactive group) at the terminal of the film compound and a hydroxyl group (an example of a surface functional group) on the surface of the substrate 22 or a silanol group on the polysiloxane molecule 24. It is fixed to the surface of the substrate 22 and the polysiloxane molecules 24 covering the surface of the substrate 22 in a mesh form through the formed bonds (Si—O— bonds).

The water / oil repellent transparent member 20 is made by bringing a membrane compound having a hydrocarbon group on the surface of a base material 22 and a treatment liquid in which alkoxysilane and / or alkoxypolysiloxane are mixed and dispersed in a solvent into contact with each other. 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 The surface of the base material 22 on which the organic thin film 28 is formed is subjected to low-pressure plasma treatment, so that part 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 of forming the fluorine-containing organic thin film 21 substituted with one or both, and if necessary, the surface of the base material 22 before the step A has a surface roughness and irregularities within the above ranges. Produced by the process and a step B of roughened cormorants.
Hereinafter, a method for producing the water / oil repellent transparent member 20 will be described.

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 in the manufacture of the water / oil repellent transparent member 10 according to the first embodiment, and therefore will be described in detail. Omitted.

The treatment liquid used in Step C is prepared by mixing and dispersing the film compound and alkoxysilane and / or alkoxypolysiloxane in a solvent. Since 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 for producing the water / oil repellent transparent member 10, detailed description thereof is omitted.

The treatment liquid used for the production of the water / oil repellent transparent member 20 contains alkoxysilane and / or alkoxypolysiloxane in order to improve the durability of the water / oil repellent transparent member 20 obtained. Alkoxysilane is a compound represented by the formula _{SiH x (OA) 4-x} ( formula (VI)), alkoxy polysiloxanes of 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 water / oil / oil repellent transparent member 20 whose water / oil / oil repellent and antifouling properties are maintained over a long period of time, the composition ratio of the film compound to alkoxysilane and / or alkoxypolysiloxane (the number of silicon atoms) Ratio) is preferably 1:10 to 1: 0, more preferably 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 water / oil repellent transparent member 20 comprises a film compound and alkoxysilane and / or alkoxypolysiloxane and a solvent (preferably water containing a surfactant and / or alcohol). The mixture 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 water- and oil-repellent transparent member 10. The processing conditions of the base material 22 with the processing liquid thus obtained are the same as in the case of manufacturing the water / oil repellent transparent member 10 according to the first embodiment. As shown in FIG. 6, the resulting 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).

Subsequently, the hydrogen atom in the hydrocarbon group contained in the organic thin film 28 is obtained by subjecting the surface of the substrate 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. Is formed by substituting one or both of fluorine atoms and fluorocarbon groups with a fluorine-containing organic thin film 21 to obtain a water / oil repellent transparent member 20. Since it is the same as that of the manufacturing method of the water / oil repellent transparent member 10 which concerns on 1 embodiment, detailed description is abbreviate | omitted. Similarly, detailed description of the process B is also omitted.

The water / oil repellent transparent member 20 thus obtained can be used in the same manner as the water / oil repellent transparent member 10 according to the first embodiment.

Next, a water / oil repellent transparent member 30 according to a third embodiment of the present invention will be described with reference to FIG. In the water / oil repellent transparent member 30, the fluorine-containing organic thin film 31 is a polysiloxane molecule (34) fixed on the 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 film substance is a bond (Si—O— bond) formed by a reaction between an alkoxysilyl group (an example of a reactive group) at the end of the film compound and a silanol group (Si—OH) (not shown) on the polysiloxane molecule 34. ) To a coating 37 of polysiloxane molecules (34) covering the surface of the substrate 32 (see FIG. 7).

In the present embodiment, the water / oil repellent transparent member 30 first contacts a treatment liquid containing alkoxysilane and / or alkoxypolysiloxane with the surface of the substrate 32, and a polysiloxane molecule coating 37 is formed on the surface of the substrate 32. 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 surface, thereby forming a film of the film substance on the polysiloxane molecule film 37; The step A for obtaining the base material 32 on which the organic thin film 38 is formed and the 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. The process of forming the fluorine-containing organic thin film 31 by which one part or all part of the hydrogen atom in the hydrocarbon group contained in 28 is substituted by either one or both of a fluorine atom and a fluorocarbon group. And a step B of roughening the surface of the base material 32 so as to have a surface roughness and an unevenness size within the above range before the step A, if necessary. . Regarding the preparation conditions (solvent, concentration, etc.) of each solution, the coating 37 of the polysiloxane molecules (34) on the surface of the substrate 32 and the coating conditions (treatment conditions) of the film substance, the first and second implementations described above. Since it is the same as that of the manufacturing method of the water and oil repellent transparent members 10 and 20 which concern on this form, detailed description is abbreviate | omitted.

Next, a water / oil repellent transparent member 40 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 (an example of a substance having a fluorine-containing functional group) so as to cover at least a part of the surface of the substrate 42 ) 41 exists.
As shown in FIG. 8A, the surface of the base material 42 used for manufacturing the water / oil repellent / antifouling member 40 is covered with a hydrocarbon group 43. As shown in FIG. 8B, the hydrocarbon group 43 covering the surface of the base material 42 before the low pressure plasma treatment is formed on the surface of the water / oil repellent and antifouling member 40 after the low pressure plasma treatment in the step A. A part of 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 in which a base material 42 is subjected to low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group, and a surface of the base material 42 before step A if necessary. Is roughened 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 replace the hydrogen atom of the hydrocarbon group on the surface of the acrylic base material 42 with the trifluoromethyl group 43 (FIG. 8B).

For the base material 42 having a hydrocarbon group at least in the vicinity of the surface, the gas of the compound containing a fluorocarbon group is directly roughened so as to have a predetermined surface roughness and unevenness size by the step B. The water- and oil-repellent transparent member 40 is obtained by performing low-pressure plasma treatment in an atmosphere (step A). The method for producing the water- and oil-repellent transparent member according to the present embodiment for an article made of an inorganic material or its member is described below. When applying, the process C is implemented and the film which contains an organic polymer as the base material 42 is formed in the 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.

In addition, about the roughening method of the surface of the base material 42 used in the process B and the order of performing the processes A to C, the water / oil repellent transparent member 10 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.

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 were weighed to a molar ratio of 3: 1, and the ethanol was diluted to 0. 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 transparent glass plate was prepared as a substrate, and the treatment liquid prepared above was applied to the surface in air (relative humidity 57% to 70%) and then left in the air for about 1 hour. . During this time, most of the ethanol in the treatment liquid evaporates into the air and chemically bonds to the surface over the entire surface by dehydration reaction with silanol groups (Si-OH) generated by hydrolysis of alkoxysilyl groups. A film composed of a network-like polysiloxane molecule fixed through (silanol bond) and octadecylsilyl groups fixed on the surface of the glass plate or on the polysiloxane molecule was formed.

Before the coating is completely cured, the unreacted excess octadecyltrimethoxysilane and tetramethoxysilane are washed away with a water-ethanol mixed solvent (if the coating amount and the liquid concentration are properly adjusted, this step is not necessarily required. The result was almost the same even if the cleaning was not performed.) Then, from the polysiloxane molecule having a thickness of about 5 nm and the octadecylsilyl group fixed on the surface of the glass plate or on the polysiloxane molecule. The resulting film could be formed in a state of being chemically bonded to the surface of the glass plate (FIG. 6).

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

Next, the surface of the glass plate 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 water / oil repellent transparent member thus obtained was measured. The measurement was performed at five different points (I to V) 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 water / oil repellent transparent member 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 surface of the transparent glass plate 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 plate 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 nm could be formed on the surface of the glass plate.
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 water / oil repellent transparent member (glass plate) thus obtained.

It can be seen that the water droplet contact angle in the obtained water / oil repellent transparent member is greatly increased by performing the plasma surface roughening treatment. Moreover, in the water / oil repellent transparent member obtained in this example, no decrease in light transmission, generation of interference fringes, haze, and the like were 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. The measurement was performed at five different points (I to V) 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.

Articles to which the present invention can be applied include vehicles, buildings, energy-utilizing devices such as solar cells, road materials, parts used for electrical appliances, such as vehicle and building window glass, face plates such as solar cells, transparent soundproof walls of roads, etc. There is. The substrate itself may be any of an inorganic substrate , an organic substrate , and an organic-inorganic composite substrate .

DESCRIPTION OF SYMBOLS 1 Water repellent / oil repellent transparent member 2 Transparent substance having fluorine-containing functional group 3 Base material 10, 20, 30 Water repellent / oil repellent transparent member 11 Substance having fluorine-containing functional group 11a, 21, 31 Fluorinated organic thin film 12, 22, 32, 42 Base material 13, 23, 33 Film material 24, 34 having hydrocarbon group Polysiloxane molecule 24a Polysiloxane molecule 25 having silanol group 25 Silanol group 26 Organic thin film 27, 37 having silanol group Coating 27a Polysiloxane molecule coating having silanol groups 18, 28, 38 Organic thin film 19, 44 Trifluoromethyl group 41 Fluorinated organic polymer 43 Hydrocarbon group

Claims (14)

At least part of the transparent substrate is
In a gas atmosphere of a compound in which a part or all of hydrogen atoms in a polysiloxane molecule formed from alkoxysilane and / or alkoxypolysiloxane and a hydrocarbon group having 6 to 25 carbon atoms contain a fluorocarbon group By the plasma treatment, it is covered with a transparent substance including a film substance having a fluorine-containing functional group substituted with one or both of a fluorine atom and a fluorocarbon group,
The polysiloxane molecule is fixed on the surface of the substrate through a bond formed by a reaction between an alkoxysilyl group and a surface functional group present on the surface of the substrate to form a film.
A part of the film substance having a fluorine-containing functional group is directly bonded to the surface of the base material, and the rest is bonded and fixed to the surface of the base material through a film of the polysiloxane molecule. Water and oil repellent transparent member. Claim 1, wherein the polysiloxane molecule, characterized in that it is intended to be formed by a condensation reaction of alkoxy polysiloxanes represented by the alkoxysilane and / or formula represented by the following formula (VI) (VII) serial mounting of repellent transparent member.
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. 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 claim 1 or 2 repellent transparent member, wherein the substituted functional group in. 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 water / oil repellent transparent member according to any one of claims 1 to 3 , wherein

In the equation (I) ~ (V), m and n are each independently Represents an integer of 0 to 24 or less, m ≦ n. Repellent transparent member according to any one of claims 1 4, wherein the surface roughness of the substrate is 10nm or more 400nm or less. Transparent treatment liquid containing a film compound having a hydrocarbon group having 6 to 25 carbon atoms and an alkoxysilane represented by the following formula (VI) and / or an alkoxypolysiloxane represented by the following formula (VII) An organic compound having a hydrocarbon group, which is brought into contact with the surface of a base material, chemically bonded to the surface of the base material, and covering at least a part of the surface by a reaction between the membrane compound and a surface functional group of the base material Forming a thin film on the surface of the substrate; and
The surface of the base material on which the organic thin film is formed is subjected to low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group, and a part of hydrogen atoms in the hydrocarbon group of the organic thin film Or a method for producing a water- and oil-repellent transparent member, comprising a step A in which all or one of fluorine atoms and fluorocarbon groups is substituted.
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. The surface of the transparent substrate is treated with a solution containing an alkoxysilane represented by the following formula (VI) and / or an alkoxypolysiloxane represented by the following formula (VII), and the surface of the polysiloxane molecule is A film is formed, and then a treatment liquid containing a film compound having a hydrocarbon group having 6 to 25 carbon atoms is brought into contact with the surface of the polysiloxane molecule film, and the surface function of the film compound and the polysiloxane molecule film is contacted. A step C of forming an organic thin film having a hydrocarbon group by chemically bonding to the surface of the polysiloxane molecule film by reaction with a group;
The surface of the base material on which the organic thin film is formed is subjected to low-pressure plasma treatment in a gas atmosphere of a compound containing a fluorocarbon group, and a part of hydrogen atoms in the hydrocarbon group of the organic thin film Or a method for producing a water- and oil-repellent transparent member, comprising a step A in which all or one of fluorine atoms and fluorocarbon groups is substituted.
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. 8. The water / oil repellent / antifouling property according to claim 6 or 7 , wherein, in the step A, the substrate is subjected to low-pressure plasma treatment in a mixed atmosphere of a compound gas containing a fluorocarbon group and an oxygen gas. Manufacturing method of member. Prior to said step A, repellent of any one of claims 6 to 8, the surface roughness on the surface of said substrate, characterized by further comprising a step B of forming the unevenness is 10nm or more 400nm or less A method for producing a water / oil repellent transparent member. The water-repellent repellency according to any one of claims 6 to 9 , 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. A method for producing an oily transparent member. The film compound The method for producing a water and oil repellent transparent member according to any one of 0 1 claim 6, characterized in that the 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 of an alkyl group having 6 to 25 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. The water / oil repellent transparent member according to any one of claims 6 to 11 , wherein the film compound is a film compound represented by any one of the following formulas (XI) to (XV). Production 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 formulas (XI) to (XV), m and n each independently represent an integer of 0 or more and 24 or less, m ≦ n, and A represents an alkyl group. Article using the water and oil repellent antifouling transparent member according to any one of claims 1 5. The article of claim 1 3, wherein the article is a vehicle or building window glass, either of the face plate, roads transparent soundproof wall such as a solar cell.

Images