JP2009120727A - Water-repellent stain-resistant article and building windowpane, vehicle windshield, display member and optical parts composed by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent stain-resistant article imparted with excellent water repellency and slipperiness (aptness of downfall of water droplet) and having durability for these characteristics to be sustained over a long period of time, wear resistance and scratch resistance. <P>SOLUTION: The water-repellent stain-resistant article has a water-repellent stain-resistant film in which a ground film consisting of inorganic material fine particles and an organic material based binder composition is formed on a base material and thereafter a water-repellent stain-resistant material is coated or impregnated on/into the uneven parts of the surface and the inside of the voids formed by the removal of the binder by the atmospheric-pressure plasma treatment. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has an excellent water repellency, sliding property (water droplet falling property), antifouling property, and a highly durable water and antifouling article that can maintain its performance over a long period of time The present invention relates to an architectural window glass, a vehicle window glass, a display member, and an optical component.

  As a film having excellent water repellency, it is obtained by hydrolyzing a mixture of a fluoroalkyl group silane compound and polydimethylsiloxane (the same derivative) and an alkoxysilane compound in a solvent. The solution is mixed, applied to a glass substrate, dried, and heated at about 250 ° C. to form a film having a thickness of 20 to 200 nm (see, for example, Patent Document 1). Since this film is regularly segregated with a high concentration of fluoroalkylsilane component in the surface layer and the gaps are filled with methyl groups, the surface contact angle is large and the water drop falling angle is small, giving a good water repellent film. Yes. However, the water-repellent film obtained in accordance with the description in Patent Document 1 cannot sufficiently withstand the abrasion caused by a wiper as required for an automobile windshield, and has problems of wear resistance and durability.

  On a glass substrate, colloidal silica is added and applied to a hydrolyzate such as TEOS, and baked at about 250 ° C. to form an underlayer. A fluoroalkylsilane hydrolyzate is mixed with a fluororesin dispersion such as tetrafluoroethylene, and sprayed onto a substrate with a base film taken out from a heating furnace at 650 ° C. to form a water repellent film having a thickness of 4 to 1000 nm. The wear resistance can be improved (see, for example, Patent Document 2). However, in the water-repellent film obtained in accordance with the description in Patent Document 2, friction is increased due to unevenness formed by colloidal silica due to high-speed reciprocating friction with a wiper or the like, and the water-repellent film is peeled off. Abrasion resistance cannot be obtained. In addition, it cannot be applied to a base material containing a resin film such as a laminated glass that has been adopted for a windshield of an automobile in recent years because it cannot be heated and fired.

  Applying a coating solution obtained mainly from a mixture of a sol solution obtained by hydrolyzing a tetraalkoxysilane added with a metal alkoxide and a sol solution obtained by hydrolyzing an alkyltrialkoxysilane to the substrate surface; Forming a sol-gel film having a fine uneven surface layer by heating and baking, and coating the water-repellent film layer on this sol-gel film, it has high adhesion and wear resistance, and can maintain its performance over the long term A film is obtained (see, for example, Patent Documents 3 and 4). However, the water-repellent film obtained according to the description in Patent Document 3 or 4 also has a wear resistance that can withstand long-term durability as required for automobile windshields because friction tends to increase due to unevenness. The scratch resistance was not enough.

It is said that the durability of the functional coating can be improved by forming a base film having fine irregularities mainly composed of silicon oxide and forming a functional coating thereon (see, for example, Patent Document 5). The resulting water-repellent film was also insufficient in abrasion resistance and scratch resistance for the same reason as described above.
JP-A-8-12375 JP-A-8-319137 JP-A-9-309745 JP-A-2005-281132 JP 2004-136630 A

  The present invention has been made in view of the above-mentioned problems, and its purpose is to provide excellent water repellency, sliding property (water droplet tumbling property), and durability, abrasion resistance, and scratch resistance for which these characteristics last for a long time. An object of the present invention is to provide a water-repellent / antifouling article. Still another object of the present invention is to provide a water-repellent / antifouling article capable of forming a low-temperature film that can form a film even when the substrate processing temperature is limited, such as an automobile windshield.

  The above object of the present invention can be achieved by the following configuration.

  1. A base film composed of inorganic material fine particles and an organic material-based binder composition is formed on the substrate, and then the binder is removed by atmospheric pressure plasma treatment to repel the surface irregularities and voids inside the base layer. A water repellent / antifouling article comprising a water / antifouling film coated or impregnated with a water / antifouling material.

  2. A metal element-containing oxide thin film having a thickness of 5 nm to 50 nm is formed as an overcoat film on the surface of the underlayer by atmospheric pressure plasma, and then a water-repellent / antifouling material is formed on the metal element-containing oxide thin film. 2. The water-repellent / antifouling article as described in 1 above, which is coated or impregnated.

  3. 3. The undercoat film-containing base material in which a metal element-containing oxide thin film having a thickness of 5 nm to 50 nm is formed as an undercoat film on the base material by atmospheric pressure plasma as the undercoat film. Water repellent and antifouling article.

  4). 4. The water-repellent / antifouling article as described in 2 or 3 above, wherein the metal element-containing oxide thin film is an oxide thin film containing at least silicon atoms.

  5). The water repellent / antifouling article according to any one of 1 to 3, wherein the underlayer and the undercoat film are formed at a substrate temperature of 15 to 150 ° C.

  6). 6. The water / antifouling article according to any one of 1 to 5 above, wherein the entire thickness of the water / oil repellent film is from 10 nm to 200 nm.

  7. 7. The water / oil-repellent property according to any one of 1 to 6 above, wherein the water / oil-repellent material is coated or impregnated with 1 to 3 types of coupling agents before being coated / impregnated. Goods.

  8). The water repellency / antifouling material contains at least a fluorine-based resin or a fluorine-containing silicone resin and a silicate compound represented by the following general formula (1). Water and antifouling goods.

(Wherein n is an integer of 2 or more, R ¹ is all different or at least two are the same and both are monovalent organic groups having 1 to 1000 carbon atoms or hydrogen atoms, and the organic groups are oxygen atoms, (At least one selected from a nitrogen atom and a silicon atom may be contained, and a part or all of the hydrogen atoms of the organic group may be substituted with a fluorine atom.)
9. The substrate is at least one selected from a transparent glass plate, a transparent resin plate, and a transparent resin film, and the average transmittance in the visible light region of the substrate is 85% or more. The water repellent / antifouling article according to any one of -8.

  10. An architectural window glass comprising the water-repellent / antifouling article according to any one of 1 to 9 above.

  11. A vehicle window glass comprising the water-repellent / antifouling article according to any one of 1 to 9 above.

  12 A display member comprising the water-repellent / antifouling article according to any one of 1 to 9 above.

  13. 10. An optical component comprising the water-repellent / antifouling article according to any one of 1 to 9 above.

  Since the foundation layer of the uneven surface mainly composed of inorganic material formed by atmospheric pressure plasma is used as a skeleton, the entire water-repellent / antifouling film is highly hard and scratches are difficult. As a result, a water-repellent / antifouling article capable of maintaining excellent water repellency and antifouling properties with respect to abrasion resistance and scratch resistance was obtained. Moreover, since elution by impurities from the substrate was passivated by the metal element-containing oxide thin film formed by atmospheric pressure plasma, a water-repellent / antifouling article capable of suppressing the weather resistance deterioration was obtained. In addition, the subbing film formed by atmospheric pressure plasma has high adhesion to water-repellent / antifouling materials. By providing a coupling agent, the adhesion is further improved and the film is also resistant to water and chemicals. was gotten.

  The present invention will be described in more detail.

  The water-repellent / antifouling article of the present invention is formed by forming an uneven shape and a void structure with high adhesion on a substrate by atmospheric pressure plasma treatment, so that the water-repellent agent It became possible to expose the surface of the soiling agent to the minimum necessary amount. As a result, the rugged surface that is strong and has extremely high adhesion to the substrate is resistant to wear and abrasion, which was insufficient with conventional methods, such as high-speed and long-term friction due to wipers. Since the entire film can be held and the water-repellent agent and antifouling agent present around the membrane can be protected, it has become possible to obtain extremely high durability against abrasion.

  Further, by performing the method for forming the concavo-convex shape by using the atmospheric pressure plasma method, it is possible to obtain a strong underlayer having higher adhesion and further, since a baking time is not required unlike a sol-gel film. The above-mentioned strong underlayer can be formed even at a low temperature of ˜150 ° C.

≪Inorganic material fine particles≫
The inorganic material fine particles of the present invention have an average particle diameter (D1) of 2 to 100 nm, and the total thickness of the water-repellent / antifouling film is from 10 nm to 200 nm. The inorganic material is not particularly limited as long as it is an inorganic compound having transparency (transparency) to visible light, but a metal element-containing oxide, nitride, oxynitride, or the like can be used. Examples of the oxide include silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), alumina (Al ₂ O ₃ ), tin oxide (SnO ₂ ), zirconia (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), A ceramic material such as indium oxide (In ₂ O ₃ ) is preferable from the viewpoint of high permeability and hardness. In particular, silicon dioxide (SiO ₂ ) is rich in materials and is more preferable from the viewpoint of safety and cost.

≪Binder≫
Any binder can be used as the binder according to the present invention as long as it can be used to disperse the fine particles, and a polymer is generally used. Examples of polymers include polyalkylene glycol (eg, polyethylene glycol), acrylic resin, polyester, polyurethane, epoxy resin, silicone resin, fluororesin, polyvinyl acetate, polyvinyl alcohol, polyacetal, polybutyral, petroleum resin, polystyrene, fiber Examples thereof include elemental resins.

  Examples of the acrylic resin include a homopolymer or a copolymer obtained from alkyl acrylate (eg, methyl acrylate, ethyl acrylate, butyl acrylate) and / or alkyl methacrylate (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate). be able to. Moreover, the copolymer of these monomers and another copolymerizable monomer can also be mentioned. In particular, polymethyl methacrylate (PMMA) is preferable from the viewpoints of reactivity during photocuring, durability after curing, and transparency.

  A surfactant can also be used as the binder. Examples thereof include nonionic surfactants such as polyethylene glycol and polypropylene glycol, anionic surfactants, and cationic surfactants. A combination of the polymer and a surfactant can also be used.

  The inorganic material fine particles described above of the present invention are dispersed in an aqueous solution or an organic solvent solution of the binder and applied onto a substrate described later. The coating method may be any method as long as it is a known coating solution coating method. For example, gravure coating, spin coating, bar coating, blade coating, roller coating, dip coating, dipping method, spray coating, flow coating, curtain coating, slide coating, extrusion coating, air doctor coating, ink jet method, etc. it can.

  Organic solvents that can be preferably used in the present invention include hydrocarbons (toluene, xylene, etc.), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) ), Esters (such as methyl acetate, ethyl acetate, and methyl lactate), glycol ethers, and the like are preferable. These solvents can be appropriately selected from these solvents, or can be used by mixing them.

≪Atmospheric pressure plasma method≫
Next, details of an atmospheric pressure plasma processing apparatus applicable to the present invention will be described below with reference to the drawings.

  Compared with the plasma CVD method under vacuum, the atmospheric pressure plasma processing apparatus that performs plasma surface treatment or plasma CVD treatment near atmospheric pressure does not need to be reduced in pressure, so it not only increases productivity but also has a high plasma density. Due to the density, the surface treatment speed or the film forming speed is high. Furthermore, compared with the conditions of the normal CVD method, the high-pressure condition of atmospheric pressure is very short because the mean free path of gas is very short. This film is obtained.

  The atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to 110 kPa, and 93 kPa to 104 kPa is preferable in order to obtain the good effects described in the present invention.

  The excited gas as used in the present invention means that at least a part of the molecules in the gas move from the existing state to a higher state by obtaining energy. Excited gas molecules, radicalized gas molecules A gas containing ionized gas molecules corresponds to this.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is not particularly limited, but can be broadly divided into the following two methods.

  One method is a so-called plasma jet type atmospheric pressure plasma discharge treatment apparatus, in which a high-frequency voltage is applied between the counter electrodes, a mixed gas containing a discharge gas is supplied between the counter electrodes, and the mixed gas is converted into plasma. Then, surface treatment (in the present invention, removal of the binder) is performed with a plasma gas mixture gas, or a desired film forming gas is associated and mixed, and then sprayed onto the transparent substrate.

  The other method is a direct atmospheric pressure plasma discharge treatment apparatus, which introduces the above gas into the discharge space in a state where a transparent base material is supported between a mixed gas containing a discharge gas and a counter electrode. In this method, a high-frequency voltage is applied between the electrodes to form a desired film, or surface treatment (in the present invention, the binder is removed).

  FIG. 1 is a schematic view showing an example of a two-frequency jet type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

  The jet-type atmospheric pressure plasma discharge treatment apparatus has a gas supply means and an electrode temperature adjustment means (not shown in FIG. 1) in addition to the plasma discharge treatment apparatus and the electric field application means having two power sources. Device.

The atmospheric pressure plasma discharge processing apparatus 110 has a counter electrode composed of a first electrode 111 and a second electrode 112, and the frequency from the first power supply 121 is from the first electrode 111 between the counter electrodes. A _first high frequency electric field of ω ₁ , electric field strength V ₁ , and current I ₁ is applied, and a second frequency of ω ₂ , electric field strength V ₂ , and current I ₂ from the second power source 122 is applied from the second electrode 112. A high frequency electric field is applied. The first power supply 121 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power supply 122, and the first frequency ω ₁ of the first power supply 121 is higher than the second frequency ω ₂ of the second power supply 122. A low frequency can be applied.

  A first filter 123 is installed between the first electrode 111 and the first power supply 121 to facilitate passage of current from the first power supply 121 to the first electrode 111, and current from the second power supply 122. Is designed so that the current from the second power supply 122 to the first power supply 121 does not easily pass.

  In addition, a second filter 124 is installed between the second electrode 112 and the second power source 122 to facilitate passage of current from the second power source 122 to the second electrode, and from the first power source 121. It is designed to ground the current and make it difficult for the current from the first power supply 121 to the second power supply 122 to pass through.

  A gas G is introduced from the gas supply means between the opposing electrodes (discharge space) 113 between the first electrode 111 and the second electrode 112, and a high frequency electric field is applied from the first electrode 111 and the second electrode 112 to generate a discharge. The gas G is blown out in the form of a jet to the lower side of the counter electrode (the lower side of the paper) while filling the processing space formed by the lower surface of the counter electrode and the substrate F with the gas G ° in the plasma state. A desired film is formed near the processing position 114 on the substrate F conveyed from the process, or the binder is removed. During formation of a desired film or surface treatment (binder removal), the medium is heated or cooled by the medium from the electrode temperature adjusting means through the pipe. Depending on the temperature of the base material during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur as much as possible.

  FIG. 1 shows a measuring instrument used for measuring the high-frequency electric field strength (applied electric field strength) and the discharge starting electric field strength. 125 and 126 are high-frequency voltage probes, and 127 and 128 are oscilloscopes.

  FIG. 2 is a schematic view showing an example of a direct atmospheric pressure plasma discharge treatment apparatus applicable to the present invention.

  In the direct atmospheric pressure plasma discharge processing apparatus shown in FIG. 2, two electrodes 41 connected to the power source 31 are provided in parallel with the moving stage electrode 47. At least one of the electrodes 41 and 47 is covered with a dielectric 42, and a high frequency voltage is applied by the electrode 31 to a space 43 formed between the electrodes 41 and 47.

  Note that the inside of the electrode 41 and the moving stage 47 has a hollow structure 44, so that heat generated by the discharge can be removed by water, oil, etc. during discharge, and heat exchange can be performed so as to maintain a stable temperature. Yes.

  Further, by each gas supply means (not shown), the gas 22 containing the discharge gas necessary for the discharge passes through the flow path 24 and mixed with the gas necessary for forming a desired film or removing the binder. The gas 23 passes through the flow path 25 and is merged and mixed in the mixing space 45. The mixed gas G passes between the electrodes 41 and is supplied to the space 43 between the electrodes 41 and 47. When a high frequency voltage is applied to the space 43, plasma discharge is generated, and the gas G is turned into plasma. . The thin film forming gas is activated by the plasma gas G to cause a chemical reaction, and a desired film is formed on the substrate 46 or surface treatment (binder is removed).

  The stage 47 on which the substrate is mounted has a structure capable of reciprocating scanning or continuous scanning, and can perform heat exchange similar to the above electrodes so that the temperature of the substrate can be maintained as necessary. It has become.

  In addition, a waste gas exhaust passage 48 for exhausting the gas blown onto the substrate 46 can be attached as necessary. As a result, unnecessary by-products formed in the space can be quickly removed from the discharge space 45 or the substrate 46.

  In addition, as described in JP-A-2004-353077, a structure in which a discharge gas and a gas necessary for forming a void layer are mixed before discharge by attaching a dirt prevention film or the like to the electrode surface may be used. it can.

  In the apparatus shown in FIG. 2, the high frequency power supply is performed in one frequency band. For example, a method of installing power supplies of different frequencies on each electrode as in the method described in Japanese Patent Application Laid-Open No. 2003-96569. Can also be implemented.

≪Water repellent and antifouling agent≫
The water and antifouling material impregnated in the water and antifouling film of the water and antifouling article of the present invention is not particularly limited, and various water and antifouling materials can be applied. Organic fluorine compounds, organic silicon compounds, fluorine-containing organometallic compounds, and the like. Each of these compounds may be applied directly to a water-repellent / antifouling film in a solution state, dispersed in a fine particle state in an appropriate solvent, or applied in a polymerized state. .

(Organic fluorine compounds)
As an example of an organic fluorine compound applicable to the present invention, it can be applied to a water-repellent / antifouling film as a polymer obtained by reacting an organic fluorine compound and a copolymerization monomer.

  As the organic fluorine compound polymer, a polymer having a side chain represented by the following general formula (2) is preferable.

General formula (2)
CF ₃ CF (X) (CF ₂ ) ₂ −
In the above general formula (2), X represents F, CF ₃ or CF ₂ Cl.

  When the side chain represented by the general formula (2) is an Rf group, a polymer having at least one Rf group in one molecule constituting the polymer is preferable. Specific examples of the polymer having an Rf group include, for example, a homopolymer of a monomer containing an Rf group such as a perfluoroalkylethyl acrylate homopolymer and a perfluoroalkylethyl methacrylate homopolymer, and two types containing an Rf group. Copolymers of the above comonomers, comonomers containing one or more types of Rf groups, and comonomers containing one or more types of comonomers that impart solubility in solvents, film-forming properties, weather resistance, lubricity, etc. Although a polymer etc. are used, it is not specifically limited. When a copolymer of a comonomer containing an Rf group and a comonomer not containing an Rf group is used, the water repellency tends to decrease when the composition of the comonomer containing the Rf group is decreased, and the Rf group in the polymer composition The composition of the comonomer containing is preferably 20% by mass or more, and more preferably 40% by mass or more.

  The monomer containing an Rf group may contain a chlorine atom or a hydrogen atom at the other branched end as long as it contains an Rf group, but is preferably a linear or branched perfluoroalkyl group. Or a monomer containing an Rf group at the end of the perfluoroether group.

  Examples of unsaturated esters such as acrylates and methacrylates whose side chain ends of the polymer can have the structure represented by the general formula (2) are shown below.

CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₆ COOCH═CH ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 7 (} CH 2) 2 OCOC (CH 3) = CH 2
(CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) OCOC (CH ₃ ) = CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 8 (} CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ Cl) CF (CF ₂ ) ₇ CONHCOOCH═CH _{2
CH 2 = CHCOOC 2 H 4 OCOCF} (CF 3) (OC 3 F 6) 2 OC 4 F 9
CH ₂ = CHCONHC ₂ H ₄ OCOCF (CF ₃ ) OC ₃ F ₆ OC ₄ F _{9
CH 2 = C (CH 3)} CONHC 2 H 4 OCOCF (CF 3) OC 4 F 9
The comonomer that can be copolymerized with the comonomer having a side chain represented by the general formula (2) is not particularly limited, and examples thereof include ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene halide, styrene, α-methylstyrene, p-methylstyrene, (meth) acrylic acid and its alkyl ester, poly (oxyalkylene) (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N -Methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acyl Rate, 2-ethylhexyl (meth) acrylate, maleic anhydride, aziridinyl (meth) acrylate, having a polysiloxane (meth) acrylate, a N- vinylcarbazole. Here, (meth) acryl means methacryl and acryl, and (meth) acrylate means methacrylate and acrylate, respectively.

  Moreover, as an example of the organic fluorine compound applicable to the present invention, it can be applied to the water-repellent / antifouling film as a reaction product obtained by reacting an organic fluorine compound with a polyisocyanate compound.

  As an organic fluorine-type compound applicable to the said method, the compound represented by following General formula (3) can be mentioned.

General formula (3)
R ^f -Q-A
In the general formula (3), Rf represents a monovalent fluorine-containing organic group having 2 to 20 carbon atoms, Q represents a single bond or a divalent linking group, and A represents a hydrogen atom reactive with an isocyanate group. Represents a group having the same.

  The “monovalent fluorine-containing organic group” here means a monovalent organic group containing one or more fluorine atoms. The monovalent fluorine-containing organic group is preferably a “monovalent fluorine-containing hydrocarbon group” in which one or more hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms.

  Further, the monovalent fluorine-containing hydrocarbon group is a “monovalent fluorine-containing aromatic hydrocarbon group” in which one or more hydrogen atoms of the monovalent aromatic hydrocarbon group are substituted with fluorine atoms, or a monovalent aliphatic hydrocarbon It may be any “monovalent fluorine-containing aliphatic hydrocarbon group” in which one or more hydrogen atoms of the group are substituted with fluorine atoms, and a monovalent fluorine-containing aliphatic hydrocarbon group is preferable. In the monovalent fluorine-containing hydrocarbon group, one or more etheric oxygen atoms or thioetheric sulfur atoms may be inserted between carbon-carbon bonds.

  The monovalent fluorine-containing hydrocarbon group preferably has 2 to 18 carbon atoms, particularly preferably 4 to 12 carbon atoms. Moreover, 6-12 are preferable and, as for carbon number of monovalent fluorine-containing aromatic hydrocarbon group, 6-8 are especially preferable.

Specific examples of R ^f in the general formula (3) include the following structures. In the following examples, “structurally isomeric groups” which are groups having the same molecular formula but different structures are included. _{C 2 F 5 -, C 3} F 7 - [CF 3 (CF 2) 2 -, and (CF ₃₎ includes both _{2 CF-], C 4 F 9} - [CF 3 (CF 2) 3 -, _{(CF 3) 2 CFCF 2 -} , (CF 3) 3 C-, CF 3 CF 2 CF (CF 3) - _{including], C 5 F 11 - [} CF 3 (CF 2) 4 -, (CF 3) ₂ CF (CF ₂ ) ₂ —, (CF ₃ ) ₃ CCF ₂ —, CF ₃ CF ₂ CF (CF ₃ ) CF ₂ — and other structural isomeric groups], C ₆ F ₁₃ — [CF ₃ (CF ₂ ) including structurally isomeric groups such as ₂ C (CF ₃ ) _2- ], C ₈ F _17- , C ₁₀ F _21- , C ₁₂ F _25- , C ₁₅ F _31- , H (CF ₂ ) _t - (where t is 2-18 _{integer), (CF 3) 2 CF} (CsF 2) s - ( where s is an integer of 1 to 15).

_{CF 3 (CF 2) 4 OCF} (CF 3) -, F [CF (CF 3) CF 2 O] s CF (CF 3) CF 2 CF 2 -, F [CF (CF 3) CF 2 O] t CF (CF ₃ ) −, F [CF (CF ₃ ) CF ₂ O] _u CF ₂ CF ₂ −, F [CF ₂ CF ₂ CF ₂ O] _v CF ₂ CF ₂ −, F [CF ₂ CF ₂ O] _w CF ₂ CF ₂ — (wherein s and t are integers of 1 to 10, u is an integer of 2 to 6, v and w are integers of 1 to 11), C ₆ F ₅ —, C ₆ F ₅ CF _{= CF-, CH 2 = CHC 6} F 10 -, (C p F p + 1) (C q F q + 1) C = C (C r F r + 1) - ( provided that p, q, and r are Each is an integer from 0 to 3 and (p + q + r) is an integer from 2 to 10.)

A perfluoroalkyl group can also be used. The perfluoroalkyl group includes, for example, C ₄ F ₉ — (CH ₂ ) ₂ —, C ₄ F ₉ — (CH ₂ ) ₃ —, C ₄ F ₉ — (CH ₂ ) ₄ —, C ₅ F ₁₁ — (CH _{2) 2 -, C 5 F} 11 - (CH 2) 3 -, C 6 F 13 - (CH 2) 2 -, C 8 F 17 - (CH 2) 2 -, C 8 F 17 - (CH 2) _{3 -, C 8 F 17 -} (CH 2) 4 -, C 9 F 19 - (CH 2) 2 -, C 9 F 19 - (CH 2) 3 -, C 10 F 21 - (CH 2) 2 - .

C ₄ F ₉ — (CH ₂ ) ₂ —O— (CH ₂ ) ₃ —, C ₆ F ₁₃ — (CH ₂ ) ₂ —O— (CH ₂ ) ₃ —, C ₈ F ₁₇ — (CH _{2 ) 2 -O- (CH 2) 3} -, C 8 F 17 - (CH 2) 3 -O- (CH 2) 3 -, etc. are also used.

Q in the general formula (3) represents a single bond or a divalent linking group. When Q is a single bond, it means that R ^f and A are directly bonded. When Q is a divalent linking group, Q is preferably a divalent linking group containing no fluorine atom. Q is preferably a divalent hydrocarbon group having 1 to 22 carbon atoms or a divalent hydrocarbon group containing an inactive atom in the reaction of the present invention. When Q is a divalent hydrocarbon group containing an inert atom, a divalent hydrocarbon group containing an etheric oxygen atom or a thioetheric sulfur atom, or an isocyanate group and a reactive hydrogen atom are not bonded. Examples thereof include a divalent hydrocarbon group containing a nitrogen atom.

  Moreover, as A in the said General formula (3), a hydroxyl group, an amino group, an alkylamino group, or a carboxy group is preferable, and especially that it is a hydroxyl group is the solubility with respect to the organic solvent of the compound represented by General formula (3). From the viewpoints of performance, ease of synthesis, and cost.

  Specific examples of the compound represented by the general formula (3) having the above structure are shown below. However, Φ1 in the following exemplary compounds represents a 1,4-phenylene group or a 1,3-phenylene group.

CF ₃ (CF ₂ ) ₄ CH ₂ OH, CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OH, H (CF ₂ ) ₆ CH ₂ CH ₂ OH, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OH, CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OH, (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH ₂ OH, CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₂ CH ₃ ) CH ₂ CH ₂ OH CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OH, CF ₃ (CF ₂ ) ₇ CONHCH ₂ CH ₂ OH, CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OH CF ₃ (CF ₂ ) ₂ C (CF ₃ ) ═C [CF (CF ₃ ) ₂ ] OCH ₂ CH ₂ OH, (CF ₃ ) ₂ C═C (CF ₂ CF ₃ ) OΦ1COOCH ₂ CH ₂ OH, CF _{3 (CF 2) 7 SO 2} N (CH 2 CH 3) CH 2 CH 2 NHCH 3, CF 3 (CF 2) 7 CONHCH 2 CH 2 N _{CH 3, CF 3 (CF 2} ) 7 SO 2 N (CH 2 CH 3) CH 2 CH 2 NHCH 3, CF 3 (CF 2) 7 SO 2 N (CH 2 CH 3) CH 2 CH 2 COOH, CF 3 _{(CF 2) 7 CONHCH 2 CH} 2 COOH, CF 3 (CF 2) 7 COOH, [(CF 3) 2 CF] 2 C = C (CF 3) OΦ1COOH.

  Examples of the isocyanate compound used together with the compound represented by the general formula (3) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), methylene bis ( Cyclohexyl isocyanate) (H12MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), modified products thereof (nurateated modified products, prepolymer modified products, carbodiimide modified products, etc.), and as commercially available products, For example, as an isocyanurate type prepolymer of hexamethylene diisocyanate, Duranate THA-100 (manufactured by Asahi Kasei Kogyo Co., Ltd.), Duranate TPA-100 (Asahi Kasei Kogyo) Duranate 24A-100 (Asahi Kasei Kogyo Co., Ltd.), Duranate 22A-75PX (Asahi Kasei Kogyo Co., Ltd.) as a biuret type prepolymer of hexamethylene diisocyanate, etc. ), Sumidur N3200 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc., as adduct type prepolymers of hexamethylene diisocyanate, Duranate P-301-75E (manufactured by Asahi Kasei Kogyo Co., Ltd.), Sumijoule HT (Sumitomo Bayer Urethane Co., Ltd.) Manufactured).

  The above-mentioned fluorine-containing compound represented by the general formula (3) is added to a solution containing polyisocyanate, water and an organic solvent, and a mixed solution is applied onto the water-repellent / antifouling film, thereby A water-repellent / antifouling article can be obtained.

  Moreover, a fluorinated olefin polymer can also be used. The fluorinated olefin polymer refers to a polymer containing a fluorinated olefin monomer, and is dispersed or dissolved in an organic solvent. Specific examples thereof include polytetrafluoroethylene, polyvinylidene fluoride, (ethylene / tetrafluoroethylene) copolymer, (vinylidene fluoride / tetrafluoroethylene) copolymer, and (tetrafluoroethylene / hexafluoropropylene) copolymer. , Polyfluorinated vinyl ether, polychlorotrifluoroethylene, (ethylene / chlorotrifluoroethylene) copolymer, (fluorinated vinyl ether / tetrafluoroethylene) copolymer, and the like. These are paint resins such as “Lumiflon” manufactured by Asahi Glass Co., Ltd., “Fluonate” manufactured by Dainippon Ink and Chemicals, “Zaflon” manufactured by Toagosei Co., Ltd., and “Zeffle” manufactured by Daikin Industries, Ltd. It is sold as. The fluorinated olefin polymer may be a single polymer or a combination of two or more polymers, but is compatible with other acrylic components and processability such as solubility in solvents. In addition, it is desirable to contain a vinylidene fluoride polymer in that it has both rain and dripping resistance.

  It is preferable to use the general formula (2) or (3) together with the compound represented by the general formula (1). Specific examples of the compound represented by the general formula (1) include the following compounds.

  In the formula, l and m represent a positive integer of 1 to 30. Among these, the following compounds can be mentioned from the viewpoint of surface concentration, hydrolyzability, detachability, and availability.

  Examples of commercially available products include fluorine-containing silicates such as Zaffle GH-700 manufactured by Daikin Industries, Ltd .; non-fluorinated silicates such as MS57, MS56, and MS56S manufactured by Mitsubishi Chemical Corporation, but are not limited thereto. Is not to be done.

  In addition, a water-repellent resin obtained by graft polymerization of a fluororesin and a siloxane can be preferably used in the present invention, and a ZX series manufactured by Fuji Kasei Kogyo Co., Ltd. can be used as a commercial product.

  Two or more of these compounds may be used in combination. The combination to be used in combination may be appropriately selected depending on the purpose, but for example, it is preferable to use an organic compound (coupling agent) having a coupling action.

  As the coupling agent, for example, methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl isocyanate, 3-triethoxysilylpropyl isocyanate, methyltris ( Examples thereof include silane coupling agents such as ethylmethylketoxime) silane, and those containing an alkylketoxime group or an isocyanate group are preferred. In particular, a silane coupling agent having an isocyanate group or an epoxy group is preferable because recoatability is good.

≪Metal element-containing oxide thin film≫
In the water-repellent / antifouling article of the present invention, a metal element-containing oxide thin film is preferably provided on the surface of the water-repellent / antifouling film. In addition, the provision of a subbing film made of a metal element-containing oxide thin film between the base material and the water-repellent / antifouling film improves the adhesion between the base material and the water-repellent / antifouling film, From the viewpoint of protecting the eluted substances from

The metal element-containing oxide thin film according to the present invention is an inorganic compound similar to the inorganic material fine particles of the water-repellent / antifouling film according to the present invention, such as silicon dioxide (SiO ₂ ), alumina (Al ₂ O ₃ ), oxidation It is made of ceramic materials such as titanium (TiO ₂ ), indium oxide (InO ₃ ), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and has high permeability. From the viewpoint of In the present invention, as a method for forming a fine ceramic layer, it is preferable to apply the atmospheric pressure plasma method preferably used for the formation of the water-repellent / antifouling film to the formation of the metal element-containing oxide thin film in the same manner. .

≪Base material≫
The substrate applicable to the water-repellent / antifouling article of the present invention is preferably a substrate having excellent transparency, and is an inorganic transparent substrate such as a transparent glass substrate or an organic material such as a plastic substrate. Transparent resin base material.

  Examples of transparent resin base materials include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate. Cellulose esters or their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfones, polyetherketoneimide , Polyamide, fluororesin, nylon, polymethyl methacrylate Acrylic or polyarylates, or organic-inorganic hybrid resins and the like these resins and silica.

  In the present invention, the substrate is a transparent glass substrate from the viewpoint of imparting excellent properties such as water repellency / antifouling property, water slidability and durability of the present invention, and the final water repellency / antifouling property. It is preferable that the average transmittance in the visible light region is 85% or more as a functional article from the viewpoint of obtaining excellent transparency when applied to a building window glass or a vehicle window glass.

  The average transmittance in the visible light region referred to in the present invention is the sum of the transmittances in the visible light region obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm, and the average value thereof. Defined as For the transmittance at each measurement wavelength, a conventionally known measuring device can be used. For example, a spectrophotometer UVIDFC-610 manufactured by Shimadzu Corporation, a 330-type self-recording spectrophotometer manufactured by Hitachi, Ltd., a U-3210-type self-recording It can be determined by measuring using a spectrophotometer, a U-3410 type self-recording spectrophotometer, a U-4000 type self-recording spectrophotometer, or the like.

  Examples of the glass substrate applicable to the present invention include alkali-containing glass substrates such as inorganic glass, organic glass, soda lime silicate glass substrate having functional groups (hydroxyl group, amino group, thiol group, etc.) on the surface, borosilicate Examples include alkali-free glass substrates such as acid glass substrates. The glass substrate may be laminated glass, tempered glass, or the like.

≪Formation of base film≫
(Undercoat)
Colloidal silica fine particles (primary particle size: 4-6 nm) manufactured by Nissan Chemical Industries, Ltd. are dispersed in water containing 20% by mass of polyethylene glycol and acetylacetone (volume ratio: 20/1), and 0.5% by mass of silica is dispersed. A liquid was obtained. A 3 mm-thick soda lime glass (manufactured by Opton) base material that has been degreased and washed with acetone in advance and cleaned to remove contaminants on the surface by the atmospheric pressure plasma surface treatment described below is used. And dried at 120 ° C. for 30 minutes to form a coating film containing silica fine particles having a thickness of 0.05 μm as a base film.

(Undercoat with undercoat)
SiO ₂ film is 3nm using an atmospheric pressure plasma CVD process shown below on a soda lime glass substrate, 5nm, 30nm, 50nm, 75nm , and formed to be 100 nm, respectively SiO ₂ undercoating film-coated glass group A silica fine particle-containing coating film was formed on the material in the same manner as the above-described base film to form a base film with an undercoat film.

<< Formation of Underlayer >>
(Underlayer)
The base film and the base film with an undercoat film were subjected to a surface treatment for 10 seconds using the atmospheric pressure plasma surface treatment shown below to form a base layer having irregularities on the surface.

(Overcoat film)
Using the atmospheric pressure plasma CVD process shown below, an SiO ₂ film was formed on the surface of the under layer so as to have a thickness of 3 nm, 5 nm, 30 nm, 50 nm, 75 nm, and 100 nm, thereby forming an under layer with an overcoat film.

(Atmospheric pressure plasma surface treatment)
Using the jet type atmospheric pressure plasma discharge treatment apparatus shown in FIG. 1, plasma is irradiated on the surface of a glass substrate on which a base film is formed or a glass substrate on which an undercoat film with an undercoat film is formed under the following conditions. Thus, an underlayer was formed.

<Power supply conditions>
High frequency side: High frequency power supply (13.56 MHz) manufactured by Pearl Industrial Co., Ltd. 6 W / cm ²
Low frequency side: SEREN high frequency power supply (100 kHz) 5 W / cm ²
<Electrode conditions>
As the plate-like electrode (length: 50 mm), two electrodes in which a metal base material and a ceramic with a thickness of 1 mm were sprayed on the surface were used. The gap between the two electrodes was set to 1 mm, and each electrode was discharged by passing water for cooling (25 ° C.).

<Gas conditions>
Discharge gas; Nitrogen gas 2 slm / cm
Reaction gas: Oxygen gas 0.1 slm / cm
* Slm / cm ... Standard Liter per Minute / Unit gas supply width (cm)
Standard state: flow rate of gas supplied per minute at 25 ° C. and 1 atm (1.01325 × 10 ⁵ ) (in L units)
<Processing time>
Surface treatment was performed by reciprocating the substrate so that the accumulated time during which the object to be treated was exposed to discharge was 10 seconds.

(Atmospheric pressure plasma CVD treatment)
An undercoat film or an overcoat film was formed under the following conditions using the direct type atmospheric pressure plasma discharge treatment apparatus shown in FIG.

<Power supply conditions>
High frequency side: High frequency power source (13.56 MHz) manufactured by Pearl Industrial Co., Ltd. 8 W / cm ²
Low frequency side: SEREN high frequency power supply (100 kHz) 6 W / cm ²
<Electrode conditions>
Two 30 mm-square rod electrodes and a plate electrode for fixing the substrate are used. The base material of the rod-like electrode and the plate-like electrode is stainless steel (SUS304), but ceramic is sprayed on the surface with a thickness of 1 mm. The distance (discharge gap) between the rod-shaped electrode and the substrate surface was set to 1 mm, and a cooling refrigerant (water) was passed through the electrode at a temperature of 25 ° C. for discharge.

<Gas conditions>
TEOS (tetraethoxysilane) was vaporized by bubbling as a source gas and supplied to the discharge space, and a SiO ₂ film was formed on the surface of the substrate using a decomposition reaction by plasma energy.

Discharge gas; Nitrogen gas 2 slm / cm
Reaction gas: Oxygen gas 0.1 slm / cm
Gas for forming a thin film: 200 ml of TEOS raw material is prepared in a 500 ml glass bubbling container and kept at 25 ° C. Nitrogen gas 0.1 slm / cm is supplied as a carrier gas for supplying vaporized TEOS to the discharge space.

≪Coupling agent formation≫
An amino-based silane coupling agent TSL8331 manufactured by GE Toshiba Silicon Corporation was diluted to 1% with IPA to prepare a coupling agent.

(coating)
It applied so that the dry film thickness on various base materials might be set to 0.01 micrometer using the bar coater.

≪Formation of water repellent and antifouling materials≫
(Preparation of water repellent / antifouling material-1)
Fluorine resin material ZX-007C manufactured by Fuji Chemical Industry Co., Ltd. and curing agent Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd. are mixed at a ratio of 1.2: 1 of NCO and hydroxyl value (OH), and sufficient at room temperature. Then, the mixture was diluted with MEK solvent so that the solid content concentration was 1% to prepare a water-repellent / antifouling material-1.

(Preparation of water repellent / antifouling material-2)
(Preparation of silicate material)
Deionized water was added at 7% by mass to a silicate MSH-4 main agent solution manufactured by Mitsubishi Chemical Corporation, and the mixture was agitated and hydrolyzed while being kept at 60 ° C. to prepare a silicate solution.

  The silicate solution, a fluorine resin material ZX-022-H (non-volatile component 45%) manufactured by Fuji Kasei Kogyo Co., Ltd., and a dilution solvent IPA were added at a ratio of 70: 13.3: 16.7, respectively, and 60 ° C. The mixture was aged while stirring at a temperature to prepare a fluororesin silicate mixed solution. The fluororesin silicate mixed solution was diluted with MEK solvent so as to have a solid content concentration of 1% to prepare a water repellent / antifouling material-2.

(coating)
The water-repellent / antifouling materials -1 and 2 were applied to the surface of each substrate with a base layer using a bar coater so that the dry film thickness was 0.05 μm, and Examples 1 to 1 shown in Table 1 were applied. 20 and the water-repellent / antifouling articles of Comparative Examples 1 and 2 were produced. Each feature is shown below.

Example 1
Only a base layer was formed on a glass substrate, and then coated with water repellent / antifouling material-1.
Comparative Example 1
Only the water repellent / antifouling material-1 was coated without an underlayer,
Examples 2-5
Coated undercoat film (difference in film thickness) on glass substrate,
Examples 6 and 7
Also coated with an undercoat film, but the film thickness is too thick.
Comparative Example 2
A glass substrate was coated with an undercoat film (50 nm), and a water-repellent / antifouling material-1 was coated without forming an underlayer.
Examples 8-11
An overcoat was applied on the underlayer.
Examples 12 and 13
The same overcoat was applied, but the film thickness was too thick.
Examples 14-16
Both undercoat and overcoat,
Example 17
Also with undercoat and overcoat. However, the film thickness is too thick,
Example 18
No silane coupling agent,
Examples 19 and 20
Water repellent / antifouling material-1 was changed to water repellent / antifouling material-2.

Evaluation Method ≪Initial water repellency: static contact angle measurement of water≫
3 μL of water is dropped on the surface of the water-repellent / antifouling article, and the static contact angle 15 seconds after dropping is measured using a contact angle measuring device (contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd.). The initial water repellency was evaluated based on the following criteria.
◎ Static contact angle is 110 ° or more ○ Static contact angle is 100 ° or more and less than 110 ° △ Static contact angle is 90 ° or more and less than 100 ° x Static contact angle is less than 90 °.

≪Initial sliding property: water falling angle measurement≫
A stage in which 50 μL of water is dropped onto the surface of the water / oil repellent article and the water repellent / antifouling article of the contact angle measuring device (contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd.) is held. The angle is gradually tilted from 0 ° (horizontal) to 90 ° (vertical), and the angle at which water drops begin to move through the water-repellent / antifouling article is measured. It was evaluated.
◎ Rolling angle is less than 10 ° ○ Rolling angle is 10 ° or more and less than 20 ° △ Rolling angle is 20 ° or more and less than 30 ° x Rolling angle is 30 ° or more.
≪Anti-fouling test≫
Magic ink repellency and wiping properties Using oil-based magic (ZEBURA Mackey bold), draw a 6 x 50 mm line on the surface of a water-repellent and antifouling article. Evaluation was made as one of the antifouling evaluations.
◎ Magic ink repels in a dot shape ○ Ink can be written in a line, but can be easily wiped (within 5 times) with a tissue △ Ink can be written and wiped with a tissue 5 times or more to wipe Even if it is written and wiped with a tissue, it is difficult to wipe off, and traces may remain.

≪Ease of wiping fingerprints≫
The index finger was pressed against the surface of the water-repellent / antifouling article for 5 to 10 seconds, and the fingerprint was wiped off with a tissue.
○ Fingerprints can be wiped off △ Fingerprints are difficult to wipe off but no traces are left × Fingerprints are difficult to wipe off and traces may remain.

≪Abrasion resistance test≫
As the wear resistance test, attaching the felt (0.63 g / cm ³⁾ as a wear member to a reciprocating abrasion tester (manufactured by Shinto Scientific Co., Ltd. HEIDON-14DR), the water-repellent-under a load of 600 g / cm ² The surface of the antifouling article was slid back and forth 10,000 times at a speed of 100 mm / sec. At that time, the felt wear material was replaced with a new one at the end of the 5000 reciprocations, and the reciprocating sliding was continued 5000 times for a total of 10,000 reciprocating slides. The water repellency and sliding property at the end of 10,000 times were evaluated according to the above-mentioned evaluation criteria, and the abrasion resistance was evaluated.

≪Scratch resistance test≫
As a scratch resistance test, the surface of a water-repellent / antifouling article was subjected to a reciprocating friction of 10 times at a stroke width of 100 mm and a speed of 100 mm / sec by applying a load of 400 gf / cm ² to # 0000 steel wool. Was observed visually and with a microscope (Digital Microscope VHX-600 manufactured by KEYENCE Co., Ltd.) and evaluated according to the following criteria to evaluate scratch resistance.

≪Ease of noticeable wounds≫
◎ No scratches can be seen visually, and no scratches can be confirmed even by microscopic observation ○ No scratches can be seen by visual observation, but scratches can be confirmed by microscopic observations Δ Visible × Many visible scratches are visible.

≪Taber test≫
In the Taber Abrasion Tester, the surface of the water-repellent / antifouling article was subjected to a total of 1000 rotation wear tests under a load speed of 4.9 N using a wear wheel CS-10F at a rotation speed of 60 rpm. The haze value showing the highest value was measured and evaluated according to the following criteria, and the evaluation was made for the Taber test.
ΔH = (maximum haze value during Taber test) − (haze value before Taber test)
[Delta] H is less than 0.3 [Delta] H is 0.3 or more and less than 1.0 [Delta] H is 1.0 or more and less than 2.0 x [Delta] H is 2.0 or more.

≪Weather resistance test≫
As a weather resistance test, using a UV resistance tester (Isuper UV Tester W-13, manufactured by Iwasaki Electric Co., Ltd.), the surface of each water-repellent / antifouling article was 340 nm in wavelength and 0.6 W / cm ^{2 in} strength. In the black panel temperature of 48 ± 2 ° C., ion-exchanged water showering was performed for 30 seconds every hour in a cycle of irradiation time of 20 hours + darkness of 4 hours, and ultraviolet irradiation was performed for a total of 400 hours. After this test, the water repellency / antifouling article surface was subjected to the above water repellency evaluation (initial water repellency) and antifouling evaluation (magic ink repellency / wiping property), and evaluated according to the following criteria: The evaluation was a weather resistance test.
◎ Static contact angle is 100 ° or more ○ Static contact angle is 90 ° or more and less than 100 ° △ Static contact angle is 80 ° or more and less than 90 ° x Static contact angle is less than 80 °.

≪Hot water resistance≫
As a warm water resistance test, each water repellent / antifouling article was immersed in ion exchange water at 50 ° C. for 500 hours, taken out and dried, then measured for water contact angle, and evaluated according to the following criteria. It was a sex test.
○ Static contact angle is 90 ° or more △ Static contact angle is 80 ° or more and less than 90 ° x Static contact angle is less than 80 ° ≪Chemical resistance≫
As a chemical resistance test, each water-repellent / antifouling article was immersed in a 1.0 M / l NaOH aqueous solution for 1 hour, washed and dried, then measured for water contact angle, and evaluated according to the following criteria. A chemical resistance test was conducted.
○ Static contact angle is 90 ° or more △ Static contact angle is 80 ° or more and less than 90 ° x Static contact angle is less than 80 °.

≪Optical characteristics≫
≪Transmissivity≫
For water-repellent / antifouling articles, the average transmittance in the visible light region is measured using an integrating sphere type light transmittance measuring device (HGM-2DP manufactured by Suga Test Instruments Co., Ltd.), and evaluated according to the following criteria: The transmittance was evaluated. The visible light region has a wavelength of 400 to 720 nm.
◎ Average transmittance in the visible light region is 90% or more ○ Average transmittance in the visible light region is 85% or more and less than 90% △ Average transmittance in the visible light region is 80% or more and less than 85% × Average transmittance in the visible light region Is less than 80%.

≪Haze≫
About the base material before forming a water-repellent / anti-fouling article and a water-repellent / anti-fouling film, the haze value was measured using an integrating sphere type light transmittance measuring device (HGM-2DP manufactured by Suga Test Instruments Co., Ltd.). The haze value increase ΔH due to film formation was determined according to the following formula, and evaluated according to the following criteria to evaluate haze.
ΔH = (Haze value of water-repellent / antifouling article) − (Haze value of base material only before film formation)
[Delta] H is less than 0.3 [Delta] H is 0.3 or more and less than 1.0 [Delta] H is 1.0 or more and less than 2.0 x [Delta] H is 2.0 or more.

≪Anti-fouling test≫
Magic ink repellency and wiping properties Using oil-based magic (ZEBURA Mackey bold), draw a 6 x 50 mm line on the surface of a water-repellent and antifouling article. Evaluation was made as one of the antifouling evaluations.
◎ Magic ink repels in a dot shape ○ Ink can be written in a line, but can be easily wiped (within 5 times) with a tissue △ Ink can be written and wiped with a tissue 5 times or more to wipe Even if it is written and wiped with a tissue, it is difficult to wipe off, and traces may remain.

≪Ease of wiping fingerprints≫
The index finger was pressed against the surface of the water-repellent / antifouling article for 5 to 10 seconds, and the fingerprint was wiped off with a tissue.
○ Fingerprints can be wiped off △ Fingerprints are difficult to wipe off but no traces are left × Fingerprints are difficult to wipe off and traces may remain.

  It can be seen from Table 2 that all of the samples of the present invention have excellent water repellency and sliding property (water drop slidability), and these properties have durability, abrasion resistance, and scratch resistance that last for a long time.

It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the 2 frequency jet system useful for this invention. It is the schematic which shows an example of the direct type atmospheric pressure plasma discharge processing apparatus applicable to this invention.

Explanation of symbols

21, 110 Atmospheric pressure plasma discharge treatment apparatus 22, G, G ° gas 23 Mixed gas 31 Power supply 31a, 31b High frequency power supply 41a, 41b Electrode 42 Dielectric 43 Discharge space 46, F substrate 47 Moving stage, Moving stage electrode 111 First 1 electrode 112 2nd electrode 121 1st power supply 122 2nd power supply 123 1st filter 124 2nd filter 126 High frequency voltage probe 127,128 Oscilloscope

Claims (13)

A base film composed of inorganic material fine particles and an organic material-based binder composition is formed on the substrate, and then the binder is removed by atmospheric pressure plasma treatment to repel the surface irregularities and voids inside the base layer. A water repellent / antifouling article comprising a water / antifouling film coated or impregnated with a water / antifouling material. A metal element-containing oxide thin film having a thickness of 5 nm to 50 nm is formed as an overcoat film on the surface of the underlayer by atmospheric pressure plasma, and then a water-repellent / antifouling material is formed on the metal element-containing oxide thin film. The water-repellent / antifouling article according to claim 1, wherein the article is coated or impregnated. 3. An undercoat film-containing substrate in which a metal element-containing oxide thin film having a thickness of 5 nm to 50 nm is formed as an undercoat film on the substrate by atmospheric pressure plasma as the undercoat film. Water repellent and antifouling goods. The water repellent / antifouling article according to claim 2 or 3, wherein the metal element-containing oxide thin film is an oxide thin film containing at least silicon atoms. The water repellent / antifouling article according to any one of claims 1 to 3, wherein the underlayer and the undercoat film are formed at a substrate temperature of 15 to 150 ° C. The water / repellent / antifouling article according to any one of claims 1 to 5, wherein a film thickness of the entire water / repellent / antifouling film is 10 nm or more and 200 nm or less. The water / repellent / antifouling material according to any one of claims 1 to 6, wherein the water / repellent / antifouling material is coated or impregnated with one to three coupling agents before being coated or impregnated. Sex goods. The water-repellent / antifouling material contains at least a fluorine-based resin or a fluorine-containing silicone resin and a silicate compound represented by the following general formula (1). Water repellent and antifouling article.

(Wherein n is an integer of 2 or more, R ¹ is all different or at least two are the same and both are monovalent organic groups having 1 to 1000 carbon atoms or hydrogen atoms, and the organic groups are oxygen atoms, (At least one selected from a nitrogen atom and a silicon atom may be contained, and a part or all of the hydrogen atoms of the organic group may be substituted with a fluorine atom.) The base material is at least one selected from a transparent glass plate, a transparent resin plate, and a transparent resin film, and the average transmittance of the visible light region of the base material is 85% or more. The water repellent / antifouling article according to any one of 1 to 8. An architectural window glass comprising the water-repellent / antifouling article according to any one of claims 1 to 9. A vehicle window glass comprising the water-repellent / antifouling article according to any one of claims 1 to 9. A display member comprising the water-repellent / antifouling article according to any one of claims 1 to 9. An optical component comprising the water repellent / antifouling article according to any one of claims 1 to 9.

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