JP5407869B2 - Water-repellent or antifouling articles, architectural window glass, vehicle window glass, display members, optical components constructed using the same - Google Patents

Description

  The present invention is a highly durable water-repellent or antifouling article that has excellent water repellency, sliding property (water droplet fallability), antifouling property, and 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, obtained by hydrolyzing a mixture of a fluoroalkyl group silane compound and polydimethylsiloxane (the same derivative) and an alkoxysilane compound in a solvent. The obtained 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 (for example, see Patent Document 1). This film regularly segregates with a high concentration of fluoroalkylsilane component on the surface layer, and the gaps are filled with methyl groups, so the surface contact angle is large, the water drop falling angle is small, and a good water-repellent film is obtained. It is said.

  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 the wear resistance and durability are problems.

  A colloidal silica is added to a hydrolyzate such as TEOS on a glass substrate and applied, and then baked at about 250 ° C. to form an underlayer, and a fluoroalkylsilane hydrolyzate is coated with fluorine such as tetrafluoroethylene. A resin dispersion is mixed 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 film thickness of 4 to 1000 nm, thereby improving wear resistance (for example, Patent Documents) 2).

  However, in the water-repellent film obtained according to the description of Patent Document 2, the friction is increased by the unevenness formed by the colloidal silica due to high-speed reciprocating friction by a wiper or the like, and the water-repellent film is peeled off. Abrasion resistance cannot be obtained. Further, in recent years, it cannot be applied to a base material containing a resin film such as a laminated glass used for a windshield of an automobile because it cannot be heated and fired.

  In addition, 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 is applied to the substrate surface. By heating and baking to form a sol-gel film having a fine uneven surface layer, and coating the sol-gel film with a water-repellent film layer, the adhesion and wear resistance are high, and the performance is maintained over the long term. It is said that a water repellent film that can be obtained is obtained (for example, see Patent Document 3).

  However, since the water-repellent film obtained according to the description of Patent Document 3 also tends to increase friction due to unevenness, it has abrasion resistance and scratch resistance that can withstand long-term durability required for automobile windshields. Sex was not enough.

  Furthermore, 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 4).

However, the water-repellent film obtained according to the description in Patent Document 4 is also insufficient in wear resistance and scratch resistance for the same reason as described above.
JP-A-8-12375 JP-A-8-319137 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, wear resistance, and scratch resistance for which these characteristics last for a long time. It is to provide a water-repellent or antifouling article having Moreover, it is providing the window glass for constructions, the window glass for vehicles, the display member, and the optical component which were comprised using this water repellent or antifouling article.

  The above object of the present invention is achieved by the following configurations.

1. A base layer in which an inorganic material is present as particles or agglomerates on the surface of the substrate is formed using an atmospheric pressure plasma method, so that water repellent or antifouling materials are exposed from the periphery or gaps of the particles or agglomerates. a water-repellent or antifouling article, wherein the underlying layer is coated or impregnated with the water repellent or antifouling material.

  2. 2. The water repellent or antifouling article according to 1 above, wherein an undercoat film is formed between the base layer and the substrate.

  3. 3. The water repellent or antifouling article as described in 2 above, wherein the undercoat film is formed by an atmospheric pressure plasma method.

  4). 4. The water-repellent or antifouling article according to any one of items 1 to 3, wherein the base layer is formed at a substrate temperature of 15 ° C. or higher and 150 ° C. or lower.

  5. 5. The water repellent or antifouling article according to any one of 1 to 4 above, wherein the atmospheric pressure plasma method is an ejection type plasma method.

  6). 6. The water repellency according to any one of 1 to 5 above, wherein the average particle diameter (D1) of the particles of the underlayer is 2 to 100 nm, and the average film thickness of the entire underlayer is 5 to 200 nm. Antifouling article.

  7). 7. The water repellency or antifouling property according to any one of 1 to 6 above, wherein the water repellency or antifouling material coated or impregnated on the underlayer has a thickness of 2 to 100 nm. Goods.

  8). 8. The repellent according to any one of 1 to 7 above, wherein the underlayer is coated or impregnated with at least one coupling agent before the water repellent or antifouling material is coated or impregnated. Water or antifouling article.

  9. Plasma treatment of the surface of the underlayer is performed before the coating or impregnation with the water repellent or antifouling material, or the coating or impregnation with the water repellent or antifouling material after the coating or impregnation with the coupling agent. 9. The water-repellent or antifouling article according to any one of 1 to 8 above.

  10. 10. The water repellent or 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 or antifouling article.

(In the formula, n is an integer of 1 or more, R ¹ is all different or at least two are the same, both are monovalent organic groups or hydrogen atoms having 1 to 1000 carbon atoms, and the organic groups are oxygen atoms, One type 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.)
11. 11. The water repellency according to any one of 1 to 10 above, wherein the substrate is a transparent glass substrate or a transparent resin substrate, and the average transmittance in the visible light region is 85% or more. Antifouling article.

  12 An architectural window glass comprising the water-repellent or antifouling article according to any one of 1 to 11 above.

  13. A vehicle window glass comprising the water repellent or antifouling article according to any one of 1 to 11 above.

  14 A display member comprising the water-repellent or antifouling article according to any one of 1 to 11 above.

  15. An optical component comprising the water-repellent or antifouling article according to any one of 1 to 11 above.

  Since the present invention uses a base layer mainly composed of an inorganic material as a skeleton, the water-repellent film as a whole is a high-hardness film that is difficult to scratch, and because it is an optically thin film, the scratch is less conspicuous and wear and scratch resistance. It is possible to maintain water repellency or antifouling properties that are extremely excellent in performance. Moreover, since elution due to impurities from the substrate is passivated by the underlayer or the undercoat film, it is possible to suppress the weather resistance deterioration. The underlayer formed by atmospheric pressure plasma has high adhesion to the substrate, and by providing an undercoat film, the adhesion is further improved, and a film having high water resistance and chemical resistance can be obtained.

It is the schematic which shows an example of the direct type atmospheric pressure plasma discharge processing apparatus applicable to this invention. It is the schematic which shows an example of the other direct frequency atmospheric pressure plasma discharge processing apparatus of the other 2 frequency system which installed the power supply of a different frequency in each electrode. 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 plasma jet type atmospheric pressure plasma discharge processing apparatus which concerns on this invention.

Explanation of symbols

21, 110 Atmospheric pressure plasma discharge treatment device 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 101a, 101b High-frequency filter 111 First electrode 112 Second electrode 121 First power supply 122 Second power supply 123 First filter 124 Second filter 126 High-frequency voltage probe 127, 128 Oscilloscope

  Hereinafter, the present invention will be described in detail.

  The water-repellent or antifouling article of the present invention forms a strong particle or agglomerate underlayer with good adhesion on the substrate by an atmospheric pressure plasma method, and is coated around or around the particle or agglomerate. It has become possible to expose the surface of the water repellent or antifouling material to the minimum necessary amount. As a result, even under high-speed and long-term friction due to wipers, etc., which was insufficient with the conventional method, the foundation layer portion that is strong and has extremely high adhesion to the substrate retains the film structure. In addition, since it is possible to protect the water-repellent or antifouling material present in the vicinity thereof, it has become possible to obtain extremely high durability against wear.

  In addition, by performing the formation method of the underlayer using an atmospheric pressure plasma method, it is possible to obtain a stronger underlayer with a higher adhesion, and further does not require a baking time like a sol-gel film, The above-mentioned strong underlayer can be formed even at a low temperature of 150 ° C. or lower.

  Further, by setting the film thickness of the water-repellent or antifouling material to 100 nm or less, even if scratches are made, it is hardly noticeable optically and its performance can be sufficiently exhibited.

<Underlayer>
The particle or agglomerate underlayer in the present invention has an average particle diameter (D1) mainly composed of an inorganic material of 2 to 100 nm and an average film thickness of the entire underlayer of 5 to 200 nm, preferably 10 to 50 nm. Say. Note that the term “granular shape” refers to a shape in which particles are partially fused. The inorganic material is preferably an inorganic compound having transparency (transparency) to visible light, and metal element-containing oxides, nitrides, oxynitrides, and 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 ), and indium oxide (In ₂ O ₃ ). A ceramic material such as 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. The average particle diameter (D1) is measured by surface SEM, surface TEM, cross-sectional SEM, and cross-sectional TEM observation. Although there is no particular limitation in the cross-sectional observation, a sample for cross-sectional observation is created using focused ion beam (FIB) processing (for example, using SMI2050 manufactured by SII), and then the particle or agglomerated particle size is measured by SEM and TEM. Is preferable because it can be measured easily and without changing the structure of the underlayer.

<Undercoat>
In the water-repellent or antifouling article of the present invention, it is preferable to provide an undercoat film between the base layer and the substrate. The subbing film is used to passivate impurities such as alkali components from the base material and prevent deterioration of the water-repellent or antifouling material. The film thickness is 200 nm or less, preferably 5 to 50 nm. In the present invention, it is preferable to provide an undercoat film made of a metal element-containing oxide thin film from the viewpoint of improving the smoothness of the base material and improving the adhesion between the base material and the water-repellent or antifouling film.

Examples of the metal element-containing oxide thin film according to the present invention include silicon dioxide (SiO ₂ ), alumina (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), indium oxide (InO ₃ ), and tin oxide (SnO ₂ ). It is preferable that it is made of a ceramic material such as tantalum oxide (Ta ₂ O ₅ ) or zirconia (ZrO ₂ ) from the viewpoint of obtaining high permeability. In the present invention, as a method for forming a fine ceramic layer, the atmospheric pressure plasma method is preferably applied to the formation of a metal element-containing oxide thin film in the same manner.

"Base material"
The substrate applicable to the water-repellent or antifouling article of the present invention is preferably a substrate having excellent transparency, and 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, polyether ketone, polyimide, polyether sulfone, polysulfones, polyether ketone imide , Polyamide, fluororesin, nylon, polymethyl methacrylate Over DOO, acrylic or polyarylates, or organic-inorganic hybrid resin and the like these resins and silica.

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

  The average transmittance in the visible light region referred to in the present invention is obtained by integrating 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. Define what you want. 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 spectrum It can be determined by measurement using a photometer, a U-3410 type self-recording spectrophotometer, a U-4000 type self-recording spectrophotometer, or the like.

  As a transparent glass substrate applicable to the present invention, an inorganic glass or organic glass having a functional group (such as a hydroxyl group, an amino group, a thiol group) on the surface, an alkali-containing glass substrate such as a soda lime silicate glass substrate, An alkali-free glass substrate such as a borosilicate glass substrate can be used. The transparent glass substrate may be laminated glass, tempered glass, or the like.

  In the present invention, the base material temperature is 15 ° C. or higher and 150 ° C. or lower when the base layer is formed.

《Water repellent or antifouling material》
The water repellent or antifouling material used in the present invention is not particularly limited, and various water repellent / antifouling materials can be applied. For example, organic fluorine compounds, organic silicon compounds, fluorine-containing organic metals A compound etc. can be mentioned. Each of these compounds may be directly applied in a solution state, dispersed in an appropriate solvent in the form of fine particles, or may be provided after polymerization.

(Organic fluorine compounds)
As an example of the organic fluorine compound applicable to the present invention, it can be provided 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 reduced, 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, preferably a linear or branched perfluoroalkyl group, Or the monomer which contains Rf group as the terminal of a perfluoro ether group is preferable.

  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) acrylic Over DOO, 2-ethylhexyl (meth) acrylate, maleic anhydride, aziridinyl (meth) acrylate, having a polysiloxane (meth) acrylate, and the like 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 provided 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) Rf-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” as used herein 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” which is a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms.

  Furthermore, 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 Rf 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 _{1~15), 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- (where 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) - ( where, p, q and r each represent an integer of 0 to 3, and (p + q + r) is an integer of 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 Rf 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 inert 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 the solubility with respect to the organic solvent of the compound represented by General formula (3) that it is a hydroxyl group From the viewpoint of 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 (Asahi Kasei Kogyo Co., Ltd.), Duranate TPA-100 (Asahi Kasei) Duminate 24A-100 (Asahi Kasei Kogyo Co., Ltd.), Duranate 22A-75PX (Asahi Kasei Kogyo Co., Ltd.) as a biuret-type prepolymer of hexamethylene diisocyanate. ), 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.), Sumidur 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 to obtain the water-repellent or antifouling article of the present invention. Can do.

  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. , Polyvinyl fluoride ether, polychlorotrifluoroethylene, (ethylene / chlorotrifluoroethylene) copolymer, (fluorovinyl 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. It is desirable to contain a vinylidene fluoride polymer in that it has both rain and dripping resistance.

In the general formula (1), n is an integer of 1 or more, R ¹ is all different or at least two are the same, and each is a monovalent organic group having 1 to 1000 carbon atoms or a hydrogen atom, and the organic group May contain one kind selected from an oxygen atom, a nitrogen atom and a silicon atom, and a part or all of the hydrogen atoms of the organic group may be substituted with a fluorine atom. Here, even if the organic group remains without undergoing a hydrolysis reaction, a material that does not deteriorate the water repellency or antifouling performance is good, and a part or all of the general formulas C _x H _{2x + 1} and H are substituted with fluorine atoms. What was made can be used preferably.

  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. It is not limited.

  In addition, a water-repellent resin obtained by graft polymerization of a fluororesin and 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 according to the purpose. For example, it is preferable to use an organic compound (coupling agent) having a coupling action.

<Coupling agent>
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 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.

<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.

  For the underlayer according to the present invention, a raw material described later is applied by a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method, a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure described later, and the like. Can be formed.

  However, it is difficult to obtain smoothness at the molecular level (nm level) by wet methods such as spraying and spin coating. Therefore, in the present invention, it is preferable to apply the atmospheric pressure plasma method because it is a film forming method that does not require a decompression chamber or the like and enables high-speed film formation and high productivity. Details of the layer forming conditions of the atmospheric pressure plasma method will be described later.

  For example, silicon oxide can be obtained by using a silicon compound as a raw material compound and oxygen as a decomposition gas, and silicon carbonate is generated by using carbon dioxide as a decomposition gas. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such an inorganic material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. In addition, since these dilution solvents are decomposed | disassembled into a molecular form and an atomic form during a plasma discharge process, the influence can be almost disregarded.

  Examples of the silicon compound that forms such an underlayer include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, and dimethyldimethoxy. Silane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, Bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) Carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldi Silazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyl Limethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetra Examples include methylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, and M silicate 51.

  In addition, as a decomposition gas for obtaining a silicon oxide film by decomposing a source gas containing these silicon atoms, for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas Nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc. .

  Various silicon carbides, silicon nitrides, silicon oxides, silicon halides, and silicon sulfides can be obtained by appropriately selecting a source gas containing silicon element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are particularly preferably used.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas to 50% or more of the entire mixed gas.

(Atmospheric pressure plasma treatment method)
Next, the atmospheric pressure plasma method (atmospheric pressure plasma CVD method) will be described in more detail.

  The conventionally known plasma CVD method is also called plasma-assisted chemical vapor deposition method or PECVD method, and various inorganic materials have good coverage and adhesion even in a three-dimensional shape, and the substrate temperature is too low. This is a technique that enables film formation without increasing the film thickness.

  In ordinary CVD (chemical vapor deposition), volatile and sublimated organometallic compounds adhere to the surface of a high-temperature substrate, causing a decomposition reaction due to heat, producing a thermally stable inorganic thin film. That's it. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and cannot be used for film formation on a resin base material.

  On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where a gas in a plasma state exists, and a volatilized / sublimated organometallic compound is introduced into the plasma space. The inorganic thin film is formed by spraying on the base material after the decomposition reaction occurs. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the gas temperature is kept low, the electron temperature is very high. The organometallic compound that is a raw material of the inorganic film can be decomposed even at a low temperature because it is in contact with an excited state gas such as ions or radicals. Therefore, it is a film forming method that can lower the temperature of a substrate on which an inorganic material is formed, and can sufficiently form a film on a plastic substrate.

  However, in the plasma CVD method, since it is necessary to apply an electric field to gas to ionize it to be in a plasma state, the film is usually formed in a reduced pressure space of about 0.1 to 10 kPa. When filming, the equipment is large and the operation is complicated, and this method has a problem of productivity.

  On the other hand, a plasma CVD method near atmospheric pressure (hereinafter referred to as an atmospheric pressure plasma CVD method or an atmospheric pressure plasma method) that can be suitably used in the present invention is reduced in pressure compared to a plasma CVD method under vacuum. In addition to high productivity and high plasma density, the film formation speed is high. In addition, compared with the normal conditions of the CVD method, under high pressure conditions such as atmospheric pressure, gas Since the mean free path is extremely short, a very flat film can be obtained. Such a flat film has good optical properties. From the above, in the present invention, it is preferable to apply the atmospheric pressure plasma CVD method to the plasma CVD method under vacuum.

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

  In addition, the excited gas referred to in the present invention means that at least part of the molecules in the gas move from the current state to a higher state by obtaining energy, and the 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 broadly includes the following two methods.

  One method is a plasma jet type atmospheric pressure plasma discharge treatment, 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, the mixed gas that has been converted to plasma is sprayed onto the surface of the base material to treat the surface of the base material, or is associated with and mixed with a desired film-forming gas, and then sprayed onto the transparent base material.

  The other method is a so-called direct atmospheric pressure plasma discharge treatment. In the state where a transparent base material is supported between a mixed gas containing a discharge gas and a counter electrode, the gas is introduced into the discharge space between the counter electrodes. In this method, a high-frequency voltage is applied to form a desired film, or the substrate surface is treated.

  FIG. 4 is a schematic view showing an example of a plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention. The present invention is not limited to this. In addition, the following description may include affirmative expressions for terms and the like, but it shows preferred examples of the present invention and limits the meaning and technical scope of the terms of the present invention. It is not a thing.

  In FIG. 4, the atmospheric pressure plasma discharge processing apparatus 21 has two pairs of electrodes 41 a and 41 b connected to a power supply 31 arranged in parallel. At least one of the electrodes 41a and 41b is covered with a dielectric 42, and a high frequency voltage is applied by a power source 31 to a discharge space 43 formed between the electrodes.

  The inside of the electrodes 41a and 41b has a hollow structure 44 so that heat generated by the discharge can be taken by water, oil, etc. during discharge and heat exchange can be performed so as to maintain a stable temperature.

  Further, gas 22 containing a discharge gas necessary for discharge is supplied to the discharge space 43 through the flow path 24 by each gas supply means not described, and a high frequency voltage is applied to the discharge space 43 to generate plasma discharge. As a result, the gas 22 including the discharge gas is turned into plasma. The plasmaized gas 22 is ejected into the mixing space 45.

  On the other hand, the mixed gas 23 supplied by each gas supply means (not shown) and containing the metal oxide gas necessary for forming the underlayer passes through the flow path 25 and is also carried to the mixed space 45 where it is converted into the plasma. The discharge gas 22 is merged and mixed, and sprayed onto the transparent substrate 46 placed on the moving stage 47.

  The underlayer-forming gas in contact with the plasma mixed gas is activated by the plasma energy and causes a chemical reaction, whereby an underlayer is formed on the substrate 46.

  This plasma jet type atmospheric pressure plasma discharge treatment apparatus has a structure in which a mixed gas containing a gas necessary for forming an underlayer is sandwiched or surrounded by an activated discharge gas.

  The moving stage 47 on which the substrate is mounted has a structure that can perform reciprocating scanning or continuous scanning, and can perform heat exchange similar to the electrode 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.

  This plasma jet type atmospheric pressure plasma discharge treatment apparatus has a structure in which a discharge gas is activated by being turned into plasma and then merged with a mixed gas containing a gas necessary for forming an underlayer. As a result, deposition of a film-formed product on the electrode surface can be prevented, but by adhering an antifouling film or the like to the electrode surface, the discharge gas and the gas necessary for forming the underlayer are mixed before discharge. It can also be a structure.

  FIG. 3 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 processing apparatus is not shown in FIG. 3 in addition to the plasma discharge processing apparatus and the electric field applying means having two power sources, but is an apparatus having a gas supply means and an electrode temperature adjusting means. It is.

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 the second frequency ω _{2 of} the second power supply 122. A lower 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 the passage of current from the second power source 122 to the second electrode, and the current from the first power source 121. Is designed to make it difficult to pass current from the first power supply 121 to the second power supply 122.

  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. The substrate surface is processed in the vicinity of the processing position 114 on the substrate F conveyed from the process. During the discharge treatment, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means. Depending on the temperature of the base material during the plasma discharge treatment, the degree of surface treatment and the like 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. 3 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. 1 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. 1, two electrodes 41 connected to a 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 taken by water, oil, etc. during the discharge, and heat exchange can be performed so that the temperature can be kept stable. 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 the mixed gas 23 containing the gas necessary for forming the underlayer passes through the flow path 25, They are 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 gas for forming the underlayer is activated by the gas G that is converted into plasma, causing a chemical reaction, and an underlayer is formed on the substrate 46.

  The stage 47 on which the base material is mounted has a structure capable of reciprocating scanning or continuous scanning, and can perform heat exchange similar to the electrode so that the temperature of the base material can be maintained as necessary. ing.

  Further, a waste gas exhaust passage 48 for exhausting the gas blown onto the base material 46 can be provided 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, by depositing a dirt prevention film or the like on the electrode surface, it is possible to prevent film-forming dirt on the electrode surface.

  In the apparatus shown in FIG. 1, 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.

  FIG. 2 is a schematic view showing an example of another two-frequency direct atmospheric pressure plasma discharge treatment apparatus in which power sources having different frequencies are installed on the respective electrodes.

  2, the basic configuration is the same as in FIG. 1, but the first high-frequency filter 101 a and the first high-frequency power source 31 a are connected to the two electrodes 41, and the second stage 41 is connected to the moving stage electrode 47. The high-frequency filter 101b and the second high-frequency power source 31b are connected, and two different high-frequency voltages are applied.

  By arranging these direct type atmospheric pressure plasma discharge treatment apparatuses in the scanning direction of a plurality of stages, it is possible to increase the film forming ability.

  In addition, although not shown in this direct type atmospheric pressure plasma discharge treatment apparatus, by surrounding the electrode and the entire stage and making a structure so that outside air does not enter, the inside of the apparatus can be in a constant gas atmosphere, A desired high-quality thin film can be formed.

  In the plasma CVD apparatus described above, as a high frequency power source, Shinko Electric high frequency power source (3 kHz), Shinko Electric high frequency power source (5 kHz), Shinko Electric high frequency power source (15 kHz), Shinko Electric high frequency power source (50 kHz), HEIDEN High frequency power source manufactured by Research Institute (continuous mode use, 100 kHz), high frequency power source manufactured by SEREN (100 kHz), high frequency power source manufactured by Pearl Industries (200 kHz), high frequency power supply manufactured by Pearl Industries (800 kHz), high frequency power supply manufactured by Pearl Industries (2 MHz), Japan An electronic high frequency power supply (13.56 MHz), a pearl industrial high frequency power supply (27 MHz), a pearl industrial high frequency power supply (150 MHz), or the like can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.

In the present invention, the power applied between the opposing electrodes is to supply a power (power density) of 1 W / cm ² or more to the second electrode (second high frequency electric field) to excite the discharge gas to generate plasma, Energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area in the range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density can be improved while maintaining the uniformity of the second high frequency electric field. it can. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode and an intermittent oscillation mode called ON / OFF intermittently called a pulse mode. Either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  It is preferable to perform post-plasma treatment after the foundation layer is formed and before applying the water repellent or antifouling material, so that the durability can be further improved. By activating the surface or particle-like surface of the underlayer by post-plasma treatment, the wettability of the water-repellent or antifouling material is improved, and the adhesion between the water-repellent or antifouling material and the underlayer is improved. Therefore, the inventor believes that durability is improved. Although there is no particular limitation as long as the wettability of the water-repellent or antifouling material can be improved, the post-plasma treatment is preferably a plasma treatment by mixing an oxidizing reaction gas with a discharge gas from the viewpoint of the treatment effect, and safety. It is most preferable to use oxygen gas as a reaction gas, including the processing efficiency and material cost.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

  Hereinafter, each process for producing the water-repellent or antifouling articles of Examples and Comparative Examples will be described for each process.

<Formation of undercoat film>
An atmospheric pressure plasma CVD process-2 shown below was used to form SiO ₂ films on the soda lime glass substrate that had been previously degreased with alcohol so as to have a thickness of 5 nm, 50 nm, 100 nm, and 200 nm.

(Atmospheric pressure plasma CVD treatment-2)
The undercoat film was formed under the following conditions using the direct 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 of 0.1 slm / cm is supplied as a carrier gas for supplying vaporized TEOS to the discharge space.

<Formation of underlayer by atmospheric pressure plasma>
(Atmospheric pressure plasma CVD treatment-1)
A particle / granular underlayer was formed under the following conditions using the direct system atmospheric pressure plasma discharge treatment apparatus shown in FIG. Soda lime glass was used as a base material, and after degreasing treatment with alcohol in advance, the base material was set in a processing apparatus, and a treatment time was set according to the desired film thickness to form an underlayer. When the substrate had an undercoat film, the soda lime glass was degreased with alcohol in advance, and then the undercoat film was formed, and then the base layer was formed.

<Power supply conditions>
High frequency power supply (13.56 MHz) manufactured by Pearl Industrial Co., Ltd. 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) as a source gas is vaporized by bubbling and supplied to the discharge space, and a particle / agglomerate underlayer mainly composed of SiO ₂ is formed on the surface of the substrate using a decomposition reaction by plasma energy. Formed.

Discharge gas: Argon gas 2 slm / cm
Reaction gas: Oxygen gas 0.01 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. Argon gas of 0.05 slm / cm is supplied as a carrier gas for supplying vaporized TEOS to the discharge space.

<Formation of the underlayer by the jet-type plasma method>
(Atmospheric pressure plasma CVD treatment-3)
Using the plasma jet atmospheric pressure plasma discharge treatment apparatus shown in FIG. 4, a particle / granular underlayer was formed under the following conditions. As the substrate, soda lime glass was used, and after degreasing treatment with alcohol in advance, an undercoat film was formed. This base material was set in an apparatus, and a treatment time was set according to the desired film thickness to form an underlayer.

<Power supply conditions>
High frequency power supply (13.56 MHz) manufactured by Pearl Industrial Co., Ltd. 6 W / cm ²
<Electrode conditions>
Using two 30 mm square rod electrodes and two plate electrodes, a discharge is formed in the gap between the rod electrodes and the plate electrodes. 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-like electrode and the plate-like electrode 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>
The discharge gas 22 flows through the gas passage between the rod-like electrode and the plate-like electrode, the source gas 23 flows through the gas passage between the plate-like electrode, and both gases are mixed on the surface of the substrate to be formed into a film. The gas decomposes and reacts on the surface of the base material by the energy of the plasma formed by the discharge gas, and is formed on the surface of the base material as a base layer of a particle / granular structure mainly composed of SiO ₂ .

  A gas mixture of argon gas and oxygen gas was used as the discharge gas, and TEOS (tetraethoxysilane) was vaporized by bubbling as the source gas.

Discharge gas: Argon gas 2 slm / cm + 2 slm / cm
Reaction gas: Oxygen gas 0.01 slm / cm + 0.01 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. Argon gas 0.05 slm / cm is supplied as a carrier gas for supplying vaporized TEOS to the discharge space.

<Atmospheric pressure plasma surface treatment (post-plasma treatment)>
Using the plasma jet atmospheric pressure plasma discharge treatment apparatus shown in FIG. 3, the surface of the underlayer was subjected to plasma surface treatment under the following conditions.

<Power supply conditions>
High frequency side: High frequency power supply (13.56 MHz) 5 W / cm ² manufactured by Pearl Industrial Co., Ltd.
Low frequency side: SEREN high frequency power supply (100 kHz) 5 W / cm ²
<Electrode conditions>
Two plate-like electrodes are used, and the gap between the electrodes is set to 1 mm. A discharge is formed in the gap, and plasma is ejected from the electrodes toward the substrate surface, whereby the substrate surface is plasma treated. The base material of the plate electrode is stainless steel (SUS304), but ceramic is sprayed on the surface with a thickness of 1 mm. A cooling refrigerant (water) was passed through the electrode at a temperature of 25 ° C. for discharging.

<Gas conditions>
A discharge gas and a reaction gas were allowed to flow between the two plate electrodes to form a discharge.

Discharge gas: Argon gas 2 slm / cm
Reaction gas: Oxygen gas 0.1 slm / cm
<< Formation of film with water repellent or antifouling material >>
(Water repellent or antifouling material-1)
2 g of heptadecafluorodecyltrichlorosilane (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ ) was added to 98 g of decamethylcyclopentasiloxane ((SiO (CH ₃ ) ₂ ) ₅ ) with stirring; Water repellent or antifouling material-1 was obtained.

(Coating method)
Various substrates are immersed in a glass container containing the above water-repellent or antifouling material-1 for 3 minutes, then pulled up, thoroughly washed with ethanol to remove unreacted material on the surface, and then water-repellent or antifouling. Articles were made.

(Water repellent or antifouling material-2)
Fluorine resin material ZX-007C manufactured by Fuji Kasei Kogyo Co., Ltd. and Curing Agent Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd. were mixed at a ratio of 1.2: 1 of NCO and hydroxyl value (OH), And then sufficiently diluted with an MEK solvent so that the solid content concentration becomes 1% to obtain a water repellent or antifouling material-2.

(Coating method)
Water repellent or antifouling material-2 is applied to various substrates using a bar coater so that the dry film thickness is 50 nm, and after natural drying, it is baked in a thermostatic bath at 150 ° C. for 30 minutes. Water or antifouling articles were made.

(Water repellent or antifouling material-3)
Deionized water was added at 7% by mass to the silicate MSH-4 main agent solution manufactured by Mitsubishi Chemical Corporation, and the mixture was stirred and hydrolyzed while maintaining the temperature at 60 ° C. to prepare a silicate preparation solution.

  The above silicate preparation solution, fluorochemical material ZX-022-H (non-volatile component 45%) manufactured by Fuji Kasei Kogyo Co., Ltd., and 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 obtain water repellent or antifouling material-3.

(Coating method)
Water-repellent or antifouling material-3 is applied to various substrates using a bar coater so that the dry film thickness is 50 nm, and after natural drying, it is baked in a thermostatic bath at 150 ° C. for 30 minutes. Water or antifouling articles were made.

<Treatment with coupling agent>
GE Toshiba Silicone Co., Ltd. amino-based silane coupling agent TSL8331 was diluted to 1% with IPA to prepare a coupling agent. It applied so that the dry film thickness on various base materials might be set to 0.01 micrometer or less using the bar coater.

[Production of water-repellent or antifouling articles]
Comparative Example 1
Tetrachlorosilane (SiCl ₄ : manufactured by Shin-Etsu Silicone) 0.5 g was added to 99.5 g of decamethylcyclopentasiloxane (KF-995: manufactured by Shin-Etsu Silicone) with stirring to obtain a coating solution for forming an underlayer.

  Water repellent or antifouling material-1 was used as the water repellent or antifouling material.

  A soda lime glass is used as a base material, and after degreasing with alcohol in advance, the coating solution for forming the underlayer is applied by a flow coating method at a relative humidity of 30% at room temperature, and the coating solution is used for 1 minute. The substrate surface was left still with the substrate wet, and the same coating solution was applied again on the substrate in the same manner, and left still for 1 minute with the substrate wet. In a state where the coating solution for forming the underlayer is wet, the water repellent or antifouling material-1 is applied by the flow coating method, and left still for 1 minute with the coating solution, and then ethanol is added. The water-repellent or antifouling material on the surface was completely washed away and naturally dried to produce a water-repellent or antifouling article of Comparative Example 1. The underlayer is produced by a conventional sol-gel method.

Example 1
An underlayer is formed with a film thickness of 50 nm by atmospheric pressure plasma CVD-1, and after post-plasma treatment, it is treated with water-repellent or antifouling material-1 in the same manner as in Comparative Example 1 to produce water-repellent or antifouling. A characteristic article was produced.

Examples 2-5
A water-repellent or antifouling article was produced in the same manner as in Example 1 except that an undercoat film of 5 nm, 50 nm, 100 nm, and 200 nm was formed by atmospheric pressure plasma CVD-2, respectively.

Examples 6 and 7
A water repellent or antifouling article in the same manner as in Example 1 except that an undercoat film of 10 nm was formed by atmospheric pressure plasma CVD-2 and an underlayer of 100 nm and 200 nm was formed by atmospheric pressure plasma CVD-1 respectively. Was made.

Comparative Example 2
A subbing film of 50 nm was formed by atmospheric pressure plasma CVD-2, and a water-repellent or antifouling material-1 was applied without forming an underlayer to produce a water-repellent / antifouling article.

Example 8
A water repellent or antifouling article was produced in the same manner as in Example 1 except that a 10 nm undercoat film was formed by atmospheric pressure plasma CVD-2 and a 50 nm underlayer was formed by atmospheric pressure plasma CVD-3. .

Example 9
An undercoat film of 10 nm is formed by atmospheric pressure plasma CVD-2, an underlayer of 30 nm is formed by atmospheric pressure plasma CVD-1, a post-plasma treatment is performed, and then a treatment with a coupling agent is performed. Alternatively, antifouling material-2 was applied to produce a water-repellent or antifouling article.

Example 10
A water-repellent or antifouling article was produced in the same manner except that the treatment with the coupling agent was not performed in the production of Example 9.

Example 11
In the production of Example 9, a water-repellent or antifouling article was produced in the same manner except that post-plasma treatment was not performed.

Example 12
A water repellent or antifouling article was prepared in the same manner as in Example 9 except that the water repellent or antifouling material-2 was used instead of the water repellent or antifouling material-2.

Evaluation Method << Initial water repellency: Measurement of static contact angle of water >>
3 μL of water is dropped on the surface of the water-repellent 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 above.

◎: 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 ° ×: Static contact angle is less than 90 ° .

<Initial sliding property: Measurement of water falling angle>
50 μL of water is dropped on the surface of the water-repellent article, and the angle of the stage holding the water-repellent article of the contact angle measuring device (contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd.) is changed from 0 ° (horizontal). The angle was gradually tilted in the 90 ° (vertical) direction, the angle at which water droplets began to move through the water-repellent article was measured, and evaluated according to the following criteria as the initial sliding property evaluation.

A: The sliding angle is less than 10 °. O: The falling angle is 10 ° or more and less than 20 °. Δ: The falling angle is 20 ° or more and less than 30 °. X: The falling 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 / anti-fouling article. Based on the degree of magic ink repellency and wiping properties, the following criteria are used. Evaluation was made as one of the antifouling evaluations.

◎: Magic ink repels in a dot pattern ○: The ink can be written in a linear shape, but can be easily wiped (within 5 times) by wiping with a tissue △: The ink can be written and wiped with a tissue at least 5 times to wipe it off X: Ink can be written, and even if wiped with a tissue, it is difficult to wipe off, and marks may remain.

<Ease of wiping fingerprints>
An 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 lightly Δ: 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. At the end of 10,000 times, the water repellency and the sliding property were evaluated according to the above evaluation criteria to determine the abrasion resistance.

《Scratch resistance test》
As a scratch resistance test, the surface of a water-repellent or antifouling article is subjected to a load of 400 gf / cm ² on # 0000 steel wool and subjected to 10 reciprocating frictions at a stroke width of 100 mm and a speed of 100 mm / sec. Was visually observed and observed with a microscope (Digital Microscope VHX-600 manufactured by KEYENCE Corporation) and evaluated according to the following criteria to evaluate scratch resistance.

◎: Scratches are not visible at all and cannot be confirmed even by microscopic observation ○: Scratches are not visible at all by visual observation, but scratches can be confirmed by microscopic observation △: Slightly visible scratches are observed by microscopic observation Many scratches are visible ×: Many scratches are clearly visible by visual inspection.

《Taber test》
In the Taber abrasion tester, the surface of a water-repellent / antifouling article is subjected to a total of 1000 revolution wear tests using a wear wheel CS-10F under a load speed of 4.9N and a rotation speed of 60 rpm, and the process of 1000 revolution wear The haze value showing the highest value was measured and evaluated according to the following criteria to obtain the Taber test.

ΔH = (maximum haze value during Taber test) − (haze value before Taber test)
：: ΔH is less than 0.3 ○: ΔH is 0.3 or more and less than 1.0 Δ: ΔH is 1.0 or more and less than 2.0 ×: ΔH is 2.0 or more.

《Weather resistance test》
As a weather resistance test, using a UV resistance tester (Isuperki UV Tester W-13 manufactured by Iwasaki Electric Co., Ltd.), the surface of each water-repellent / antifouling article has a wavelength of 340 nm and an intensity of 0.6 W / cm ² . Under the condition of a black panel temperature of 48 ± 2 ° C., ultraviolet rays were subjected to ion exchange water showering 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 above-mentioned water repellency evaluation (initial water repellency) and antifouling evaluation (magic ink repellency / wiping properties) were performed on the surface of the water-repellent or antifouling article, 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 ° ×: 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. Δ: 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 is immersed in a 1N NaOH aqueous solution for 1 hour, washed with water, dried, measured for water contact angle, and evaluated according to the following criteria. Tested.

○: Static contact angle is 90 ° or more. Δ: Static contact angle is 80 ° or more and less than 90 °. X: Static contact angle is less than 80 °.

"optical properties"
Transmittance For water-repellent / antifouling articles, the average transmittance in the visible light region is measured using an integrating sphere 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.

A: The average transmittance of the visible light region is 90% or more. ○: The average transmittance of the visible light region is 85% or more and less than 90%. Δ: The average transmittance of the visible light region is 80% or more and less than 85%. The average transmittance is less than 80%.

Haze Water repellent or antifouling article and substrate before forming water repellent or antifouling film, haze value using 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)
：: ΔH is less than 0.3 ○: ΔH is 0.3 or more and less than 1.0 Δ: ΔH is 1.0 or more and less than 2.0 ×: ΔH is 2.0 or more.

  It can be seen from Table 2 that all 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. . The difference in performance between Examples 9 and 10 is due to the silane coupling agent, and the difference between Examples 9 and 11 is due to post-plasma treatment. Further, it can be seen that the difference between Examples 7 and 8 is 50 nm, which is the difference in the underlayer film thickness.

Claims (15)

A base layer in which an inorganic material is present as particles or agglomerates on the surface of the substrate is formed using an atmospheric pressure plasma method, so that water repellent or antifouling materials are exposed from the periphery or gaps of the particles or agglomerates. a water-repellent or antifouling article, wherein the underlying layer is coated or impregnated with the water repellent or antifouling material. The water repellent or antifouling article according to claim 1 , wherein an undercoat film is formed between the base layer and the base material. The water-repellent or antifouling article according to claim 2 , wherein the undercoat film is formed by an atmospheric pressure plasma method. The underlying layer forming the base material temperature of 15 ℃ or higher, water-repellent or antifouling product according to any one of claims 1 to 3, characterized in that formed at 0.99 ° C. or less. The water repellent or antifouling product according to any one of claims 1 to 4 atmospheric pressure plasma method is characterized in that it is a blow-type plasma method. The average particle size of the underlying layer of the particles (D1) is 2 to 100 nm, the average thickness of the entire undercoat layer is according to any one of claims 1 to 5, characterized in that the 5~200nm Water repellent or antifouling article. The water repellent or the water repellent according to any one of claims 1 to 6 , wherein the water repellent or antifouling material coated or impregnated on the underlayer has a thickness of 2 to 100 nm. Antifouling article. To any one of claims 1 to claim 7, wherein the water-repellent or antifouling material coats or impregnating the base layer with at least one coupling agent prior to being coated or impregnated The water-repellent or antifouling article described. Plasma treatment of the surface of the underlayer is performed before the coating or impregnation with the water repellent or antifouling material, or the coating or impregnation with the water repellent or antifouling material after the coating or impregnation with the coupling agent. water repellent or antifouling product according to any one of claims 1 to 8, characterized. Any of claims 1 to 9 wherein the water repellent or antifouling material characterized by containing a silicate compound represented by at least a fluorine-based resin or fluorine-containing silicone resin and the following general formula (1) 1 The water-repellent or antifouling article according to Item.
(In the formula, n is an integer of 1 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, One type 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 said base material is a transparent glass base material or a transparent resin base material, and the average transmittance | permeability of visible region is 85% or more, The any one of Claims 1-10 characterized by the above-mentioned. Water repellent or antifouling article. Claims 1 to 11 architectural window glass, characterized in that it is constructed using a water repellent or antifouling product according to any one of. Claims 1 to 11 for a vehicle window glass, characterized in that it is constructed using a water repellent or antifouling product according to any one of. Display member characterized by being constituted by using a water repellent or antifouling product according to any one of claims 1 to 11. Optical component characterized in that it is constituted by using a water repellent or antifouling product according to any one of claims 1 to 11.