JP6456669B2 - Functional membrane - Google Patents

Description

  The present invention relates to a functional membrane.

  In recent years, due to the global warming phenomenon, people's awareness of the environment has increased, and a new energy system that does not generate carbon dioxide and other warming gases has attracted attention. For example, environmentally friendly renewable energy such as solar cell power generation, solar thermal power generation, and wind power generation does not emit gas that is said to induce warming, such as carbon dioxide. Therefore, renewable energy has been actively researched and developed as clean energy, and is considered to attract more attention in the future because of its excellent safety and ease of handling.

  Here, taking solar power generation among renewable energies, typical solar power generation methods include a concentrated method (central tower method), a distributed method (parabolic trough), and a dish / sterling method. In these methods, sunlight is condensed on a part by a reflecting mirror, and electric energy is obtained by performing thermoelectric conversion from the collected heat. In these methods, it is important to increase the light collection efficiency, but as a factor for reducing the light collection efficiency, there is a decrease in reflectance due to dirt on the reflecting mirror. Dirt on the reflector can be removed by maintenance, but is expensive. Therefore, in order to reduce this maintenance cost, a technique for forming a film having a predetermined antifouling property on the surface of the resin base material of the reflecting mirror for the purpose of preventing dirt has been proposed.

  For example, Patent Document 1 applies a coating solution in which tungstic acid dissolved in ammonia water and distilled water are added to an anatase-type titanium oxide-containing layer, and is subjected to a baking treatment at 700 ° C. to form a layer made of tungsten oxide. A technique for forming and forming a surface layer is disclosed. Patent Document 2 discloses a coating film using an aqueous polymer dispersion excellent in mechanical strength, transparency, weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties and the like. Is disclosed. Furthermore, Patent Document 3 discloses a coating composition that is excellent in antifouling property, transparency, and hydrophilicity and can maintain surface hydrophilicity even in a high-temperature environment. Patent Document 4 has a photocatalytic function, is hydrophilic, Patent Document 5 discloses a coating composition having good weather resistance and antifouling performance and good protection of a resin base material, which is a light reflecting mirror capable of exhibiting stain resistance for a long period of time. In addition, Patent Document 6 discloses a film mirror that is excellent in antifouling property and scratch resistance and has an antifouling layer in which inorganic fine particles are dispersed in the outermost layer of a resin film-like support. Each of the techniques described in Patent Documents 1 to 6 is a technique for imparting antifouling properties by making a coating film hydrophilic.

  As a technique other than hydrophilizing the coating film, Patent Document 7 discloses a technique for imparting antifouling properties by forming a water / oil repellent coating film.

JP-A-10-114545 International Publication No. 2007/069596 Pamphlet International Publication No. 2010/104146 Pamphlet JP 2010-60722 A JP 2009-286859 A JP 2012-232538 A JP 2013-173939 A

  However, the film described in Patent Document 1 requires a baking process at a high temperature or a process with ultraviolet rays, so that applicable substrates are limited. Moreover, although the film | membrane of patent documents 2-6 shows hydrophilicity and expresses an antifouling function, when high temperature environments, such as a desert, continue for a long time, antifouling persistence is not enough. . Further, in such a high temperature environment, water-repellent dirt tends to adhere to the film. Further, in the film described in Patent Document 7, it is necessary to use a halogen-based material having a concern about toxicity in order to impart water and oil repellency.

  Accordingly, an object of the present invention is to obtain a functional film that maintains antistatic properties and maintains oil repellency even when exposed to a dry state for a long period of time.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have a substrate and a coating film having a specific composition located on the surface of the substrate, and the moisture content of the coating film is in a specific range. The functional film contained therein was found to be excellent in maintaining antistatic properties and oil repellency, and the present invention was completed.

That is, the present invention is as follows.
[1] having a base and a film positioned on the surface of the base;
The coating comprises emulsion particles (B) and a hydrolyzable silicon compound condensate,
Metal oxide fine particles (D);
Including
The mass ratio of (D) / (B) is 50/100 or more and 300/100 or less,
The moisture content of the coating is 1.5% to 4% ,
The emulsion particles include acrylic silicon emulsion particles;
The hydrolyzable silicon compound is tetraethoxysilane,
The emulsion particles have a swelling ratio with respect to water of 5% to 40%,
The condensate of the hydrolyzable silicon compound has a weight average molecular weight of 10,000 or more and 50,000 or less.
A functional membrane that is less than below.
[2] The functional film according to [1] , wherein the metal oxide fine particles (D) are hollow silica.

  According to the functional film of the present invention, excellent antistatic properties and excellent oil repellency can be obtained even when exposed to a dry state for a long period of time.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to the following embodiment. The present invention can be implemented with various modifications within the scope of the gist. In this specification, “(meth) acryloyl group”, “(meth) acryl”, and “(meth) acrylate” refer to both acryloyl group and methacryloyl group corresponding to acryl and the corresponding methacrylic group. Both and both acrylate and its corresponding methacrylate are meant.

[Functional membrane]
The functional film of this embodiment has a base and a coating film located on the surface of the base. The coating film includes emulsion particles and a hydrolyzable silicon compound condensate, and has a water content of 0.1% to 80%. Further, the emulsion particles include at least one selected from the group consisting of acrylic emulsion particles, styrene emulsion particles, acrylic styrene emulsion particles, acrylic silicon emulsion particles, silicon emulsion particles, and urethane resin emulsion particles. In addition, the condensate of the hydrolyzable silicon compound has a weight average molecular weight of 8000 or more and less than 500,000.

[Substrate (A)]
The functional film of the present embodiment has a substrate (A). Specific examples of the material for the substrate (A) include glass, metal; polyester resin, polyolefin resin, acrylic resin, polyamide resin, polyvinylidene chloride resin, ethylene-vinyl acetate resin, polyimide resin, polyethylene terephthalate resin, polysulfone resin, Thermoplastic resins such as polyvinylidene fluoride resin and PTFE; polylactic acid resin, polyhydroxybutyrate resin, polycaprolacto resin, polybutylene succinate resin, polybutylene adipate terephthalate resin, polybutylene succinate terephthalate resin, phenol resin, urea Thermosetting resins such as resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, silicon resin, acrylic urethane resin, urethane resin It is.

  The form of the substrate is not particularly limited because it can be appropriately changed according to the purpose of use and the type of oil to be treated, and specifically, a woven fabric, a knitted fabric, a nonwoven fabric, etc. composed of a fibrous material made of resin. Examples thereof include a fibrous structure. Various shapes and sizes can be adapted to the intended use.

[Coating]
The functional film of this embodiment has a film. The coating contains emulsion particles (B) and a condensate of the hydrolyzable silicon compound (C). Moreover, a film is obtained by curing at a temperature of 20 ° C. or higher and 200 ° C. or lower after being formed on the substrate surface. The temperature is preferably 40 ° C. or higher and 150 ° C. or lower, and more preferably 50 ° C. or higher and 90 ° C. or lower. When the temperature is 200 ° C. or lower, the deterioration of the substrate (A) is suppressed, and the energy loss tends to be small in the production process. Further, when the temperature is 20 ° C. or higher, productivity for film formation is maintained, and there is a tendency that variations in performance such as durability do not easily occur.

  The film produced by the above-described method has a surface water contact angle at 25 ° C. of preferably 30 degrees or less, more preferably 20 degrees or less, and even more preferably 10 degrees or less. When the surface water contact angle at 25 ° C. is 30 degrees or less, the hydrophilicity of the coating film tends to be excellent. In order to obtain a film having a water contact angle on the surface in such a range, the water content of the film may be increased. Moreover, the water contact angle on the surface is measured by the method described in Examples described later.

  The moisture content of the film is from 0.1% to 80%, preferably from 0.5% to 50%, more preferably from 1% to 15%. When the water content is 0.1% or more, due to moisture present on the surface of the functional film, even if the dry state continues, the antifouling property is hardly lowered, and in particular, the antistatic property is hardly lowered. Moreover, water resistance is maintained because a moisture content is 80% or less. In order to obtain a film having a moisture content in such a range, it is sufficient to control by a combination of these, such as control of the functional group of the polymer terminal and control of the molecular weight. The moisture content of the film is measured by the method described in the examples described later.

[Emulsion particles (B)]
The coating film of this embodiment contains emulsion particles (B) (hereinafter sometimes simply referred to as “component (B)”). The emulsion particles (B) include at least one selected from the group consisting of acrylic emulsion particles, styrene emulsion particles, acrylic styrene emulsion particles, acrylic silicon emulsion particles, silicon emulsion particles, and urethane emulsion particles. These emulsion particles are emulsion resin particles obtained by polymerizing a monomer component having an unsaturated bond through the intervention of radicals, cations, or anions, and urethane bonds by polyaddition reaction of isocyanate groups and polyols. Emulsion resin particles in the molecule. Among these, it is preferable that it contains a hydrophilic functional group, and is an emulsion particle obtained by polymerizing at least one selected from the group consisting of a hydrolyzable silicon compound (b1) and a vinyl compound (b2) described later. Is more preferable.

  The component (B) may contain the following anionic polyurethane particles in addition to those described above. Specifically, trade names “Superflex 126”, “Superflex 130”, “Superflex 150”, “Superflex 170”, “Superflex 210”, “Superflex 300” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “Superflex 420”, “Superflex 460”, “Superflex 470”, “Superflex 740”, “Superflex 800”, “Superflex 860”, trade names “NeoRez R-9660” manufactured by DMS, NeoRez R-972, NeoRez R-9737, NeoRez R-9679, NeoRez R-989, NeoRez R-2150, NeoRez R-966, NeoRez R-967, NeoR “ez R-9603”, “NeoRez R-940”, “NeoRez R-9403”, trade names “Yukot UX-485”, “Yukot UWS-145”, “Permarin UA-368T”, “Permarine” manufactured by Sanyo Kasei Co., Ltd. "UA-200", "Euprene UXA307", trade names "NeoRez R-600", "NeoRez R-650", "NeoRez R-9617", "NeoRez R-9621", "NeoRez R-9330" manufactured by DSM Non-ionic polyurethane particles, trade names “Superflex 500M”, “Superflex E2000”, “Superflex E4800” manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Product name "Superflex 620", “Superflex 650” may be mentioned.

  The emulsion particles (B) preferably have a swelling ratio with respect to water of 1% to 300%, more preferably 3% to 100%, and still more preferably 5% to 40%. . When the swelling ratio is 1% or more, due to moisture present on the surface of the functional film, the antifouling property tends to be difficult to decrease even if the dry state continues, and in particular, the antistatic property decreases. It tends to be difficult. Moreover, it exists in the tendency for water resistance to be maintained easily because swelling rate is 300% or less. In order to obtain the component (B) having a swelling ratio in such a range, the terminal functional group and the molecular weight may be controlled. The measuring method of the swelling rate of a component (B) is measured by the method as described in the Example mentioned later.

  The number average particle size of the component (B) is preferably from 10 nm to 800 nm, more preferably from 10 nm to 100 nm, from the viewpoint of improving the durability of the functional film in the water dispersion state. In order to obtain a component (B) having a number average particle size in such a range, polymerization using seed particles having a uniform particle size or phase transition using a nonionic surfactant and a solvent that does not dissolve in water. Then, there are a method of creating particles by removing the solvent, and a method of forcibly creating particles by adjusting the rotation speed and time of a high-pressure homogenizer. In addition, the number average particle diameter of a component (B) is measured by the method as described in the below-mentioned Example.

<Hydrolyzable silicon compound (b1)>
The hydrolyzable silicon compound (b1) having hydrolyzability and containing a silicon atom is represented by the hydrolyzable silicon-containing compound (h1) represented by the following formula (1) and the following formula (2). Examples thereof include at least one compound selected from the group consisting of a hydrolyzable silicon-containing compound (h2) and a hydrolyzable silicon-containing compound (h3) represented by the following formula (3).

R ¹ _n SiX _4-n (1)
(In formula (1), R ¹ is a hydrogen atom, a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, or an alkyl group having 1 to 10 carbon atoms which may have an epoxy group. , An alkenyl group, an alkynyl group, or an aryl group, X represents a hydrolyzable group, and n is an integer of 0 to 3.)

X ₃ Si—R ² _n —SiX ₃ (2)
(In formula (2), X represents a hydrolyzable group, R ² represents an alkylene group having 1 to 6 carbon atoms or a phenylene group. N is 0 or 1.)

  The hydrolyzable group in the above formula (1) and the above formula (2) is not particularly limited as long as it is a group that generates a hydroxyl group by hydrolysis. Specifically, a halogen atom, an alkoxy group, an acyloxy group, an amino group, Examples include phenoxy group and oxime group.

R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (3)
(In the formula (3), R ³ is, .n represents an alkyl group having 1 to 6 carbon atoms is an integer of 2-8.)

  Specific examples of the hydrolyzable silicon-containing compounds (h1) and (h2) include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, and tetra (n-butoxy). Silane, tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimeth Sisilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis ( Triethoxysilyl) ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriet Sisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylic Roxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloro Acetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, Trabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethylketoxime) silane, tris (methylethylketoxime) silane, methyltris (methylethylketo) Ximem) silane, phenyltris (methylethylketoxime) silane, bis (methylethylketoxime) silane, methylbis (methylethylketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethyl Examples include silane, bis (dimethylamino) methylsilane, and bis (diethylamino) methylsilane. These may be used alone or in combination of two or more.

  As the hydrolyzable silicon-containing compound (h3), specifically, a partial hydrolysis condensate of tetramethoxysilane (for example, trade name “M silicate 51” manufactured by Tama Chemical Industry Co., Ltd., trade name “MSI 51” manufactured by Colcoat Co., Ltd.) ", Trade names" MS51 "and" MS56 "manufactured by Mitsubishi Chemical Corporation), partial hydrolysis condensates of tetraethoxysilane (for example, trade names" Silicate 35 "and" Silicate 45 "manufactured by Tama Chemical Industry Co., Ltd., Colcoat) Product names "ESI40", "ESI48"), co-hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" manufactured by Tama Chemical Industry Co., Ltd.) EMSi 48 "). These may be used alone or in combination of two or more.

<Vinyl compound (b2)>
The vinyl compound (b2) (hereinafter sometimes simply referred to as “component (b2)”) is selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an ether group, an amide group, an epoxy group, and a sulfonic acid group. A vinyl compound having at least one functional group. Component (b2) tends to further improve the antistatic property of the functional film by having these functional groups.

  Specific examples of the hydroxyl group-containing vinyl compound (b2) include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; polyether polyols such as polyethylene glycol; and (meth) acrylic acid Monoesters of polyoxyalkylene glycols obtained from unsaturated carboxylic acids; adducts of the above-mentioned various hydroxyl group-containing compounds with lactones such as ε-caprolactone; Epoxys such as glycidyl (meth) acrylate Adducts of silyl group-containing unsaturated monomers and acids such as acetic acid; other than unsaturated carboxylic acids such as (meth) acrylic acid and epoxides of α-olefins such as the product name “Cardura E” manufactured by Shell of the Netherlands And adducts with monoepoxy compounds. Moreover, polyvinyl alcohol, modified polyvinyl alcohol, and polyvinyl pyrrolidone are also mentioned. As commercial products, trade names “Kuraray Poval PVA117” and “Kuraray Poval R1130” manufactured by Kuraray Co., Ltd. may be mentioned.

  Specific examples of the vinyl compound (b2) having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid, and fumaric acid; Monoesters of unsaturated dicarboxylic acids and saturated monohydric alcohols such as monomethyl acid, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate (Half esters); monovinyl esters of saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; anhydrides of saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride and trimellitic anhydride And an addition reaction product of the above-mentioned vinyl compound (b2) having a hydroxyl group; Compounds obtained by addition reaction between these and lactones thereof.

  Specific examples of the vinyl compound (b2) having an amino group include 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3 -(Meth) acrylic acid esters having a tertiary amino group such as dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, N- [2- (meth) acryloyloxy] ethylmorpholine; vinylpyridine Aromatic vinyl compounds having a tertiary amino group such as N-vinylcarbazole and N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) Acrylamide, N- (2-di-n-propylamino) ethyl (me ) Tertiary amino groups such as acrylamide, N- (3-dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide, N- [2- (meth) acrylamide] ethylmorpholine, etc. (Meth) acrylamides having: N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide, N- (2-di-n-propylamino) ethylcrotonamide, N Crotonic acid amides having a tertiary amino group such as-(3-dimethylamino) propylcrotonic acid amide and N- (4-dimethylamino) butylcrotonic acid amide; 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether, 4-dimethyl Vinyl ethers having a tertiary amino group, such as Le aminobutyl vinyl ether.

  Specific examples of the vinyl compound (b2) having an ether group include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene-polyoxypropylene block copolymers, and the like. Examples include vinyl ethers having an ether chain in the side chain, allyl ethers, and (meth) acrylic acid esters. Here, the number of oxyethylene units in the polyoxyethylene chain of the above compound is preferably 2 or more and 30 or less. When the number of oxyethylene units is 2 or more, the flexibility of the functional film tends to be maintained, and when the number of oxyethylene units is 30 or less, the functional film does not become too soft and has blocking resistance. Tend to be better.

  Vinyl compounds (b2) having an ether group are commercially available from Nippon Oil & Fats Co., Ltd. under the trade names “Blemmer PE-90”, “PE-200”, “PE-350”, “PME-100”, “PME-”. 200 ”,“ PME-400 ”,“ AE-350 ”, trade names“ MA-30 ”,“ MA-50 ”,“ MA-100 ”,“ MA-150 ”,“ RA-1120 ”manufactured by Nippon Emulsifier Co., Ltd. ”,“ RA-2614 ”,“ RMA-564 ”,“ RMA-568 ”,“ RMA-1114 ”,“ MPG130-MA ”.

  Specific examples of the vinyl compound (b2) having an amide group include N-alkyl (meth) acrylamide and N-alkylene-substituted (meth) acrylamide. More specifically, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-N -N-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroa Pin, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N′-methylenebisacrylamide, N, N′-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, Examples include diacetone methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide. Moreover, polyvinylpyrrolidone is also mentioned, and a commercial name "K-90" manufactured by Nippon Shokubai Co., Ltd. is also mentioned as a commercial product.

  Specific examples of the vinyl compound (b2) having an epoxy group include a vinyl compound having a glycidyl group. Examples of the vinyl compound having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.

  The amount of the vinyl compound having an epoxy group is preferably 0.01% by mass or more and 50% by mass or less, and more preferably 0.05% by mass or more and 20% by mass or less with respect to the total vinyl compound (b2) (100% by mass). More preferred.

  Specific examples of the vinyl compound (b2) having a sulfonic acid group include vinyl sulfonic acid.

  Component (b2) is preferably a primary amide group, a secondary amide group, a tertiary amide group, and a vinyl compound having two or more of these from the viewpoint of further improving the antistatic properties of the functional film. A component (b2) may be used individually by 1 type, and may use 2 or more types together.

<Hydrolyzable silicon compound (C)>
The film of the present embodiment includes a condensate of the hydrolyzable silicon compound (C) (hereinafter sometimes simply referred to as “component (C)”). By including the condensate of component (C), the antistatic property and durability of the functional film are excellent. The condensate refers to a product obtained by condensing the component (C) by causing a dehydration reaction under predetermined conditions.

  Component (C) is a hydrolyzable silicon-containing compound (c1) represented by the following formula (4), a hydrolyzable silicon-containing compound (c2) represented by the following formula (5), and the following formula (6). Or at least one compound selected from the group consisting of hydrolyzable silicon-containing compounds (c3).

R ¹ nSiX ₄ −n (4)
(In the formula (4), R ¹ is a hydrogen atom, a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group or an epoxy group, and an alkyl group having 1 to 10 carbon atoms, An alkenyl group, an alkynyl group or an aryl group, X represents a hydrolyzable group, and n is an integer of 0 to 3.)

X ₃ Si—R ² _n —SiX ₃ (5)
(In formula (5), X represents a hydrolyzable group, R ² represents an alkylene group having 1 to 6 carbon atoms or a phenylene group. N is 0 or 1.)

  The hydrolyzable group in the above formula (4) and the above formula (5) is not particularly limited as long as it is a group that generates a hydroxyl group by hydrolysis, and specifically, a halogen atom, an alkoxy group, an acyloxy group, an amino group, Examples include phenoxy group and oxime group.

R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (6)
(In the formula (6), R ³ the .n represents an alkyl radical having 1-6 carbon atoms is an integer of 2-8.)

  Specific examples of the hydrolyzable silicon-containing compounds (c1) and (c2) include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, and tetra (n-butoxy). Silane, tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimeth Sisilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis ( Triethoxysilyl) ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriet Sisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylic Roxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloro Acetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, Trabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethylketoxime) silane, tris (methylethylketoxime) silane, methyltris (methylethylketo) Ximem) silane, phenyltris (methylethylketoxime) silane, bis (methylethylketoxime) silane, methylbis (methylethylketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethyl Examples include silane, bis (dimethylamino) methylsilane, and bis (diethylamino) methylsilane. These may be used alone or in combination of two or more.

  As the hydrolyzable silicon-containing compound (c3), specifically, a partial hydrolysis condensate of tetramethoxysilane (for example, trade name “M silicate 51” manufactured by Tama Chemical Industry Co., Ltd., trade name “MSI 51” manufactured by Colcoat Co., Ltd.) "MS51" and "MS56" manufactured by Mitsubishi Chemical Co., Ltd., partially hydrolyzed condensates of tetoethoxysilane (for example, trade names "Silicate 35" and "Silicate 45" manufactured by Tama Chemical Industry Co., Ltd., manufactured by Colcoat Co., Ltd.) Trade name “ESI40”, “ESI48”), co-hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (for example, trade name “FR-3” manufactured by Tama Chemical Industry Co., Ltd., trade name “Colcoat” EMSi 48 "). These may be used alone or in combination of two or more.

  In addition, as the hydrolyzable silicon-containing compound (c3), trade names “KBE-402”, “KBM-803”, “KBM-802”, “KBE-403”, “KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd. ”,“ KBM-1403 ”,“ KBM-9659 ”,“ KBM-585 ”,“ KBM-846 ”,“ KBM-9007 ”,“ KP-64 ”,“ KP-851 ”,“ KR-220L ”, “KR-242A”, “KR-251”, “KR-89”, “KR-500”, “KR-400”, “KR-255”, “KR-271”, “KR-282”, “KR” Various silane coupling agents such as “−300”, “KR-311”, “KR-212”, “KR-213”, and “KR-9218” are also included.

  The weight average molecular weight of the condensate of the hydrolyzable silicon compound (C) is 8000 or more and 500,000 or less, preferably 8000 or more and 200,000 or less, more preferably 8000 or more and 100,000 or less, more preferably 20000 in terms of polystyrene. It is more preferably 85,000 or less and even more preferably 10,000 or more and 50,000 or less. When the weight average molecular weight is 8000 or more, the hydrophilicity of the functional film is maintained, and when the weight average molecular weight is 500,000 or more, the functional film becomes brittle and is prevented from peeling. In order to obtain a hydrolyzable silicon-containing compound (C) having a weight average molecular weight in such a range, for example, acid in a mixed solvent of water / alcohol in the presence of an acid catalyst such as dodecylbenzenesulfonic acid. What is necessary is just to control the addition amount, the mixing ratio of the solvent, the reaction temperature, and the reaction time. As a measuring method of a weight average molecular weight, it measures by the method as described in the Example mentioned later.

(Metal oxide particles (D))
It is preferable that the coating film of this embodiment further includes metal oxide particles (D) (hereinafter sometimes simply referred to as “component (D)”).

  The number average particle diameter of the component (D) (may be a mixture of primary particles and secondary particles or only one of primary particles and secondary particles) may be 1 nm or more and 400 nm or less. Preferably, it is 1 nm or more and 100 nm or less, more preferably 3 nm or more and 80 nm or less, and further preferably 5 nm or more and 50 nm or less. By setting the number average particle diameter of the component (D) within such a range, it tends to contribute to both hydrophilicity and oil repellency of the functional film.

  The metal oxide which is a material constituting the component (D) is not particularly limited, and a known material can be used. From the viewpoint of interaction with the component (B) described above, silicon dioxide, aluminum oxide, At least one metal oxide selected from the group consisting of antimony oxide, titanium oxide, indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, and cerium oxide is preferable. Among these metal oxides, a group consisting of silicon dioxide (silica), aluminum oxide (alumina), zirconium oxide, antimony oxide, and complex oxides thereof from the viewpoint of having many surface hydroxyl groups and improving strength. More preferred are at least one metal oxide selected from the above.

  A component (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Component (D) is preferably in the form of powder, dispersion, or sol. The term “dispersion liquid” and “sol” as used herein means that the component (D) has a concentration of 0.01% by mass to 80% by mass in water, a hydrophilic organic solvent, or a mixed solvent thereof, preferably 0. It means a state where it is dispersed as at least one of primary particles or secondary particles at a concentration of 1% by mass or more and 50% by mass or less.

  Among the above components (D), acidic colloidal silica using water as a dispersion medium, basic colloidal silica using water as a dispersion medium, and colloidal silica using a water-soluble solvent as a dispersion medium include component (B) and From the viewpoint of blending stability of

  As acidic colloidal silica using water as a dispersion medium, trade names “Snowtex (registered trademark) -O”, “Snowtex-OS”, “Snowtex-OXS”, “Snowtex-OL” manufactured by Nissan Chemical Industries, Ltd. ”,“ Light Star (registered trademark) ”, trade name“ Adelite (registered trademark) AT-20Q ”manufactured by ADEKA, and trade names“ Clevosol (registered trademark) 20H12 ”,“ Crebosol 30CAL25 ”manufactured by Clariant Japan, Nalco The product name “NALCO1115” manufactured by the company is mentioned.

  Specific examples of basic colloidal silica using water as a dispersion medium include silica stabilized by addition of alkali metal ions, ammonium ions, or amines. Commercially available products include “Snowtex-20”, “Snowtex-30”, “Snowtex-C”, “Snowtex-C30”, “Snowtex-CM40”, “Snow” manufactured by Nissan Chemical Industries, Ltd. "Tex-N", "Snowtex-N30", "Snowtex-K", "Snowtex-XL", "Snowtex-YL", "Snowtex-ZL", "Snowtex PS-M", "Snow “Tex PS-L”, trade names “Adelite AT-20”, “Adelite AT-30”, “Adelite AT-20N”, “Adelite AT-30N”, “Adelite AT-20A”, “Adelite AT” manufactured by ADEKA -30A "," Adelite AT-40 "," Adelite AT-50 ", trade names" Cataloid SI Series "manufactured by JGC Catalysts & Chemicals ”,“ Cataloid S Series ”,“ Thruglia ”, trade names“ Clevosol 30R9 ”,“ Crebosol 30R50 ”,“ Crebosol 50R50 ”manufactured by Clariant Japan, and“ Ludox® HS-40 ”manufactured by DuPont , “Ludox HS-30”, “Ludox LS”, and “Ludox SM-30”.

  As colloidal silica using a water-soluble solvent as a dispersion medium, specifically, "MA-ST-M" (methanol dispersion type having a number average particle diameter of 20 nm to 25 nm) and "IPA-ST" manufactured by Nissan Chemical Industries, Ltd. (Isopropyl alcohol dispersion type with a number average particle diameter of 10 nm to 15 nm), “EG-ST” (ethylene glycol dispersion type with a number average particle diameter of 10 nm to 15 nm), “EG-ST-ZL” (Number average particle diameter is 70 nm to 100 nm ethylene glycol dispersion type) and “NPC-ST” (ethylene glycol monopropyl ether dispersion type having a number average particle diameter of 10 nm to 15 nm).

  The metal oxide fine particles (D) are preferably hollow metal oxide fine particles and more preferably hollow silica from the viewpoint of the water content of the functional membrane. Moreover, it is also preferable that it is a hollow metal oxide fine particle which has a pore diameter (mesopore) in particle | grains. In order to obtain hollow metal oxide fine particles, for example, silica particles may be formed using an emulsifier as a template, and the silica particles may be extracted. Specific examples of hollow silica include trade name “Light Star LA-S233A” manufactured by Nissan Chemical Industries, Ltd. as water-dispersed colloidal silica.

Component (D) preferably has a particle size of 50 nm to 800 nm, a specific surface area of preferably 80 m ² / g to 300 m ² / g, and a pore diameter of 2 nm to 50 nm. preferable.

  The various colloidal silicas described above may be used alone or in combination of two or more.

  The mass ratio ((D) / (B)) of component (D) to component (B) described above is preferably 50/100 or more and 10,000 / 100 or less, and 110/100 or more and 1000 or less, from the viewpoint of antistatic properties and strength. / 100 or less is more preferable, and 150/100 or more and 300/100 or less is more preferable. By setting the mass ratio in such a range, the antistatic property, oil repellency, and strength of the obtained functional film tend to be improved.

  The mass ratio ((C) / (D)) of the component (C) to the component (D) is preferably 1/100 or more and 1000/100 or less, more preferably 10/100 or more and 200/100 or less, and 40 / More preferably, it is 100 or more and 120/100 or less. When the mass ratio is 1/100 or more, the resulting functional film tends to have improved erosion resistance due to its ability to maintain antistatic properties and oil repellency even under running water.

[Use]
The functional film of the present embodiment is preferably used outdoors, and more preferably used for a cover glass for solar cells, a mirror for solar power generation, and a light collecting material.

  Hereinafter, the present embodiment will be described in more detail with specific examples and comparative examples. However, the present embodiment is not limited to the following examples and comparative examples unless they exceed the gist thereof. . Various physical properties and evaluation in Synthesis Examples, Examples, and Comparative Examples described later were measured and evaluated by the following methods. In Examples and Comparative Examples, “%” and “parts” are based on mass unless otherwise specified.

(Physical property 1) Swelling rate (%)
From the ratio of the number average particle diameter (Da) in water and the number average particle diameter (Db) in the following water to the sample of emulsion particles (B), the swelling ratio is calculated using the following formula (7). Asked.
Swelling ratio of component (B) = (Da−Db) / Db × 100 (7)

  The number average particle size (Da) in water is diluted by adding purified water so that the solid content in the sample is 0.1% by mass or more and 20% by mass or less. And trade name “Microtrac UPA-9230”).

  The number average particle size (Db) in the dry state was diluted 100 times, and after rapid freezing by the metal contact method, the solvent was used in the sample chamber of a scanning electron microscope: SEM (manufactured by HITACHI, trade name “S-4800”). Was measured using a SEM set at an acceleration voltage of 1 kV.

(Physical property 2) Weight average molecular weight A sample of the condensate of hydrolyzable silicon compound (C) was manufactured by Tosoh Corporation HLC-8220GPC (column: TSKgel superAWM-H, eluent: DMF (LiBr 5 mmol / L, sample amount 50 μl ( 1 mg / mL), detector: RI, polystyrene equivalent molecular weight).

(Physical property 3) Moisture content A sample of the functional membrane was cured at 80 ° C. for 5 minutes and allowed to stand for 24 hours in an open air environment at 23 ° C. and 50% RH. Thereafter, thermal analysis was performed with a differential heat / thermogravimetric analyzer (TG / DTA220, manufactured by Seiko Instruments Inc., sample amount: 5 mg, heating rate: 10 ° C./min, nitrogen flow rate: 250 ml / min, platinum pan), 200 From the thermogravimetric value at ° C., the moisture content of the film was determined using the following formula (8).
Water content (%) = reduced weight / initial weight × 100 (8)

(Physical property 4) Water contact angle A drop of deionized water was placed on the surface of the functional membrane sample and allowed to stand at 23 ° C. for 10 seconds, and then a contact angle measurement device (DM-501 type contact angle meter manufactured by Kyowa Interface Science Co., Ltd.) It measured using.

(Test 1) Durability Test A functional membrane sample was allowed to stand for 500 hours in an environment of a temperature of 150 ° C. and a humidity of 30% using an environmental tester (EHS-411, manufactured by Espec Corp.).

(Evaluation 1) Antistatic property After the powder (1 type 3) powder (silica sand) of JIS Z 8901 test powder (corresponding to hydrophilic dirt) was evenly sprinkled on the substrate on which the coating film was formed, Gently shake the base material and drop the powder. The state in which the powder remained was judged visually, the presence or absence of antistatic property (hydrophilicity) of the functional film was judged, and evaluated according to the following criteria.
○: Almost no powder adheres, so there is antistatic property.
(Triangle | delta): The powder has adhered slightly and there exists some antistatic property.
X: Powder is adhered and there is no antistatic property.

(Evaluation 2) Oil repellency Carbon black powder (corresponding to hydrophobic dirt) classified with a 100-mesh sieve is evenly sprinkled on a substrate on which a film is formed, and then lightly vibrated after the substrate is stood. Give and drop the carbon black powder. The state in which the powder remained was judged visually, the presence or absence of oil repellency of the functional film was judged, and the following criteria were evaluated.
○: Almost no powder adheres, so there is oil repellency.
(Triangle | delta): The powder has adhered slightly and there is some oil repellency.
X: Powder is adhered and there is no oil repellency.

[Synthesis Example 1] Synthesis of emulsion particles (B-1) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 212 parts of water and a trade name “ADEKA rear soap SE1025N” (manufactured by ADEKA) 1 part of 25% aqueous solution was added, and the inside of the reaction vessel was set to 80 ° C. Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate, and 1 part of 2-hydroxyethyl methacrylate were mixed, and this monomer mixture was mixed with “ADEKA rear soap SE1025N”. A mixture of 10 parts of a 25% aqueous solution and 10 parts of a 2% aqueous solution of ammonium persulfate was made into a pre-emulsion liquid by a homogenizer and added into the reaction vessel from a dropping tank over 2 hours. The temperature in the reaction vessel was kept at 80 ° C. during the addition and for another hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Next, 150 parts of butyl acrylate, 30 parts of tetraethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane and 165 parts of diethylacrylamide, 3 parts of acrylic acid, reactivity A reaction vessel was prepared by mixing 13 parts of an emulsifier (manufactured by ADEKA, trade name “ADEKA rear soap SR-1025”, 25% by weight aqueous solution of solid content), 40 parts of 2% by weight aqueous solution of ammonium persulfate, and 1900 parts of ion-exchanged water. It was dripped simultaneously over about 2 hours in the state which maintained the inside temperature at 80 degreeC. Furthermore, as heat curing, the temperature in the reaction vessel was set to 80 ° C. and stirred for about 4 hours. Thereafter, the mixture was cooled to room temperature, filtered through a 400 mesh wire net, and adjusted with ion exchange water to obtain polymer emulsion particles (B-1) having a solid content of 10% by mass and a number average particle diameter of 90 nm. The swelling rate was 5%.

[Synthesis Example 2] Synthesis of emulsion particles (B-2) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 212 parts of water and 1 part of a 25% aqueous solution of “ADEKA rear soap SE1025N” were added. The reaction vessel was charged at 80 ° C. Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate, and 1 part of 2-hydroxyethyl methacrylate were mixed, and this monomer mixture was mixed with “ADEKA rear soap SE1025N”. A mixture of 10 parts of a 25% aqueous solution and 10 parts of a 2% aqueous solution of ammonium persulfate was made into a pre-emulsion liquid by a homogenizer and added into the reaction vessel from a dropping tank over 2 hours. The temperature in the reaction vessel was kept at 80 ° C. during the addition and for another hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Next, 150 parts of butyl acrylate, 30 parts of tetraethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane and polyvinyl alcohol (saponification degree 99 mol%, polymerization degree) 1700, made by Kuraray Co., Ltd., trade name “Kuraray Poval PVA117”) 50% 10% aqueous solution, 165 parts diethyl acrylamide, 3 parts acrylic acid, 13 parts reactive emulsifier (“Adekaria soap SR-1025”), ammonium persulfate A mixed solution of 40 parts of a 2% by weight aqueous solution and 1900 parts of ion-exchanged water was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, as heat curing, the temperature in the reaction vessel was set to 80 ° C. and stirred for about 4 hours. Thereafter, the mixture was cooled to room temperature, filtered through a 400 mesh wire mesh, and adjusted with ion exchange water to obtain polymer emulsion particles (B-2) having a solid content of 10% by mass and a number average particle diameter of 150 nm. The swelling rate was 20%.

[Synthesis Example 3] Synthesis of emulsion particles (B-3) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 212 parts of water and 1 part of a 25% aqueous solution of “ADEKA rear soap SE1025N” were added. The reaction vessel was charged at 80 ° C. Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate, and 1 part of 2-hydroxyethyl methacrylate were mixed, and this monomer mixture was mixed with “ADEKA rear soap SE1025N”. A mixture of 10 parts of a 25% aqueous solution and 10 parts of a 2% aqueous solution of ammonium persulfate was made into a pre-emulsion liquid by a homogenizer and added into the reaction vessel from a dropping tank over 2 hours. The temperature in the reaction vessel was kept at 80 ° C. during the addition and for another hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Next, a mixed solution of 150 parts of butyl acrylate, 30 parts of tetraethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane and silicone-modified polyvinyl alcohol (saponification degree: 98 mol%, Average polymerization degree 1700, manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval R1130” 50% 10% aqueous solution, 165 parts diethyl acrylamide, 3 parts acrylic acid, 13 parts reactive emulsifier (“ADEKA rear soap SR-1025”), A mixture of 40 parts of a 2% by weight aqueous solution of ammonium persulfate and 1900 parts of ion-exchanged water was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, as heat curing, the temperature in the reaction vessel was set to 80 ° C. and stirred for about 4 hours. Then, it cooled to room temperature, filtered with a 400 mesh metal-mesh, adjusted with ion-exchange water, and obtained the polymer emulsion particle (B-3) with a solid content of 10 mass% and a number average particle diameter of 180 nm. The swelling rate was 40%.

[Synthesis Example 4] Synthesis of emulsion particles (B-4) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 212 parts of water and 1 part of a 25% aqueous solution of “ADEKA rear soap SE1025N” were added. The reaction vessel was charged at 80 ° C. Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate, and 1 part of 2-hydroxyethyl methacrylate were mixed, and this monomer mixture was mixed with “Adekari Soap SE1025N”. A mixture of 10 parts of a 25% aqueous solution and 10 parts of a 2% aqueous solution of ammonium persulfate was made into a pre-emulsion liquid by a homogenizer and added into the reaction vessel from a dropping tank over 2 hours. The temperature in the reaction vessel was kept at 80 ° C. during the addition and for another hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Next, a mixture of 150 parts of butyl acrylate, 30 parts of tetraethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane and polyvinylpyrrolidone (product name “K” manufactured by Nippon Shokubai Co., Ltd.) -90 ") 200 parts of a 5% methanol solution, 165 parts of diethyl acrylamide, 3 parts of acrylic acid, 13 parts of a reactive emulsifier (" Adekaria soap SR-1025 "), 40 parts of a 2% by weight aqueous solution of ammonium persulfate, ion exchange A mixture of 1900 parts of water was added dropwise over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C. Furthermore, as heat curing, the temperature in the reaction vessel was set to 80 ° C. and stirred for about 4 hours. Then, it cooled to room temperature, filtered with a 400 mesh metal-mesh, adjusted with ion-exchange water, and obtained polymer emulsion particle | grains (B-4) with a solid content of 10 mass% and a number average particle diameter of 200 nm. The swelling rate was 60%.

[Synthesis Example 5] Synthesis of emulsion particles (B-5) Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 1600 g of ion-exchanged water and 4 g of dodecylbenzenesulfonic acid were added and stirred. The temperature was warmed to 80 ° C. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. For about 1 hour. Next, 150 parts of butyl acrylate, 30 g of dimethyldimethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane and 168 parts of butyl acrylate, a reactive emulsifier (“Adekalia Soap SR-1025 ") 13 parts, 40 parts of a 2% by weight aqueous solution of ammonium persulfate, and 1900 parts of ion-exchanged water were simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. did. Furthermore, as heat curing, the temperature in the reaction vessel was set to 80 ° C. and stirred for about 4 hours. Then, it cooled to room temperature and filtered with the 400 mesh metal-mesh, and obtained the polymer emulsion particle | grains (B-5) with a solid content of 14 mass% and a number average particle diameter of 40 nm. The swelling rate was 2%.

[Synthesis Example 6] Synthesis of emulsion particles (B-6) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 212 parts of water and 1 part of a 25% aqueous solution of “ADEKA rear soap SE1025N” were added. The reaction vessel was charged at 80 ° C. Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate, and 1 part of 2-hydroxyethyl methacrylate were mixed, and this monomer mixture was mixed with “Adekari Soap SE1025N”. A mixture of 10 parts of a 25% aqueous solution and 10 parts of a 2% aqueous solution of ammonium persulfate was made into a pre-emulsion liquid by a homogenizer and added into the reaction vessel from a dropping tank over 2 hours. The temperature in the reaction vessel was kept at 80 ° C. during the addition and for another hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Next, a mixture of 150 parts of butyl acrylate, 30 parts of tetraethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane and 5% of polyvinylpyrrolidone ("K-90") A mixed solution of 300 parts of methanol solution, 165 parts of diethyl acrylamide, 3 parts of acrylic acid, 13 parts of reactive emulsifier (“ADEKA rear soap SR-1025”), 40 parts of 2% by weight aqueous solution of ammonium persulfate, and 1900 parts of ion-exchanged water, Were simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, as heat curing, the temperature in the reaction vessel was set to 80 ° C. and stirred for about 4 hours. Thereafter, the mixture was cooled to room temperature, filtered through a 400-mesh wire mesh, and adjusted with ion-exchanged water to obtain polymer emulsion particles (B-6) having a solid content of 6% by mass and a number average particle size of 240 nm. The swelling rate was 120%.

[Example 1]
Tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., described as “TEOS” in the table) as the hydrolyzable silicon compound (C) is 1 mol / L nitric acid aqueous solution so that the SiO ₂ equivalent concentration is 16% by mass. Was added to 2-propanol so as to be 20 moles of tetraethoxysilane. This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, the polymer emulsion particles (B-1) synthesized in Synthesis Example 1 and water-dispersed colloidal silica having an average particle size of 5 nm as metal oxide fine particles (D) (trade name “Snowtex OXS, manufactured by Nissan Chemical Industries, Ltd.”) (In the table, described as “ST-OXS”), solid content of 10% by mass) and the condensate (C ′) were mixed so that the solid content mass ratio described in Table 1 was obtained, and the solid content of 6 % Was adjusted with 20% ethanol water to obtain a coating composition (1). The “D / B / C ′ ratio” in the table is the composition ratio (similar to the mass ratio of each component calculated in terms of solid content of the coating composition) and the mass of the metal oxide fine particles (D). The mass of the polymer emulsion particles (B-1) to (B-6) and the mass of the condensate (C ′) of the hydrolyzable silicon compound are represented by a ratio. Note that (C ′) is a hydrolysis condensate of the hydrolyzable silicon compound (C). When the molecular weight of (C ′) was measured, the weight average molecular weight was 39500.

The coating composition (1) was applied to a white glass of 5 cm × 5 cm by roll coating, dried at room temperature for 15 minutes, and then dried at 130 ° C. for 10 minutes to obtain a functional film. The dry coating mass of the coating composition (1) at that time was 1 g / m ² and the moisture content of the coating was 1.5%. The evaluation results are shown in Table 1.

[Examples 2 and 3, Reference Example 4, Example 5, Reference Example 6 and Reference Example 8]
A functional film was produced in the same manner as in Example 1 except that the type of emulsion particles used and the composition ratio of the coating composition were changed as shown in Table 1. Table 1 shows the physical properties and evaluation results of these functional films.

[ Reference Example 7]
Tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as the hydrolyzable silicon compound (C) is S
The 0.1 mol / L nitric acid aqueous solution was added to 2-propanol so as to be 4 times mol of tetraethoxysilane so that the iO ₂ equivalent concentration was 16% by mass. This is 24 at 25 ° C.
A time reaction was performed to obtain a condensate (C ′). Next, emulsion particles synthesized in Synthesis Example 1 (
B-1), water-dispersed colloidal silica (“Snowtex OXS”) having an average particle diameter of 5 nm as metal oxide fine particles (D), and a condensate (C ′) After mixing with 20% ethanol water so that the solid content was 6%, a coating composition (7) was obtained. When the molecular weight of (C ′) was measured, the weight average molecular weight was 9900.

A coating composition (7) was applied to white glass of 5 cm × 5 cm by a roll coating method, dried at room temperature for 15 minutes, and then dried at 130 ° C. for 10 minutes to obtain a functional film. The dry film mass of the coating composition (7) at that time was 1 g / m ² and the water content of the film was 2%. The evaluation results are shown in Table 1.

[ Reference Example 9]
Tetramethoxysilane oligomer (manufactured by Mitsubishi Chemical Co., Ltd., trade name “MS56”, described as “MS56” in the table) as the hydrolyzable silicon compound (C) is such that the SiO ₂ equivalent concentration is 16% by mass, A 1 mol / L nitric acid aqueous solution was added to 2-propanol so as to be 20 moles of water of tetramethoxysilane. This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, the emulsion particles (B-1) synthesized in Synthesis Example 1 and water-dispersed colloidal silica (“Snowtex OX”) having an average particle diameter of 5 nm as metal oxide fine particles (D).
S ") and the condensate (C ') are mixed so as to have a solid content mass ratio shown in Table 2, and the solid content is 6%.
The coating composition (8) was obtained after adjusting with 20% ethanol water so that. (C
When the molecular weight measurement of ') was performed, the weight average molecular weight was 425,000.

The coating composition (8) was applied on white glass of 5 cm × 5 cm by roll coating, dried at room temperature for 15 minutes, and then dried at 130 ° C. for 10 minutes to obtain a functional film. The dry film mass of the coating composition (8) at that time was 1 g / m ² , and the water content of the film was 1.8%. The evaluation results are shown in Table 2.

[ Reference Example 10]
The tetramethoxysilane oligomer as the hydrolyzable silicon compound (C) is adjusted so that the SiO ₂ equivalent concentration is 16% by mass so that the 1 mol / L nitric acid aqueous solution is 20 times mol of the tetramethoxysilane oligomer (“MS56”). To 2-propanol. This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, emulsion particles (B)
(Made by Daiichi Kogyo Seiyaku Co., Ltd., trade name “Superflex 126”), 20% ethanol water was added to adjust the solid content to 10%, and silicone-modified polyvinyl alcohol (saponification degree 98 mol%, average polymerization degree) 1700, manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval R1130”)
5% by mass of a 10% aqueous solution was added and reacted at 30 ° C. for 2 hours to obtain emulsion particles (B-7). Next, the condensate (C ′) was added to form a shell layer of (C ′) around (B). Subsequently, water-dispersed colloidal silica having an average particle diameter of 4 nm (made by Nalco Company, trade name “NALCO1115”) as spherical metal oxide fine particles (D).
, 16.5% by mass of solid content, described as “Nalco1115” in the table), and adjusted to 20% ethanol water so that the solid content is 6%. Thus, a coating composition (9) was obtained. It was subjected to molecular weight measurement of (C '), and a weight average molecular weight 42500 0.

A coating composition (9) was applied to white glass of 5 cm × 5 cm by roll coating, and dried at room temperature for 15 minutes and then at 130 ° C. for 10 minutes to obtain a functional film. The dry film mass of the coating composition (9) at that time was 1 g / m ² and the water content of the film was 3%. The evaluation results are shown in Table 2.

[ Reference Example 11]
Tetramethoxysilane oligomer (“MS56”) as hydrolyzable silicon compound (C)
1 mol / L nitric acid aqueous solution was added to 2-propanol so as to be 20 times mol of the tetramethoxysilane oligomer so that the SiO ₂ equivalent concentration was 16% by mass. This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, emulsion particles (B-1) synthesized in Synthesis Example 1 and hollow water-dispersed colloidal silica (manufactured by Nissan Chemical Industries, trade name “Light Star LA-S233A”, particle size as metal oxide fine particles (D)) 300 nm,
A specific surface area of 250 m ² / g, a pore volume of 0.74 cm ³ / g, a pore diameter of 16 nm, a solid content of 23% by mass, and described in the table as “LA-S233A”), and a condensate (C ′), After mixing so that it might become solid content mass ratio of Table 2, and adjusting with 20% ethanol water so that solid content might be 6%, coating composition (10) was obtained. When the molecular weight of (C ′) was measured, the weight average molecular weight was 425,000.

The coating composition (10) was applied to white glass of 5 cm × 5 cm by roll coating, and dried at room temperature for 15 minutes and then at 130 ° C. for 10 minutes to obtain a functional film. The dry film mass of the coating composition (10) at that time was 1 g / m ² and the water content of the film was 5%. The evaluation results are shown in Table 2.

[Comparative Example 1]
Tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as the hydrolyzable silicon compound (C) is ² % so that the SiO ² equivalent concentration is 16% by mass, and the 1 mol / L nitric acid aqueous solution is 20 times mol of tetraethoxysilane. -Added to propanol. This was reacted at 60 ° C. for 96 hours to obtain a condensate (C ′). Next, the emulsion particles (B-1) synthesized in Synthesis Example 1, the water-dispersed colloidal silica (“Snowtex OXS”) having an average particle diameter of 5 nm as the metal oxide fine particles (D), and the condensate (C ′) Were mixed with the solid content mass ratio shown in Table 2 and adjusted with 20% ethanol water so that the solid content was 6% to obtain a coating composition (11). When the molecular weight of (C ′) was measured, the weight average molecular weight was 500,000.

The coating composition (11) was applied on white glass of 5 cm × 5 cm by roll coating, dried at room temperature for 15 minutes, and then dried at 130 ° C. for 10 minutes to obtain a functional film. At that time, the dry film weight of the coating composition (11) was 1 g / m ² , and the moisture content of the film was 0.05%. The evaluation results are shown in Table 2.

[Comparative Example 2]
A functional membrane was produced in the same manner as in Example 1 except that the emulsion particles (B-1) were changed to the emulsion particles (B-5). The results are shown in Table 2.

[Comparative Example 3]
A functional membrane was produced in the same manner as in Example 1 except that the emulsion particles (B-1) were changed to the emulsion particles (B-6). The results are shown in Table 2.

  As shown in Tables 1 and 2, it was found that the functional film of each example maintained antistatic properties and oil repellency even when exposed to a dry state for a long period of time.

  The functional film according to the present invention can be used not only as a cover glass for solar cells, a mirror for solar power generation and a light collecting material, but also as a separating material that requires both antistatic properties and oil repellency. Have.

Claims (2)

A substrate and a coating positioned on the surface of the substrate;
The coating comprises emulsion particles (B) and a hydrolyzable silicon compound condensate,
Metal oxide fine particles (D);
Including
The mass ratio of (D) / (B) is 50/100 or more and 300/100 or less,
The moisture content of the coating is 1.5% to 4% ,
The emulsion particles include acrylic silicon emulsion particles;
The hydrolyzable silicon compound is tetraethoxysilane,
The emulsion particles have a swelling ratio with respect to water of 5% to 40%,
The condensate of the hydrolyzable silicon compound has a weight average molecular weight of 10,000 or more and 50,000 or less.
Below is the functional membrane. The functional film according to claim 1 , wherein the metal oxide fine particles (D) are hollow silica.