JP2012086506A - Defogging film and defogging glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a defogging film which maintains a defogging function and shows high flexibility, as well as a defogging glass using the same.SOLUTION: This defogging film includes a microvoid layer formed on a transparent resin film and containing an inorganic oxide particle, a polymer with reactive functional group, and a crosslinking agent which reacts with the reactive functional group. In the microvoid layer, the water absorption in 0.8 sec. of contact time based on the Bristow's method is 5 to 50 ml/m.

Description

  The present invention relates to an antifogging film having a fine void layer, which has a high flexibility of a film, is easy to be applied to glass or the like, and has excellent antifogging maintenance properties, and an antifogging glass using the antifogging glass. .

  Anti-fogging technology to prevent fogging of general window glass, automobile glass, bathroom mirrors, etc., by placing hot wires on the glass surface or blowing warm air to bring the glass surface above the dew point temperature. A method for preventing condensation by heating is known. However, these methods require a power supply facility, and in particular in a high humidity environment, there is a risk of electrical leakage.

  As another method, there is known a method in which a surfactant or photocatalytic titanium oxide is applied to the surface to impart hydrophilicity, and a copolymer such as urethane is applied to absorb moisture. However, in the method of applying a surfactant, the surfactant is gradually dissolved in water, so that the hydrophilicity cannot be maintained. In the method of applying photocatalytic titanium oxide, not only the effect does not last long in the place where light does not reach, but also at night, the binder resin etc. deteriorates due to the catalytic activity, the adhesion of the coating film deteriorates, the coloring and transparency deteriorate Resulting in. Furthermore, the method of applying a water-absorbing polymer has various problems such as film breakage and distortion due to swelling of the polymer.

  To solve these problems, a method for forming a porous film to absorb moisture is to form a film with metal alkoxide, oxidized fine particles and a water-soluble organic polymer, and then use water or a mixed solution of water and alcohol to form a water-soluble organic compound. A method of forming an antifogging thin film having a porous structure by washing out a polymer and then baking at a high temperature (see, for example, Patent Document 1), polyorganosiloxane, oxide fine particles, and a hydrophilic organic solvent. A method of forming a porous film using the contained coating liquid (for example, see Patent Document 2) is disclosed.

  However, in the methods described in these patent documents, it is necessary to perform baking at a high temperature for a long time in order to cure the film. As a support that can be applied, a substrate having a high temperature resistance such as glass is used. However, it is difficult to process on a general film substrate because it is additionally processed after a window or the like is once attached.

  Furthermore, even if it is formed on a film having high temperature resistance, since the flexibility of the formed film is poor, workability when pasting on glass or the like is poor, and it is difficult to stick uniformly. .

Japanese Patent Laid-Open No. 9-295835 JP 2004-292754 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a highly flexible anti-fogging film excellent in maintainability of the anti-fogging function and an anti-fogging glass using the same.

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

1. In the antifogging film having a fine void layer containing inorganic oxide particles, a polymer having a reactive functional group, and a crosslinking agent that reacts with the reactive functional group on a transparent resin film, the fine void layer is An anti-fogging film having a water absorption of 5 ml / m ² or more and 50 ml / m ² or less when the contact time by the Bristow method is 0.8 seconds.

  2. 2. The antifogging film as described in 1 above, wherein the polymer having a reactive functional group has a weight average molecular weight of 50,000 or more and 500,000 or less.

  3. 3. The antifogging film as described in 1 or 2 above, wherein the fine void layer contains an inorganic polymer represented by the following general formula (1).

General formula (1)
(M (O) _l (OR ¹ ) _m (OR ² ) _n (X) _i (Y) _j ) _k
[Wherein, i and j are each 0 or 1, k is an integer of 2 or more, l, m, and n are each an integer of 0 to 2, and l + m + n = 2. M represents an aluminum atom, a zirconyl atom or a halfnium atom. R ¹ and R ² each represents an alkyl group, an acyl group, or a hydrogen atom, and may be the same or different. X and Y each represent OH, a halogen atom, NO ₃ , SO ₄ , CO ₃ , R ³ COO or H ₂ O, and R ³ represents an alkyl group or a hydrogen atom. ]
4). 4. The antifogging film as described in 3 above, wherein the inorganic polymer represented by the general formula (1) has a repeating unit represented by the following general formula (2) or (3).

[Wherein b and c are each 0 or 1; M, R ¹ , R ² , X and Y are each synonymous with those in the general formula (1). A solid line represents a covalent bond, and a broken line represents a coordination bond, an ionic bond, or a covalent bond. ]
5. 5. An antifogging glass, wherein the antifogging film according to any one of 1 to 4 above is bonded to a surface of a glass substrate.

  According to the present invention, an anti-fogging film excellent in maintainability of an anti-fogging function and having high flexibility and an anti-fogging glass using the same can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the present inventor, on a transparent resin film, contains inorganic oxide particles, a polymer having a reactive functional group, and a crosslinking agent that reacts with the reactive functional group. In the antifogging film having a fine void layer, the fine void layer has a water absorption amount of 5 ml / m ² or more and 50 ml / m ² or less when the contact time by Bristow method is 0.8 seconds. It has been found that a defogging film is excellent in maintainability of the defogging function and can be realized with high flexibility, and the present invention has been achieved.

That is, in the process of intensive study by the present inventors, a fine void layer is formed with a polymer having inorganic oxide particles, a reactive functional group, and a crosslinking agent that reacts with the reactive functional group, and the contact time by Bristow method is 0. When the water absorption amount in 8 seconds is 5 ml / m ² or more and 50 ml / m ² or less, an anti-fogging film that is highly flexible and easy to apply can be obtained while maintaining the anti-fogging function. I found.

  Further, by containing the inorganic polymer represented by the general formula (1) in the fine void layer, the dispersibility of the inorganic oxide particles is improved, and a more uniform void layer can be formed, so that the flexibility is higher. It has been found that an antifogging film can be obtained.

  Hereinafter, the components of the antifogging film of the present invention will be described in detail.

<Anti-fog film>
[Water absorption]
The antifogging film of the present invention has a fine void layer containing inorganic oxide particles, a polymer having a reactive functional group, and a crosslinking agent that reacts with the reactive functional group on the transparent resin film, and the fine void layer The water absorption amount at a contact time of 0.8 seconds measured by the Bristow method is 5 ml / m ² or more and 50 ml / m ² or less, preferably 15 ml / m ² or more and 45 ml / m ² or less. It is. If the amount of water absorbed at a contact time of 0.8 seconds is 5 ml / m ² or more, sufficient anti-fogging performance can be exhibited, and if it is 50 ml / m ² or less, it has excellent durability and durability. Fog performance can be realized.

  In the present invention, as a method for controlling the water absorption amount at a contact time of 0.8 seconds by the Bristow method within the range specified in the present invention, inorganic oxide particles (F) and a polymer having a reactive functional group (B) The ratio F / B can be controlled by adjusting the kind and amount of the crosslinking agent that reacts with the reactive functional group of the polymer.

The water absorption amount in the present invention is a method for measuring the liquid absorption behavior of a water-absorbing material in a short time. TAPPI paper pulp test method no. It is measured according to the liquid absorptivity test method (Bristow method) of 51-87 paper or paperboard, and is represented by the amount of water absorption (ml / m ² ) at a contact time of 0.8 seconds. In the above measurement method, pure water (ion exchange water) is used for the measurement, but in order to facilitate the determination of the measurement area, the present invention contains less than 2% water-soluble dye. May be.

  An example of a specific measurement method will be described below.

As a method for measuring the amount of water absorption, an anti-fogging film having a fine void layer is allowed to stand for 12 hours or more in an atmosphere of 25 ° C. and 50% RH. This is measured using a Bristow tester type II (pressure type). In the present invention, the amount of pure water transfer (ml / m ² ) at a contact time of 0.8 seconds is taken as the amount of water absorption.

[Transparent resin film]
There is no restriction | limiting in particular as a transparent resin film applied to the anti-fogging film of this invention, A various transparent resin film can be used, for example, polyolefin films (for example, polyethylene, polypropylene, etc.), polyester films (for example, polyethylene) Terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, triacetyl cellulose and the like can be used, and a polyester film is preferred. Although it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components. Examples of the main dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid. Examples include acids, cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, Examples thereof include bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.

  Among the polyesters having these as main constituent components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred. Furthermore, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

  The transparent resin film according to the present invention preferably has a thickness of 10 to 300 μm, and more preferably 20 to 150 μm.

[Inorganic oxide particles]
The fine void layer according to the present invention is characterized by containing inorganic oxide particles together with a polymer having a reactive functional group and a crosslinking agent that reacts with the reactive functional group.

  Examples of inorganic oxide particles that can be used in the present invention include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, Zinc sulfide, zinc carbonate, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite, magnesium hydroxide And white inorganic pigments.

  As the inorganic fine particles, either inorganic fine particles whose surface is anionic and not fixable to the dye, or inorganic fine particles whose surface fixable to the dye is cationic can be used.

  When using inorganic fine particles whose surface is anionic, a cationic polymer is usually used together. However, when a cationic polymer is added to inorganic fine particles whose surface is anionic, the cationic polymer stays on the surface of the inorganic fine particles. It is presumed that the dye is immobilized by being immobilized on the immobilized cationic polymer.

  In the present invention, silica or colloidal silica synthesized by a gas phase method is preferable as inorganic fine particles having an anionic surface because of low cost and low refractive index fine particles capable of obtaining a high reflection density. .

  The surface-cationic inorganic fine particles have a surface charge by coupling a silane coupling agent having a quaternary ammonium base to the surface of the inorganic fine particles as described in JP-A-8-34160. Inorganic fine particles converted to cationic properties are also included.

  The inorganic fine particles of the present invention are preferably fine particles having a low refractive index and a small average particle diameter, and examples thereof include fine particles such as silica, colloidal silica, calcium silicate, calcium carbonate, boehmite aluminum hydroxide, or a hydrate thereof. Silica fine particles are preferable.

  In addition, when the fine particles are silica fine particles synthesized by a vapor phase method, the primary average particle diameter is preferably 6 to 20 nm.

  The production method of silica fine particles is roughly divided into a dry method (gas phase method) and a wet method, and the dry method includes a method by vapor phase hydrolysis of silicon halide at a high temperature (flame hydrolysis method), and silica sand. A method (arc method) is known in which coke is heated and reduced and vaporized by an arc in an electric furnace and is oxidized in air. As a wet method, there is known a method in which activated silica is produced by acid decomposition of silicate and then excessively polymerized to cause aggregation and precipitation.

  In the present invention, among silica fine particles, silica synthesized by a gas phase method is most preferable.

  The fine particle silica synthesized by the vapor phase method is usually a silica powder having an average primary particle diameter of 5 to 500 nm obtained by burning silicon tetrachloride with hydrogen and oxygen at a high temperature. What has an average primary particle diameter is preferable at the point of glossiness.

  Various types of Aerosil manufactured by Nippon Aerosil Co., Ltd. are currently available as the vapor phase silica.

  The colloidal silica preferably used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or passing through an ion exchange resin layer, and this colloidal silica is used for ink jet recording paper. For example, JP-A-57-14091, JP-A-60-219083, JP-A-60-219084, JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, Kaihei 4-93284, 5-278324, 6-92011, 6-183134, 6-297830, 7-81214, 7-101142, No. 7-179029, No. 7-137431, and International Patent Publication No. WO94 / 26530 It is described, for example, broadcast.

  The average particle diameter of colloidal silica is usually 5 to 100 nm, but an average particle diameter of 7 to 30 nm is particularly preferable.

  Silica and colloidal silica synthesized by the vapor phase method may be those whose surfaces are cation-modified, or those treated with Al, Ca, Mg, Ba, or the like.

[Polymer having reactive functional group]
The polymer having a reactive functional group that can be used in the present invention is not particularly limited as long as the polymer has a functional group that reacts with a crosslinking agent described later.

  Here, the reactive functional group includes a hydroxyl group, carboxyl group, carbonyl group, amino group, isocyanate group, organic halogen group, epoxy group, oxetanyl group, alkoxide group, vinyl group, aldehyde group, etc. Of these, a hydroxyl group or a carboxyl group is preferred. Examples of the polymer having these functional groups include polyvinyl alcohol, polyacrylic acid (and salts thereof), polyacrylamide, polyvinyl pyrrolidone, saccharides, and gelatin. Other polymers having reactive functional groups or reactive functional groups with polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, aramid, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, etc. as the main skeleton. Copolymers with monomers may also be used.

  Among these, polyvinyl alcohol and polyacrylic acid are preferable, and polyvinyl alcohol is particularly preferable because it is industrially inexpensive and has a hydroxyl group that is easy to control the reaction.

  The polyvinyl alcohol preferably used in the present invention includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group. Alcohol is also included.

  The polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, and particularly preferably has an average degree of polymerization of 1,500 to 5,000. The degree of saponification is preferably 70 to 100%, particularly preferably 80 to 99.5%.

  Examples of the cation-modified polyvinyl alcohol have primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-110483. Polyvinyl alcohol, which is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

  Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1, 1-dimethyl-3-dimethylaminopropyl) acrylamide and the like.

  The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.

  Anion-modified polyvinyl alcohol is, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-2060888, as described in JP-A-61-237681 and JP-A-63-330779, Examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

  Nonionic modified polyvinyl alcohol is, for example, a polyvinyl alcohol derivative obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and described in JP-A-8-25595. And a block copolymer of a vinyl compound having a hydrophobic group and vinyl alcohol. Polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.

  The molecular weight of the polymer having a reactive functional group according to the present invention is preferably 50,000 or more and 500,000 or less as a weight average molecular weight in terms of styrene by GPC measurement. More preferably, the weight average molecular weight is 100,000 or more and 250,000 or less. If it is 50,000 or more, it is easy to form a fine void layer that reacts with the crosslinking agent and has high strength and hardly swells in water, and if it is 500,000 or less, the viscosity improvement of the coating solution for the fine void layer can be suppressed. This is preferable from the point of tendency. Further, two or more kinds having different molecular weights may be mixed and used.

The ratio of the polymer having a reactive functional group and the inorganic oxide particles in the fine void layer of the present invention is preferably about 1:10 to 1: 3 in mass ratio. If the ratio between the polymer having a reactive functional group and the inorganic oxide particles is 1: 3 or more, a fine void layer can be formed uniformly, and water is absorbed when the contact time by the Bristow method is 0.8 seconds. The amount is 5 ml / m ² or more, and the desired antifogging performance is obtained. A ratio of the polymer having a reactive functional group to the inorganic oxide particles is preferably 1:10 or less from the viewpoint of maintaining the strength of the fine void layer.

[Crosslinking agent]
The curing agent that can be used in the present invention is not particularly limited as long as it causes a curing reaction with the reactive functional group of the polymer, but boric acid and its salts are preferable, but other known ones are used. In general, a compound having a group capable of reacting with a polymer having a reactive functional group or a compound that promotes the reaction between different groups of a polymer having a reactive functional group, It is appropriately selected depending on the type of polymer to be used. In the crosslinking agent applicable to this invention, when the polymer which has a reactive functional group is polyvinyl alcohol, boric acid, its salt, and an epoxy-type hardening | curing agent are preferable.

  Specific examples of the curing agent include, for example, an epoxy curing agent (for example, diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N- Diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde-based curing agents (for example, formaldehyde, glioxal, etc.), active halogen-based curing agents (for example, 2,4-dichloro-4-hydroxy) -1,3,5, -s-triazine, etc.), active vinyl compounds (for example, 1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like. .

  Boric acid or a salt thereof refers to an oxygen acid having a boron atom as a central atom and a salt thereof, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaboron. Examples include acids and their salts.

  Boric acid having a boron atom and a salt thereof as a curing agent may be used alone or in combination of two or more. Particularly preferred is a mixed aqueous solution of boric acid and borax.

  The aqueous solutions of boric acid and borax can be added only in relatively dilute aqueous solutions, respectively, but by mixing them both can be made into a concentrated aqueous solution and the coating solution can be concentrated. Further, there is an advantage that the pH of the aqueous solution to be added can be controlled relatively freely.

  The total amount of the curing agent used is preferably 1 to 600 mg per 1 g of the polymer having a reactive functional group according to the present invention.

[Inorganic polymer]
The fine void layer according to the present invention preferably contains an inorganic polymer represented by the following general formula (1). In the present invention, the use of an inorganic polymer represented by the following general formula (1) as the binder is preferable from the viewpoint of improving water absorption and durability.

General formula (1)
(M (O) _l (OR ¹ ) _m (OR ² ) _n (X) _i (Y) _j ) _k
In the general formula (1), i and j are each 0 or 1, k is an integer of 2 or more, l, m, and n are each an integer of 0 to 2, and l + m + n = 2. M represents an aluminum atom, a zirconyl atom or a halfnium atom. R ¹ and R ² each represents an alkyl group, an acyl group, or a hydrogen atom, and may be the same or different. X and Y each represent OH, a halogen atom, NO ₃ , SO ₄ , CO ₃ , R ³ COO or H ₂ O, and R ³ represents an alkyl group or a hydrogen atom.

  Furthermore, from the viewpoint of further improving durability, the inorganic polymer represented by the general formula (1) preferably has a repeating unit represented by the following general formula (2) or (3).

In the said General formula (2) and General formula (3), b and c are 0 or 1, respectively. M, R ¹ , R ² , X and Y are each synonymous with those in the general formula (1). A solid line represents a covalent bond, and a broken line represents a coordination bond, an ionic bond, or a covalent bond.

  In the inorganic polymer which concerns on this invention, in General formula (2), (3), you may have multiple types of repeating unit from which X, Y, b, and c differed.

  In the above general formulas (1) to (3), M is preferably a zirconyl atom or an aluminum atom.

In the general formula (2), M is preferably a zirconyl atom, R ¹ is preferably a hydrogen atom, and X is preferably OH.

In the general formula (3), M is preferably an aluminum atom, R ¹ and R ² are each preferably a hydrogen atom, and X is preferably H ₂ O.

  Specific examples of the inorganic polymer containing a zirconyl atom of the general formulas (1) to (3) include, for example, zirconyl difluoride, zirconyl trifluoride, zirconyl tetrafluoride, hexafluorozirconylate (for example, potassium salt) ), Heptafluorozirconylate (for example, sodium, potassium and ammonium salts), octafluorozirconylate (for example, lithium salt), fluorinated zirconyl, zirconyl dichloride, zirconyl trichloride, zirconyl tetrachloride, hexachloro Zirconylates (eg, sodium and potassium salts), zirconyl oxychloride (zirconyl chloride), zirconyl dibromide, zirconyl tribromide, zirconyl tetrabromide, zirconyl bromide oxide, zirconyl triiodide, zirconyl tetraiodide , Zirconyl peroxide, zirconyl hydroxide, zirco sulfide Zirconyl sulfate, zirconyl p-toluenesulfonate, zirconyl sulfate, sodium zirconyl sulfate, acidic zirconyl sulfate trihydrate, potassium zirconyl sulfate, zirconyl selenate, zirconyl nitrate, zirconyl nitrate, zirconyl phosphate, zirconyl carbonate, zirconyl carbonate Ammonium, zirconyl acetate, zirconyl acetate, zirconyl ammonium acetate, zirconyl lactate, zirconyl citrate, zirconyl stearate, zirconyl phosphate, zirconyl oxalate, zirconyl isopropylate, zirconyl butyrate, zirconyl acetylacetonate, acetylacetone zirconyl butyrate, stearin Acid zirconyl butyrate, zirconyl acetate, bis (acetylacetonato) dichlorozirconyl, tris (acetylacetate) G) chloro zirconyl and the like.

  Among these compounds, zirconyl chloride, zirconyl sulfate, sodium zirconyl sulfate, acidic zirconyl sulfate trihydrate, zirconyl nitrate, zirconyl carbonate, zirconyl ammonium carbonate, zirconyl acetate, zirconyl ammonium acetate, zirconyl stearate are more preferable. Zirconyl carbonate, zirconyl ammonium carbonate, zirconyl acetate, zirconyl nitrate and zirconyl chloride, particularly preferably zirconyl ammonium carbonate, zirconyl chloride and zirconyl acetate. Specific product names of the above compounds include Zircozole ZA-20 (Zirconyl Acetate) manufactured by Daiichi Rare Element Chemical Industry, Zircosol ZC-2 (Zirconyl Chloride) manufactured by Daiichi Rare Element Chemical Industry, First Rare Element Chemical Industry Zircosol ZN (zirconyl nitrate) and the like manufactured by the company are listed.

  Structural formulas of typical compounds among the inorganic polymers containing the zirconyl atom are shown below.

  However, s and t represent integers of 1 or more.

  The inorganic polymer containing a zirconyl atom may be used alone, or two or more different compounds may be used in combination.

  Specific examples of the inorganic polymer containing aluminum atoms of the general formulas (1) to (3) include aluminum fluoride, hexafluoroaluminic acid (for example, potassium salt), aluminum chloride, basic aluminum chloride (for example, Polyaluminum chloride), tetrachloroaluminate (eg, sodium salt), aluminum bromide, tetrabromoaluminate (eg, potassium salt), aluminum iodide, aluminate (eg, sodium salt, potassium salt, calcium) Salt), aluminum chlorate, aluminum perchlorate, aluminum thiocyanate, aluminum sulfate, basic aluminum sulfate, potassium aluminum sulfate (alum), ammonium aluminum sulfate (ammonium alum), sodium aluminum sulfate, phosphoric acid Aluminum, Aluminum nitrate, Hydrogen phosphate, Aluminum carbonate, Aluminum polysulfate, Aluminum formate, Aluminum acetate, Aluminum lactate, Aluminum oxalate, Aluminum isopropylate, Aluminum butyrate, Ethyl acetate Aluminum diisopropylate, Aluminum tris (acetylacetonate) ), Aluminum tris (ethyl acetoacetate), aluminum monoacetylacetonate bis (ethyl acetoacetonate), and the like.

  Among these, aluminum chloride, basic aluminum chloride, aluminum sulfate, basic aluminum sulfate, and basic aluminum sulfate silicate are preferable, and basic aluminum chloride and basic aluminum sulfate are most preferable. Specific product names of the above compounds include Takibine # 1500 manufactured by Taki Chemical.

  The structural formula of Takibine # 1500 is shown below.

  However, s, t, and u represent an integer of 1 or more.

  1-100 mass parts is preferable with respect to 100 mass parts of inorganic oxide particles, and, as for the addition amount of the said inorganic polymer, 2-50 mass parts is still more preferable.

[Other additives]
The fine void layer according to the present invention can contain various additives as required.

  For example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989, and JP-A-60-72785. No. 61-146591, JP-A-1-95091, JP-A-3-13376, etc., various surfactants of anion, cation or nonion, JP-A-59- 42993, 59-52689, 62-280069, 61-242871, and JP-A-4-219266, etc., whitening agents such as sulfuric acid, phosphoric acid, acetic acid, PH adjusters such as citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives, Antistatic agents, can also contain various known additives such as a matting agent.

[Method for producing fine void layer]
The antifogging film of the present invention is formed by applying and drying a fine void layer on a support.

  Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791. A slide bead coating method using an hopper, an extrusion coating method, or the like is preferably used.

  The viscosity at the time of applying a plurality of layers simultaneously is preferably 5 to 100 mPa · s, more preferably 10 to 50 mPa · s when the slide bead coating method is used. Moreover, when using a curtain application | coating system, the range of 5-1200 mPa * s is preferable, More preferably, it is the range of 25-500 mPa * s.

  Further, the viscosity at 15 ° C. of the coating solution is preferably 100 mPa · s or more, more preferably 100 to 30,000 mPa · s, further preferably 3,000 to 30,000 mPa · s, and most preferably 10 , 30,000 to 30,000 mPa · s.

  The viscosity in the present invention can be measured using, for example, a B-type viscometer BL manufactured by Tokyo Keiki Co., Ltd.

  As a coating and drying method, it is preferable that the coating liquid is heated to 30 ° C. or higher and applied, and then the temperature of the formed coating film is once cooled to 1 to 15 ° C. and dried at 10 ° C. or higher. More preferably, the drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. Moreover, as a cooling method immediately after application | coating, it is preferable to carry out by a horizontal set system from a viewpoint of the formed coating-film uniformity.

《Application of anti-fogging film》
The antifogging film of the present invention can be applied to a wide range of fields. For example, it is used for the purpose of preventing fogging by adhering to a window of a building, a window of a car, a mirror in a bathroom or bathroom, a window glass of a frozen showcase, etc. with an adhesive. In the present invention, in particular, the antifogging glass is constituted by laminating the antifogging film of the present invention on the surface of the glass substrate.

  The glass substrate used in the present invention is not particularly limited as long as it has high light transmittance, and the raw material, production method, shape, structure, thickness, hardness, etc. are appropriately selected from known materials. You can choose. For example, quartz glass, soda lime glass, silicate glass, aluminosilicate glass, borosilicate glass, phosphate glass, and fluorophosphate glass can be used.

  As an adhesive applicable to the present invention, an adhesive mainly composed of a photocurable or thermosetting resin can be used.

  The adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic adhesive or a silicone adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, since the peel strength can be easily controlled, a solvent system is preferable among the solvent system and the emulsion system in the acrylic adhesive. When a solution polymerization polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known monomers can be used as the monomer.

  In addition, you may add and mix | blend an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, coloring, an adhesion adjusting agent etc. suitably in a contact bonding layer.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of anti-fogging film >>
[Preparation of Sample 1]
100 ml of an aqueous solution of a crosslinking agent containing 13.5 g of silica particles (Nippon Aerosil Co., Ltd.) having an average particle diameter of 7 nm as inorganic oxide particles, 2.4% boric acid and 1.9% sodium tetraborate (borax). And dispersed with a high-speed homogenizer to prepare a silica dispersion. Next, 45 ml of a 5% aqueous solution of polyvinyl alcohol having a weight average molecular weight of 200,000 was gradually added to the silica dispersion dispersed with a high-speed homogenizer to prepare a coating solution 1.

  Next, the prepared coating solution 1 was applied onto a polyethylene terephthalate film having a thickness of 50 μm at a wet film thickness of 200 μm, cooled at 5 ° C. for 15 seconds, and then dried at 40 ° C. to prepare Sample 1.

[Preparation of Sample 2]
In preparation of Sample 1, 1.8 g of Takibine # 1500 (Exemplary Compound-6) manufactured by Taki Chemical Co., Ltd. was added as an inorganic polymer to the aqueous crosslinking agent solution used in the preparation of Coating Solution 1, and the weight average molecular weight was 4. Sample 2 was prepared in the same manner except that 50,000 polyvinyl alcohol was used.

[Preparation of Samples 3 to 6]
Samples 3 to 6 were prepared in the same manner as in the preparation of Sample 2, except that the weight average molecular weight of polyvinyl alcohol was changed as shown in Table 1.

[Preparation of Samples 7 to 10]
Samples 7 to 10 were prepared in the same manner except that the addition amount of silica particles was appropriately adjusted so as to be the ratio of inorganic particles to polymer (F / B) described in Table 1 in the preparation of Sample 5. Produced.

[Preparation of Samples 11 and 12]
In the preparation of Sample 5, polyvinyl alcohol (weight average molecular weight 200,000) was changed to each polymer shown in Table 1 as a polymer having a reactive functional group, and Denacol EX-313 (Nagase Chemtech Co., Ltd.) was used as a crosslinking agent. Samples 11 and 12 were produced in the same manner except that the amount added was changed to 4.3%.

[Production of Samples 13 and 14]
In the preparation of Sample 5, instead of silica particles (manufactured by Nippon Aerosil Co., Ltd.), alumina particles Alu-C (manufactured by Nippon Aerosil Co., Ltd.) and zirconia particle nanouse ZR30-AR (manufactured by Nissan Chemical Co., Ltd.) were used as inorganic oxide particles. Samples 13 and 14 were produced in the same manner except that they were used.

[Production of Samples 15 and 16]
In the preparation of Sample 5, instead of boric acid and sodium tetraborate (borax), Denacol EX-313 (manufactured by Nagase Chemtech) and Takenate WD720 (manufactured by Mitsui Chemicals) were used instead of boric acid and sodium tetraborate (borax), respectively. Similarly, Samples 15 and 16 were produced.

[Preparation of Samples 17 and 18]
In the preparation of Sample 5, instead of tachybaine # 1500 as an inorganic polymer, Zircozole ZC-2 (manufactured by Daiichi Rare Element Chemical Industry, Exemplified Compound-5), HAS-1 (manufactured by Colcoat, part of tetraethoxysilane) Samples 17 and 18 were prepared in the same manner except that a compound which is a partial hydrolyzate of the condensate and does not correspond to the general formulas (1) to (3) was used.

[Preparation of Sample 19]
Sample 19 was prepared in the same manner as in the preparation of Sample 5, except that no crosslinking agent was added.

[Preparation of Sample 20]
Sample 20 was prepared in the same manner as in preparation of Sample 5, except that the amount of silica added was changed so that the ratio of inorganic oxide particles to polymer (F / B) was 2.5: 1. Produced.

[Preparation of Sample 21]
Into an aqueous solution having a 10:50 molar ratio of isopropyl alcohol and pure water containing 5% of polyethylene glycol (PEG 4000) having a weight average molecular weight of 4000, alumina sol-10A (manufactured by Kawaken Fine Chemical Co., Ltd.), triethyl phosphate, ethyl silicate Was added at a molar ratio of 0.5: 0.5: 1 to prepare a coating solution 21.

  Next, the coating solution 21 prepared above was applied on a glass plate having a thickness of 2 mm, and then dried at 150 ° C. for 30 minutes. Next, the sample was immersed in a 1: 1 mixture of ethyl alcohol and pure water for 5 minutes, dried at 40 ° C., and then heat-treated at 690 ° C. for 4 minutes to produce Sample 21.

[Preparation of Sample 22]
40 g of H ₂ N (CH ₂ ) ₂ HN (CH ₂ ) ₃ Si (OCH ₃ ) ₃ was added to 100 g of 70% aqueous methanol over 20 minutes with stirring. Subsequently, after maintaining at 60 ° C. for 1 hour in an oil bath, the mixture was allowed to cool to prepare about 140 g of a polyorganosiloxane solution (concentration: about 21% by mass).

  After adding 4 g of the polyorganosiloxane solution prepared above to 56 g of isopropyl alcohol while stirring, 20 g of Snowtex CM (Nissan Chemical Industry Co., Ltd., colloidal silica) was added, and the mixture was stirred for 2 hours. Prepared.

  The prepared coating solution 22 was dip-coated on a glass substrate having a thickness of 2 mm at a pulling rate of 40 mm / min, and then heat-treated at 120 ° C. for 1 hour to prepare a sample 22.

[Preparation of Sample 23]
Sample 23 was prepared in the same manner as in the preparation of Sample 22, except that the glass substrate was changed to a polyethylene terephthalate film having a thickness of 50 μm and the heat treatment temperature after coating was changed to 80 ° C.

<Evaluation of anti-fogging film>
According to the following method, the characteristic value measurement and performance evaluation of the produced anti-fogging film were performed.

[Measurement of water absorption of anti-fogging film]
J. et al. TAPPI paper pulp test method no. Water absorption amount of pure water (ml / m ² ) at a contact time of 0.8 seconds using a Bristow tester (manufactured by Toyo Seiki Co., Ltd.) according to the 51-87 paper or paperboard liquid absorbency test method (Bristow method) ) Was measured.

[Evaluation of anti-fogging performance 1]
Each antifogging film that was allowed to stand for 1 hour in an environment of 20 ° C. and 50% relative humidity was placed on a hot water bath at 40 ° C., and the time until fogging was observed (antifogging time, minutes) was measured.

  Antifogging performance 1 in the above evaluation requires practically 0.3 minutes or more of antifogging time, more preferably 1 minute or more, and more preferably 2 minutes or more.

[Evaluation of anti-fogging maintenance]
A cycle of standing for 10 minutes in an environment of −20 ° C. and then standing for 10 minutes in an environment of 25 ° C. and 50% RH is defined as one cycle, and the state of the film surface after repeating this 10 cycles is visually observed. Antifogging durability was evaluated according to the following criteria.

◎: No change in the film state of the anti-fogging film and no fogging observed ○: No change in the film state of the anti-fogging film, but slight fogging observed △: The film of the anti-fogging film slightly lifted , Clouding is also observed ×: film peeling of the anti-fogging film occurs [Evaluation of flexibility]
About each produced anti-fog film, based on the bending test method based on JISK5600-5-1, using a bending tester type 1 (Imoto Seisakusho make, model IMC-AOF2, mandrel diameter φ20mm) 30 times The bending test was conducted.

<Evaluation of anti-fogging performance 2 after bending treatment>
With respect to the antifogging film after 30 bending tests, the antifogging time until fogging was observed was measured in the same manner as in the above antifogging performance 1, and this was designated as antifogging performance 2. The smaller the difference in antifogging performance before and after the bending test, the higher the flexibility.

<Observation of antifogging film surface>
The surface of the anti-fogging film after 30 bending tests was visually observed, and the flexibility was evaluated according to the following criteria.

◎: No folding marks or cracks are observed on the surface of the anti-fogging film. ○: Slight bending marks are observed on the surface of the anti-fogging film. Δ: Slight cracks are observed on the surface of the anti-fogging film. Many obvious cracks are generated on the surface of the antifogging film. Table 2 shows the measurement results and evaluation results obtained as described above.

  As is clear from the results shown in Table 2, the anti-fogging film of the present invention is good in both anti-fogging performance and anti-fogging sustainability, and has high film flexibility without being treated at high temperature. However, it can be seen that the film does not peel off and the antifogging performance after the bending test does not change.

Example 2
<< Preparation of anti-fog glass >>
The antifogging films 1 to 23 produced in Example 1 were polished on a 3.5 mm float glass (clear) substrate after polishing the top surface and then washed with a neutral detergent, water, and alcohol. Adhesives and an isocyanate-based curing agent were used for close adhesion to produce antifogging glasses 1-23.

<Evaluation of anti-fog glass>
About each produced antifogging glass, the antifogging performance as antifogging glass and antifogging are carried out similarly to the method described in Example 1 and the ease of application of the antifogging film and the uniformity of the application surface. As a result of evaluating the sustainability, the antifogging glass of the present invention is easy to paste relative to the comparative example, has high uniformity of the film surface at the time of pasting, and excellent in antifogging performance and antifogging sustainability. I was able to confirm that.

Claims (5)

In the antifogging film having a fine void layer containing inorganic oxide particles, a polymer having a reactive functional group, and a crosslinking agent that reacts with the reactive functional group on a transparent resin film, the fine void layer is An anti-fogging film having a water absorption of 5 ml / m ² or more and 50 ml / m ² or less when the contact time by the Bristow method is 0.8 seconds.   The anti-fogging film according to claim 1, wherein the polymer having the reactive functional group has a weight average molecular weight of 50,000 or more and 500,000 or less. The anti-fogging film according to claim 1 or 2, wherein the fine void layer contains an inorganic polymer represented by the following general formula (1).
General formula (1)
(M (O) _l (OR ¹ ) _m (OR ² ) _n (X) _i (Y) _j ) _k
[Wherein, i and j are each 0 or 1, k is an integer of 2 or more, l, m, and n are each an integer of 0 to 2, and l + m + n = 2. M represents an aluminum atom, a zirconyl atom or a halfnium atom. R ¹ and R ² each represents an alkyl group, an acyl group, or a hydrogen atom, and may be the same or different. X and Y each represent OH, a halogen atom, NO ₃ , SO ₄ , CO ₃ , R ³ COO or H ₂ O, and R ³ represents an alkyl group or a hydrogen atom. ] The antifogging film according to claim 3, wherein the inorganic polymer represented by the general formula (1) has a repeating unit represented by the following general formula (2) or (3).

[Wherein b and c are each 0 or 1; M, R ¹ , R ² , X and Y are each synonymous with those in the general formula (1). A solid line represents a covalent bond, and a broken line represents a coordination bond, an ionic bond, or a covalent bond. ]   An antifogging glass comprising the glass substrate surface and the antifogging film according to any one of claims 1 to 4 bonded together.