JP4823497B2 - Composite member having hydrophilicity - Google Patents

Description

  The present invention relates to a composite member having excellent hydrophilicity that does not produce water droplets even when water is brought into contact with it, and has antifogging performance.

  When a device equipped with an optical lens such as glasses or a video camera is moved to an environment with a large temperature difference and high humidity, moisture present in the air aggregates on the surface of the optical lens to form water droplets. Transparency and light transmittance are significantly reduced. Further, it is known that on the surface of a window glass of a train or a car, water drops are formed due to an abrupt temperature difference and the visibility is hindered, causing various problems such as traffic signs becoming unreadable.

  Also, in agricultural houses and tunnels where agricultural coating films are spread, water vapor evaporates from the soil and crops fills up, and the full steam condenses on the film surface due to the temperature difference from the outside air to form water droplets. As a result, there was a problem that the permeability was lowered and the growth of the crop was hindered, and further, water droplets dropped and adhered to the crop to cause illness.

  Various methods have been proposed in which a thin film having excellent hydrophilicity is provided on the surface of a substrate such as an optical lens or an agricultural film in order to make it easier for spread water droplets to spread on the surface of the substrate.

For example, a thin film containing photocatalyst fine particles such as titanium oxide and zinc oxide and silica fine particles is formed, and an antifogging effect is imparted by irradiating ultraviolet rays contained in sunlight to develop wettability on the surface. A method (for example, see Patent Document 1) or a solution obtained by emulsion polymerization containing an acrylic monomer, a polymerizable silane coupling agent, and colloidal silica is formed on the film surface to produce 20 colloidal silica. A method of providing a film containing ˜70% by weight (see, for example, Patent Document 2) or a solution containing colloidal alumina, colloidal silica, and a nonionic surfactant is applied to the film surface to form an antifogging layer. A method (for example, see Patent Document 3 and Patent Document 4), a water-soluble resin comprising colloidal alumina, a water-soluble resin having an average molecular weight of 100,000 to 4,000,000 and a nonionic surfactant. The method of applying the film surface (e.g., see Patent Document 5.) And, a method of applying a solution containing the necklace-shaped colloidal silica and silane derivative and the surfactant to the film surface and the like.
Japanese Patent No. 2756474 Japanese Patent Laid-Open No. 07-233270 Japanese Patent Application Laid-Open No. 09-29895 JP 2003-253243 A JP 2003-102288 A JP 2004-099694 A

  However, the above-mentioned optical lenses and films having hydrophilicity and anti-fogging properties have the following various problems.

  For example, in the method described in Japanese Patent No. 2756474, it is very difficult to form a photocatalyst layer made of titanium oxide containing silica fine particles having excellent adhesion on the film surface. There is a problem that the film surface is oxidized and deteriorated by an active species such as a superoxide anion and a hydroxyl radical having excellent oxidizability generated on a certain titanium oxide surface, and the photocatalyst layer falls off with time.

  Further, the method described in JP-A-07-233270 is an antifogging property in which an acrylic monomer, a polymerizable silane coupling agent, and colloidal silica are partially reacted by emulsion polymerization and applied to the film surface. However, the water contact angle of the obtained film is as high as about 50 to 70 °, and the expected antifogging effect is difficult to obtain.

  Further, in the methods described in JP-A 09-298954 and JP-A 2003-253243, a solution containing colloidal alumina or colloidal silica fine particles and a surfactant is applied to the film surface to provide antifogging properties. Although it is a film that forms a thin film, the anti-fogging effect is manifested initially, but fine particles such as colloidal alumina and colloidal silica that adhere to the film surface with time change easily desorb, so the anti-fogging effect increases with time. There are problems such as lowering.

  In addition, the method described in Japanese Patent Application Laid-Open No. 2003-102288 applies a solution containing colloidal alumina, colloidal silica, a water-soluble resin having an average molecular weight of 100,000 to 4 million, and a nonionic surfactant to the film surface. In the aqueous solution in which the water-soluble resin is dispersed, the zeta potential on the colloidal alumina or colloidal silica particle surface is positive and negative, so do not disperse uniformly. There is a problem that the transparency of the thin film having anti-fogging properties may be reduced.

  Furthermore, in the method described in Japanese Patent Application Laid-Open No. 2004-099694, necklace-shaped colloidal silica is used, but other basic configurations are disclosed in Japanese Patent Application Laid-Open Nos. 09-298954 and 2003-253243. Since they can be regarded as the same, there is a problem in the adhesion of a thin film having antifogging properties, and there is a demand for a composite member having hydrophilicity excellent in antifogging properties and durability.

  The present invention has been made in order to solve such a conventional problem. At least the surface made of a film, a resin plate, a fiber, a cloth, or the like is formed on the surface of a base material made of a resin. An object of the present invention is to provide a composite member that can maintain a clouding effect for a long period of time and has a hydrophilic property with excellent durability.

  As a result of intensive research, the present inventors introduced an unsaturated bond by chemically bonding a silane coupling agent having an unsaturated bond having excellent reactivity to the surface of the inorganic fine particles by a dehydration condensation reaction, and thereby introducing an inorganic bond. By reacting with the unsaturated bonds introduced on the surface of the fine particles or with the surface of the base resin, it becomes possible to maintain a strong antifogging effect on the surface of the base material and excellent durability and hydrophilicity for a long period of time. As a result of obtaining knowledge, a new hydrophilic composite member was created.

That is, the first invention is composed of a substrate having at least a surface made of resin and a first inorganic fine particle having a thin film of a silane monomer having an unsaturated bond formed on the surface, and is bonded to the surface of the first inorganic fine particle. The amount of the silane monomer is 0.001 mass relative to the weight of the first inorganic fine particles.
% To 5.0% by mass, and the resin on the surface of the substrate and the silane monomer thin film formed on the surface of the inorganic fine particles are chemically bonded by radiation graft polymerization, and the first inorganic fine particles are formed on the surface of the substrate. The present invention provides a hydrophilic composite member characterized by comprising a first inorganic fine particle layer fixed to a substrate.

Further, the present invention provides the second inorganic material according to the first invention, wherein a thin film of a silane monomer having an unsaturated bond is formed on the surface, and the second inorganic fine particle is the same or different from the first inorganic fine particles. A fine particle layer is further provided, and the second inorganic fine particle layer includes a thin film of a silane monomer formed on a surface of the first inorganic fine particle of the first inorganic fine particle layer and the second inorganic fine particle layer. A hydrophilic composite member characterized in that a thin film of silane monomer formed on the surface of the inorganic fine particles 2 is chemically bonded by radiation graft polymerization and is laminated and fixed on the first inorganic fine particle layer. It is to provide.

  Furthermore, the present invention provides the composite member according to any one of the first to second inventions, wherein one or more of amino group, carboxylic acid group, sulfonic acid group, and cyanic acid group are formed on the surface of the composite member. The present invention provides a composite member having hydrophilicity, characterized in that these functional groups are bonded.

  Furthermore, the present invention provides a composite member having hydrophilicity according to any one of the first to third inventions, wherein the inorganic fine particles are oxides.

  Furthermore, the present invention provides a hydrophilic composite member according to any one of the first to fourth inventions, wherein the inorganic fine particles are composed of an oxide and a natural radioactive rare element mineral. .

  According to the present invention, there is provided a hydrophilic composite member in which inorganic fine particles are fixed to a substrate having at least a surface made of a resin, and the silane coupling has an unsaturated bond excellent in reactivity with the substrate surface. By chemically bonding the agent to the surface of the inorganic fine particles by a dehydration condensation reaction to introduce unsaturated bonds, and reacting with the unsaturated bonds introduced to the surface of the inorganic fine particles or the base resin surface to immobilize the inorganic fine particles, It becomes possible to maintain the antifogging effect which is strong on the surface of the substrate and excellent in durability and hydrophilicity for a long period of time.

(First embodiment)
Hereinafter, the hydrophilic composite member according to the first embodiment of the present invention will be described in detail.

  FIG. 1 is an enlarged view of a part of a cross section of a hydrophilic composite member 100 according to a first embodiment of the present invention. The hydrophilic composite member 100 of this embodiment is configured by fixing inorganic fine particles 2 on a substrate 1.

  In FIG. 1, an example of the first embodiment of the present invention is schematically illustrated so that the fine particles are formed in one layer. However, a plurality of fine particles are stacked to form a fine particle layer. The fine particles may be chemically bonded to each other.

  As a material constituting the substrate 1 used in the hydrophilic composite member 100 of the present embodiment, any material that can form the chemical bond 5 by the silane coupling agent 3 having an unsaturated bond may be used. Examples of such materials include various resins, synthetic fibers, and natural fibers. Moreover, the base | substrate 1 used for the composite member 100 which has the hydrophilic property of this embodiment should just be that the surface consists of resin at least.

  Here, a synthetic resin or a natural resin is used as the resin constituting the surface or the whole of the substrate 1. For example, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic acid Methyl resin, polyvinyl acetate resin, polyamide resin, polyimide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, polyarylate resin, polysulfone resin, polyvinylidene fluoride resin Thermoplastic resins such as PTFE, polylactic acid resin, polyhydroxybutyrate resin, modified starch resin, polycaprolacto resin, polybutylene succinate resin, polybutylene adipate terephthalate resin, poly Biodegradable resins such as tylene succinate terephthalate resin and polyethylene succinate resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, Thermosetting resins such as silicon resins, acrylic urethane resins, urethane resins, silicone resins, polystyrene elastomers, polyethylene elastomers, polypropylene elastomers, elastomers such as polyurethane elastomers, and natural resins such as lacquer Can be mentioned.

  In the present embodiment, the form of the resin constituting these substrates 1 can be various shapes suitable for the purpose of use, such as plate, film, fiber, cloth, mesh, and honeycomb. A size or the like can be applied and is not particularly limited.

  These resins are laminated in the form of a film on the surface of each material when the main part of the substrate 1 is a metal material such as aluminum, magnesium, or iron, or an inorganic material such as glass or ceramics. Alternatively, it may be formed as a thin film by a coating method such as spray coating, dip coating or electrostatic coating, or a printing method such as screen printing or offset printing.

  Furthermore, these resins may be colored with pigments or dyes, and may be filled with inorganic materials such as silica, alumina, diatomaceous earth, and mica.

  The substrate 1 may be a fiber (synthetic fiber or chemical fiber) made of a synthetic resin. Examples of the synthetic fiber constituting the substrate include polyester fiber, polyamide fiber, polyvinyl alcohol fiber, and acrylic fiber. And vinyl chloride fibers, vinylidene chloride fibers, polyolefin fibers, polycarbonate fibers, fluorine fibers, polyurea fibers, elastomer fibers, and composite fibers of these fibers and the materials constituting these fibers Is mentioned.

  In addition, in the base | substrate 1 of this embodiment, since the base | substrate surface should just be resin as mentioned above, when using fibers other than a synthetic resin for a base | substrate material, resin is applied to the fiber surface by the various coating methods mentioned above. What is necessary is just to form resin as a thin film by painting. Therefore, as examples of natural fibers, cotton, hemp, silk, Japanese paper obtained from natural fibers, and the like can be used as the base material.

As the inorganic fine particles 2 used for the composite member 100 of the present embodiment, high silica zeolite, sodalite, zeolite such as mordenite, analsite, and elinite, apatites such as hydroxyapatite, alumina-silica BaTiO ₃ , PbZrO ₃ , Pb (Zr, Ti) O ₃ , KTaO ₃ , K (Ta, Nb) O ₃ , LiNbO ₃ , TiO ₂ —WO ₃ , AlO ₃ —SiO ₂ and composite oxides such as WO ₃ —ZrO ₂ and WO ₃ —SnO ₂ .

  Further, as the inorganic fine particles 2 used in the present embodiment, silicon oxide as a non-metal oxide, metal oxide, for example, magnesium oxide, barium oxide, barium peroxide, aluminum oxide, tin oxide, Examples thereof include oxides such as titanium oxide, titanium peroxide, zirconium oxide, iron oxide, iron hydroxide, tungsten oxide, bismuth oxide, indium oxide, barium titanium oxide, and cobalt aluminum oxide. The crystallinity of these inorganic fine particles may be either amorphous or crystalline.

  In the composite member of this embodiment, the inorganic fine particles 2 are fixed to the above-described substrate 1 by the chemical bond 5 (black circle portion in the figure) by the silane coupling agent 3 having an unsaturated bond.

  Specific examples of the unsaturated bond of the silane coupling agent 3 include a vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group, and an isocyanate group.

  The composite member of the present embodiment uses the silane coupling agent 3 having excellent reactivity, so that the inorganic fine particles 2 are chemically bonded to the inorganic fine particles 2 by the dehydration condensation reaction of silanol groups of the silane coupling agent 3 and the above. It is a composite member having hydrophilicity bonded to the surface of the substrate by chemical bonding 5 by graft polymerization described later to the resin surface of the substrate 1 of the functional group.

  As an example of the silane coupling agent 3 used in the composite member 100 of the present embodiment, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -Γ-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, , 3-methacryloxypropyltrimethoxysilane N'ya, 3-meth and methacryloxy propyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxysilane, 3-acrylic or trimethoxy silane, and 3-isocyanate propyl triethoxy silane.

  These silane coupling agents 3 are used singly or in combination. As a form of use, a necessary amount of the silane coupling agent 3 is dissolved in an organic solvent such as methanol, ethanol, acetone, toluene, xylene or the like. In addition, hydrochloric acid or mineral acid such as nitric acid is added to improve dispersibility.

  Solvents used include lower alcohols such as ethanol, methanol, propanol and butanol, lower alkyl carboxylic acids such as formic acid and propionic acid, aromatic compounds such as toluene and xylene, ethyl acetate and butyl acetate, etc. Esters and cellosolves such as methyl cellosolve and ethyl cellosolve may be used alone or in combination.

  The inorganic fine particles 2 used in the composite member 100 of the present embodiment are used for manufacturing in a state of being dispersed in the solution of the silane coupling agent 3 described above. The inorganic fine particles 2 are dispersed by stirring and dispersing using a homomixer or a magnetic stirrer, pulverizing / dispersing using a ball mill, sand mill, high-speed rotating mill, jet mill, or the like, or using ultrasonic waves. Is called.

  The inorganic fine particles 2 are used in the production of the composite member 100 having hydrophilicity in the state of a dispersed colloidal dispersion or a dispersion obtained by pulverization. The dispersion of the inorganic fine particles 2 is prepared by adding the silane coupling agent 3 to a colloidal dispersion or a dispersion obtained by pulverization, and then heating the mixture under reflux to heat the silane coupling agent on the surface of the inorganic fine particles 2. 3 is bonded by a dehydration condensation reaction to form a thin film made of the silane coupling agent 3.

  The amount of the silane coupling agent 3 reactively bonded to the inorganic fine particles 2 under reflux depends on the average particle size of the inorganic fine particles 2, but is 0.001% to 5% with respect to the weight of the inorganic fine particles 2 to be reactively bonded. If it is 0.0% by weight, the bond strength of the inorganic fine particles 2 is not problematic in practice. Further, there may be an excess of silane coupling agent 3 that is not deposited in the bond.

  In particular, when the inorganic fine particle layer 10 (first inorganic fine particle layer) made of the inorganic fine particles 2 is thick, the inorganic fine particle layer 10 may be deteriorated due to cohesive failure depending on the stress of the inorganic fine particle layer 10 or the use environment. As necessary after treatment, a silane coupling agent having an unsaturated bond, an alkoxysilane compound represented by Si (OR1) 4 (wherein R1 represents an alkyl group having 1 to 4 carbon atoms), Tetramethoxysilane, tetraethoxysilane, etc., R2nSi (OR3) 4-n (wherein R2 is a hydrocarbon group having 1 to 6 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and n is 1 to 3) As an example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyl In addition to this, alkoxy oligomers and the like such as disilazane and hexyltrimethoxysilane are added.

  Next, a method of chemically bonding the substrate 1 and a solution in which the inorganic fine particles 2 and the coupling agent 3 are mixed will be described. In the present embodiment, as a method for chemically bonding the substrate 1 and the inorganic fine particles 2, a bonding method by graft polymerization is used.

  Examples of the graft polymerization in the composite member 100 of the present embodiment include graft polymerization using a peroxide catalyst, graft polymerization using heat and light energy, and graft polymerization by radiation (radiation graft polymerization).

  Of these, radiation graft polymerization is particularly suitable from the viewpoints of simplicity of the polymerization process and production speed. Here, examples of the radiation used in the graft polymerization include α rays, β rays, γ rays, electron beams, ultraviolet rays, and the like. Lines and ultraviolet rays are particularly suitable.

  The manufacturing method of the composite member 100 having hydrophilicity using graft polymerization in the present embodiment is preferably manufactured by the method described below.

  As a first preferred method in the present embodiment, a solution in which inorganic fine particles 2 to which a silane coupling agent 3 is bonded is dispersed is applied to the surface (resin surface) of the substrate 1 to be bonded, and if necessary After removing the solvent by a method such as heat drying, the surface of the substrate 1 on which the inorganic fine particles 2 bound with the silane coupling agent 3 are applied is irradiated with radiation such as γ rays, electron beams, or ultraviolet rays. Thus, it is produced by so-called simultaneous irradiation graft polymerization in which the silane coupling agent 3 is graft-polymerized on the surface of the substrate 1 and the inorganic fine particles 2 are bonded at the same time.

  In addition, as a second preferred method in the present embodiment, the surface of the substrate 1 is irradiated with radiation such as γ rays, electron beams, or ultraviolet rays in advance, and then the inorganic fine particles 2 to which the silane coupling agent 3 is bonded. It is produced by so-called pre-irradiation graft polymerization in which a solution in which is dispersed is applied, the silane coupling agent 3 and the substrate 1 are reacted, and the inorganic fine particles 2 are bonded at the same time.

  In this embodiment, as described above, the composite member is manufactured by applying the solution in which the inorganic fine particles 2 to be immobilized are dispersed to the surface of the substrate 1 to be immobilized.

  As a specific method for applying the dispersion liquid of the inorganic fine particles 2, generally used spin coating method, dip coating method, spray coating method, cast coating method, bar coating method, micro gravure coating method, Various methods such as screen printing, pad printing, offset printing, dry offset printing, flexographic printing, and inkjet printing can be used as gravure coating methods or partial coating methods. There is no particular limitation as long as it can be used and can be applied according to the purpose.

  In order to perform graft polymerization of the silane coupling agent 3 efficiently and uniformly, the surface of the substrate 1 is previously subjected to corona discharge treatment, plasma discharge treatment, flame treatment, chromic acid or perchlorine. Hydrophilic treatment may be performed by chemical treatment with an aqueous solution of an oxidizing acid such as an acid or an alkaline aqueous solution containing sodium hydroxide.

  As described above, according to the composite member 100 of the first embodiment of the present invention, the composite member 100 having a hydrophilic property in which the inorganic fine particles 2 are fixed to the base 1 made of resin at least on the surface. The surface of the inorganic fine particles 2 is introduced by chemically bonding the silane coupling agent 3 having an unsaturated bond with excellent reactivity to the surface of the inorganic fine particles 2 by dehydration condensation reaction to the surface of the inorganic fine particles 2. By fixing the inorganic fine particles 2 by reacting with the unsaturated bonds introduced into the resin or the resin surface of the substrate 1, the antifogging effect is strong on the surface of the substrate 1 and has excellent durability and hydrophilicity. The period can be maintained.

  Further, according to the present embodiment, since the inorganic fine particles 2 can be firmly fixed on the substrate 1 by the chemical bond 5, it can be performed after forming into a product shape after spinning or in the process of commercialization. For this reason, there exists a merit that presence of the inorganic fine particle 2 which has various functions does not affect spinnability.

Further, since the inorganic fine particles 2 can be formed in a single particle film shape or a multilayer particle film shape on a substrate made of a film, a resin plate, a fiber, a cloth, or the like, since the texture of these substrates is not impaired, It becomes possible to provide a composite member having hydrophilicity that can be applied.
(Second Embodiment)
Next, the hydrophilic composite member of the second embodiment of the present invention will be described in detail.

  FIG. 2 is an enlarged view of a part of a cross section of the hydrophilic composite member 200 according to the second embodiment of the present invention. The hydrophilic composite member 200 of the present embodiment has an inorganic fine particle layer 30 (second inorganic particle) made of new inorganic fine particles 2b on a coating film 20 (first inorganic fine particle layer) formed of inorganic fine particles 2a. The fine particle layer is different from the composite member 100 of the first embodiment. That is, it has a form of a laminated structure in which a plurality of the same or different inorganic fine particle layers 30 are formed on the surface of the inorganic fine particle layer 10 formed in the first embodiment by a chemical reaction.

The fine particles 2b forming the inorganic fine particle layer 30 are high silica zeolite, sodalite, mordenite, zeolites such as analsite and elinite, apatites such as hydroxyapatite, alumina-silica, and BaTiO _3. PbZrO ₃ , Pb (Zr, Ti) O ₃ , KTaO ₃ , K (Ta, Nb) O ₃ , LiNbO ₃ , TiO ₂ —WO ₃ , AlO ₃ —SiO ₂ , WO ₃ -ZrO ₂ and _composite oxides such as WO 3 -SnO _2, also, silicon oxide as a non-metal oxide, a metal oxide, for example, magnesium oxide, and barium oxide, and barium peroxide, and aluminum oxide, Tin oxide, titanium oxide, titanium peroxide, zirconium oxide, iron oxide, iron hydroxide, tungsten oxide, It may be a mixture of one or more selected from oxides such as mass, indium oxide, titanium barium oxide, and cobalt aluminum oxide, and these fine particles and, for example, a material that exhibits a photocatalytic function, antibacterial It is also possible to mix a material having a property, a material that emits negative ions, a material that emits far infrared rays, a material that has antireflection properties, a material that absorbs near infrared rays, or the like.

  Note that FIG. 2 schematically shows an example of the second embodiment of the present invention in an easy-to-understand manner. In FIG. 2, the fine particles are formed as a single layer. As in the case of FIG. 1, the fine particles may be chemically bonded to each other.

  Hereinafter, the manufacturing method and the configuration of the composite member, which are different from the composite member 100 of the first embodiment, will be described. In addition, regarding the base material, the material of the fine particles, and the manufacturing method, the description of the points common to the composite member 100 of the first embodiment is omitted.

  In the composite member 200 of the present embodiment, as a suitable method for bonding the substrate 1, the coating film 20 made of the inorganic fine particles 2a, and the inorganic fine particle layer 30 made of the inorganic fine particles 2b, an inorganic material to which the silane coupling agent 3 is bonded. After the solution in which the fine particles 2a are dispersed is applied to the surface (resin surface) of the substrate 1, the solvent is removed by a method such as heat drying as necessary to form the coating thin film 20 made of fine particles, and then the inorganic fine particles 2a described above. In order to form a thin film of a silane coupling agent on the same or different kind of fine particles 2b, a solution in which the inorganic fine particles 2b are dispersed is applied on the surface of the coating thin film 20 to form a new inorganic fine particle layer 30. Then, by irradiating with radiation, the coating thin film 20 formed of the inorganic fine particles 2a, the substrate 1, and the inorganic fine particles 2 Produced by the process of bonding by graft-polymerizing at a time and a silane coupling agent 3 formed the same or different inorganic particulate 2b and.

  Even in this case, the coating film 20 is applied to the surface of the substrate 1 and then the surface of the substrate 1 is irradiated with radiation so that the coating film 20 is bonded to the surface of the substrate 11 via the silane coupling agent 3 by graft polymerization. Then, by forming the same or different inorganic fine particle layer 30 as the inorganic fine particles 2a, it is possible to manufacture a stronger laminated fine particle fixed body.

  In addition, as a method for forming the coating film 20, it is also possible to employ the pre-irradiation used in the second method in the first embodiment of the present invention.

As described above, according to the hydrophilic composite member 200 of the second embodiment of the present invention, in addition to the effects of the composite member 100 of the first embodiment, the coating film 20 is bonded to the surface of the substrate 1. Then, by forming an inorganic fine particle layer 30 of the same kind or different kind from the fine particles, it is possible to manufacture a stronger laminated composite member.
(Third embodiment)
Next, the composite member having hydrophilicity according to the third embodiment of the present invention will be described in detail.

  FIG. 3 is an enlarged view of a part of the cross section of the hydrophilic composite member 300 according to the third embodiment of the present invention. The composite member 300 having hydrophilicity in the present embodiment has a functional group bonded to the surface of the composite member in the first and second embodiments.

  Note that FIG. 3 schematically shows an example of the third embodiment of the present invention in an easy-to-understand manner. In FIG. 3, the fine particles are formed as a single layer. However, a plurality of fine particles are overlapped to form a fine particle layer 40. The fine particles may be chemically bonded to each other as in the case of FIG.

  Hereinafter, the manufacturing method of the composite member of this embodiment and the structure of the composite member will be described. In addition, regarding the base material, the material of fine particles, and the manufacturing method, the description of the points in common with the composite member of each of the above embodiments is omitted.

  In the composite member 300 of the present embodiment, one or two of at least an amino group, a carboxylic acid group, a sulfonic acid group, and a cyanic acid group are formed on the surface of the inorganic fine particle layer 40 of the hydrophilic composite member 300. The above functional groups 4 are bonded. In FIG. 3, carboxylic acid groups are shown as representatives.

  To introduce an amino group, 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl A silane coupling agent 3 containing an amino group such as trimethoxysilane and hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane is used.

  As the carboxylic acid group, methacrylic acid or a monofunctional monomer having a carboxylic acid group such as 2-methacryloyloxyethyl succinic acid is used.

  As the sulfonic acid group, aliphatic sulfonic acids such as sulfomaleic acid, sulfosuccinic acid and sulfofumaric acid, and aromatic sulfonic acids such as sulfophthalic acid and sulfosalicylic acid are used. As the cyanate group, trichlorocyanoethylsilane is used.

As described above, according to the composite member 300 of the third embodiment of the present invention, in addition to the effects of the composite member of each of the above embodiments, the hydrophilic composite member to which the inorganic fine particles 2 are immobilized is provided. Since at least one functional group 4 of amino group, carboxylic acid group, sulfonic acid group, and cyanic acid group is bonded to at least the surface, the contact angle with water on the surface is 10 ° or less. It is super hydrophilic, and even if a rapid temperature difference occurs in a high humidity environment, the surface of the optical lens or automobile window glass is hardly clouded by water droplets, and the member has a hydrophilic property with extremely excellent antifogging properties. Can be provided.
(Fourth embodiment)
Next, the hydrophilic composite member of the fourth embodiment of the present invention will be described in detail. The hydrophilic composite member of the present embodiment is one in which a natural radioactive rare element mineral is contained in the inorganic fine particles 2 of the composite member of the first to third embodiments.

  Natural radioactive rare element minerals containing trace amounts of radioactive rare elements include, for example, dabitite, senurite, blannelite, gingko stone, linca uranium, carnotite, tchaumite, metachamunite, Franceville stone, Tall stone, Coffin stone, Samarsky stone, Thorium stone, Trogam stone, Samarsky stone, Thorium stone, Trogam stone, Monazite, Tantalum stone, Baderite, Ilmenite, etc. Is mentioned. Moreover, electrofused zirconia obtained by refining a part of these minerals can be used.

  Moreover, in order to reduce the usage-amount of a natural radioactive rare element mineral, the material etc. which have spontaneous polarization, such as tourmaline, may be contained.

  In addition, although it does not specifically limit about the diameter of the inorganic fine particle 2, In order to perform graft polymerization suitably, it is preferable that an average particle diameter shall be 500 nm or less. Furthermore, if the average particle size is 300 nm or less, stronger bonding to the substrate 1 is achieved, which is more preferable from the viewpoint of durability.

  According to the composite member of the fourth embodiment of the present invention, in addition to the effects of the composite member of each of the above embodiments, a natural radioactive rare element mineral in which a part or all of the inorganic fine particles 2 contains a trace amount of a radioactive rare element is provided. Because it is used, active oxygen such as superoxide anion, hydroxy radical, and singlet oxygen is generated by the ionizing action of α-rays emitted by trace amounts of radioactive rare elements contained in natural radioactive rare element minerals. Oxygen promotes hydrophilicity and also has the effect of degrading organic substances adhering to the surface and suppressing the decrease in hydrophilicity over time, so the contact angle with water becomes 10 ° or less, and super hydrophilicity And the composite member which has the hydrophilicity provided with the outstanding anti-fogging property and the self-purification function can be provided.

  As described above, according to each embodiment of the present invention, a hydrophilic composite member in which inorganic fine particles are fixed to a substrate having at least a surface made of resin, which is reactive to the substrate surface. A silane coupling agent having an excellent unsaturated bond is chemically bonded to the surface of the inorganic fine particles by a dehydration condensation reaction to introduce unsaturated bonds, and reacts with the unsaturated bonds introduced on the surface of the inorganic fine particles or with the substrate resin surface. By fixing the inorganic fine particles, the antifogging effect having excellent durability and hydrophilicity can be maintained for a long time on the surface of the substrate.

  In each embodiment of the present invention, the substrate may be in various forms (shape, size, etc.) suitable for the purpose of use, such as film, fiber, cloth, mesh, and honeycomb. Is possible. Therefore, it becomes possible to add hydrophilic functions to various substrates in various forms, such as agricultural materials such as house films and tunnel house films, food packaging materials, outer wall materials, sashes, doors, blinds, etc. Interior materials such as building materials, wallpaper, carpets, resin tiles, clothing, innerwear, socks, gloves, shoes, etc., insoles for the footwear, pajamas, mats, sheets, pillows, pillowcases, blankets, towels Application to bedding materials such as cocoons and cocoon covers, hats, handkerchiefs, towels, carpets, curtains, air purifiers and air conditioners, ventilation fans, vacuum cleaners, fan filters, etc. or insect nets and screen printing meshes Is possible. Therefore, the present invention is a useful member that can provide various products excellent in various fields.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

  In the production of the fixed microparticles of the following Examples 1 to 3 according to the method of the present invention, an electron curtain type electron beam irradiation device, CB250 / 15 / 180L, manufactured by Iwasaki Electric Co., Ltd. Carried out. On the other hand, in the production of the hydrophilic composite member of each comparative example, an electron beam was not used, and a post-application heating and drying method was used.

Example 1
3-Methacryloxypropylmethyldiethoxysilane (Shin-Etsu Chemical Co., Ltd.) having an unsaturated bond in a methanol solution (MA-ST-S manufactured by Nissan Chemical Industries, Ltd.) in which silica fine particles having an average particle diameter of 10 nm are dispersed by 10% by weight. Manufactured by KBE-502), 0.05% by weight based on silica fine particles, and then transferred to a flask equipped with a condenser. After that, the flask was heated in an oil bath and treated under reflux for 3 hours. A silane coupling agent was bonded to the surface of the fine particles by a dehydration condensation reaction.

  And the silica fine particle dispersion | distribution methanol solution which the said silane coupling agent couple | bonded was apply | coated to the surface of a 125 micrometer polyester film (the Panac Co., Ltd. make, Lumirror) with the bar coater, and it dried at 120 degreeC for 3 minutes.

  Next, the polyester film coated with the methanol solution and dried is irradiated with an electron beam at an acceleration voltage of 200 kV for 3 Mrad, so that the silica fine particles are bonded to the polyester film surface by graft polymerization of a silane coupling agent. A composite member having was obtained.

(Example 2)
Instead of the silane coupling agent used in Example 1, a silane coupling agent having two functional groups, a vinyl group and an amino group, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxy A hydrophilic composite member was obtained under the same conditions as in Example 1 except that silane hydrochloride (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

(Example 3)
3-Aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent having an amino group in a silica fine particle-dispersed methanol solution bonded with 3-methacryloxypropylmethyldiethoxysilane used in Example 1. A composite member having hydrophilicity was obtained under the same conditions as in Example 1 except that 3.0 wt% of KBM-903) was added to the solid content.

(Example 4)
A hydrophilic composite member was obtained under the same conditions as in Example 1 except that methacrylic acid was used instead of the silane coupling agent having an amino group used in Example 3.

(Example 5)
A composite member having hydrophilicity was obtained under the same conditions as in Example 1 except that sulfomaleic acid was used in place of the silane coupling agent having an amino group used in Example 4.

(Example 6)
A mixture of fine particles of tourmaline, which is a natural mineral, and fine particles of ilmenite, which is a natural radioactive rare element mineral (manufactured by Nakazatoya Co., Ltd.), was pulverized and dispersed in a bead mill for 3 hours with a bead mill. Next, an ilmenite-dispersed methanol solution in which 3-acryloxypropyltriethoxysilane having an unsaturated bond (KBE-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was pulverized and dispersed was added in an amount of 0.5% by weight based on the solid content. After that, it was transferred to a flask equipped with a cooling tube, and then the flask was heated in an oil bath and treated under reflux for 3 hours to bond the silane coupling agent to the surface of the pulverized and dispersed tourmaline and ilmenite fine particles by a dehydration condensation reaction. I let you.

  Moreover, the said process liquid was apply | coated with the bar coater on the surface of a 125 micrometer polyester film (the Panac Co., Ltd. make, Lumirror), and it dried at 120 degreeC for 3 minutes. Next, the polyester film that had been coated with the treatment liquid and dried was irradiated with an electron beam at an acceleration voltage of 200 kV for 3 Mrad to obtain a composite member having hydrophilicity.

(Example 7)
A methanol solution in which 10% by weight of ilmenite fine particles (manufactured by Nakazatoya Co., Ltd.), a natural radioactive rare element mineral, was dispersed was pulverized and dispersed in a bead mill for 3 hours. Next, an ilmenite-dispersed methanol solution in which 3-methacryloxypropyltrimethoxysilane having an unsaturated bond (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was pulverized and dispersed was added in an amount of 0.1% by weight based on the solid content. After that, it was transferred to a flask equipped with a cooling pipe, and then the flask was heated in an oil bath and treated under reflux for 3 hours, thereby binding the silane coupling agent to the surface of the pulverized and dispersed ilmenite fine particles by a dehydration condensation reaction. .

  In addition, a methanol solution in which 10 wt% of ultrafine titanium oxide (Ishihara Sangyo Co., Ltd., TTO-S-1) was dispersed was pulverized and dispersed in a bead mill for 3 hours. Next, an ilmenite-dispersed methanol solution in which 3-methacryloxypropyltrimethoxysilane having an unsaturated bond (KBE-503, manufactured by Shin-Etsu Chemical Co., Ltd.) is pulverized and dispersed is added in an amount of 0.1% by weight based on the solid content. After that, it is transferred to a flask equipped with a cooling tube, and then the flask is heated in an oil bath and treated under reflux for 3 hours to dehydrate and condense the silane coupling agent on the surface of the pulverized and dispersed ultrafine titanium oxide. Were combined. The ilmenite-dispersed methanol solution combined with the obtained silane coupling agent and the ultrafine titanium oxide methanol solution were mixed at a weight ratio of 1: 1 to obtain a treatment solution.

  Moreover, the said process liquid was apply | coated with the bar coater on the surface of a 125 micrometer polyester film (the Panac Co., Ltd. make, Lumirror), and it dried at 120 degreeC for 3 minutes. Next, the polyester film that had been coated with the treatment liquid and dried was irradiated with an electron beam at an acceleration voltage of 200 kV for 3 Mrad to obtain a composite member having hydrophilicity.

(Example 8)
A silane coupling agent having an amino group, 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) used in Example 7 was added in an amount of 2.0% by weight based on the solid content. A composite member having hydrophilicity was obtained under the same conditions as in Example 7 except that.

Example 9
A hydrophilic composite member was obtained under the same conditions as in Example 7 except that methacrylic acid was used instead of the silane coupling agent having an amino group used in Example 8.

(Example 10)
A composite member having hydrophilicity was obtained under the same conditions as in Example 7 except that sulfomaleic acid was used instead of the silane coupling agent having an amino group used in Example 8.

(Comparative Example 1)
The silica fine particle-dispersed methanol solution used in Example 1 was applied to the surface of the polyester film used in Example 1 using a bar coater and then dried at 120 ° C. for 3 minutes to form a thin film of silica fine particles. A member was obtained.

(Comparative Example 2)
After applying the pulverized and dispersed methanol solution of tourmaline, which is a natural mineral used in Example 6, and ilmenite, which is a natural radioactive rare element mineral, to the polyester film surface used in Example 1 using a bar coater, The composite member which formed the thin film which consists of a fine particle of tourmaline and ilmenite was obtained by drying at 120 ° C. for 3 minutes.

(Comparative Example 3)
Comparative Example 1 except that 0.2% by weight of a polyether-modified silicone oil (LL-77 manufactured by Nihon Unicar Co., Ltd.), which is a nonionic surfactant, was added to the silica fine particle-dispersed methanol solution used in Comparative Example 1. A composite member in which a thin film of silica fine particles was formed under the conditions was obtained.

(Evaluation of hydrophilic composite member)
The durability is obtained by immersing the obtained composite member having hydrophilicity in methanol and irradiating with ultrasonic waves for 1 hour. The surface before and after the ultrasonic irradiation is scanned with a scanning electron microscope, and the hydrophilicity in which a thin film of fine particles is formed. The surface state of the thin film was observed.

In addition, the hydrophilicity is evaluated by immersing the composite member in methanol and using ultrasonically washed for 1 hour before and after ultrasonic cleaning on the surface of the obtained composite member using a solid-liquid interface analyzer DropMaster300 manufactured by Kyowa Interface Science Co., Ltd. Was added dropwise, and the contact angle of the formed water droplets was measured. These measurement results are shown in Table 1.

本発明で得られた親水性を有する複合部材は、実施例１〜１０の結果が示すように、得られた複合部材をアルコールに浸漬して超音波を長時間照射しても、親水性を有する薄膜の剥離は認められず、また、水に対する接触角は、その殆どが１０°以下と、超親水性を有していることを確認した。さらに、超音波洗浄後も水に対する接触角は殆ど変化していないことから、耐久性に優れていることが実証された。

As shown in the results of Examples 1 to 10, the composite member having hydrophilicity obtained in the present invention exhibits hydrophilicity even when the obtained composite member is immersed in alcohol and irradiated with ultrasonic waves for a long time. Peeling of the thin film was not recognized, and the contact angle with water was almost 10 ° or less, and it was confirmed that the film had super hydrophilicity. Furthermore, since the contact angle with respect to water hardly changed even after ultrasonic cleaning, it was proved to be excellent in durability.

  In contrast to these results, it was confirmed that in the composite member obtained in the comparative example, when the composite member was immersed in alcohol and irradiated with ultrasonic waves, most of the thin film formed on the film surface was peeled off. Furthermore, since the contact angle with water on the surface is not high, it was confirmed that the durability was poor.

It is sectional drawing of the composite member which has the hydrophilic property of 1st Embodiment of this invention. It is sectional drawing of the composite member which has hydrophilic property of 2nd Embodiment of this invention. It is sectional drawing of the composite member which has hydrophilic property of 3rd Embodiment of this invention.

Explanation of symbols

1: Substrate 2: Inorganic fine particle 3: Silane coupling agent 5: Chemical bond 10: Inorganic fine particle layer 100: Composite member

Claims (5)

A substrate having at least a surface made of resin;
The thin film of silane monomer having an unsaturated bond is composed of first inorganic fine particles formed on the surface, and the amount of the silane monomer to be bonded to the surface of the first inorganic fine particles is based on the weight of the first inorganic fine particles. 0.001% to 5.0% by weight,
A resin on the surface of the substrate and a thin film of a silane monomer formed on the surface of the inorganic fine particles are chemically bonded by radiation graft polymerization, and the first inorganic fine particles are fixed to the surface of the substrate. A hydrophilic composite member comprising: an inorganic fine particle layer. A thin layer of a silane monomer having an unsaturated bond is formed on the surface, further comprising a second inorganic fine particle layer composed of second inorganic fine particles of the same kind or different from the first inorganic fine particles,
The second inorganic fine particle layer includes a silane monomer thin film formed on a surface of the first inorganic fine particle of the first inorganic fine particle layer and a surface of the second inorganic fine particle of the second inorganic fine particle layer. 2. The hydrophilic composite member according to claim 1, wherein the thin film of the silane monomer is chemically bonded by radiation graft polymerization, and is laminated and fixed on the first inorganic fine particle layer. The surface of the composite member is formed by bonding one or two or more functional groups of amino group, carboxylic acid group, sulfonic acid group, or cyanic acid group. A composite member having hydrophilic properties. The hydrophilic composite member according to claim 1, wherein the inorganic fine particles are oxides. The hydrophilic composite member according to any one of claims 1 to 3, wherein the inorganic fine particles are made of a mixture of an oxide and a natural radioactive rare element mineral.

Images