WO2012161330A1 - Article antibuée et son procédé de production - Google Patents

Article antibuée et son procédé de production Download PDF

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Publication number
WO2012161330A1
WO2012161330A1 PCT/JP2012/063553 JP2012063553W WO2012161330A1 WO 2012161330 A1 WO2012161330 A1 WO 2012161330A1 JP 2012063553 W JP2012063553 W JP 2012063553W WO 2012161330 A1 WO2012161330 A1 WO 2012161330A1
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Prior art keywords
water
absorbing layer
antifogging
fine particles
polyepoxide
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PCT/JP2012/063553
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English (en)
Japanese (ja)
Inventor
森　勇介
知子 岸川
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旭硝子株式会社
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Publication of WO2012161330A1 publication Critical patent/WO2012161330A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2290/00—Compositions for creating anti-fogging

Definitions

  • the present invention relates to an antifogging article and a manufacturing method thereof.
  • Transparent substrates such as glass and plastic have a so-called “cloudy” state when the substrate surface falls below the dew point temperature because fine water droplets adhere to the surface and scatter transmitted light. .
  • Various proposals have been made as a means for preventing fogging. Specifically, a method of providing a water-absorbing resin layer on the substrate surface and absorbing and removing minute water droplets formed on the substrate surface, or reducing the atmospheric humidity on the substrate surface, and the like are known.
  • an anti-fogging article including a water-absorbing crosslinked resin layer obtained from polyepoxides has been proposed.
  • Patent Document 1 an anti-fogging article including a water-absorbing crosslinked resin layer obtained from polyepoxides.
  • scratch resistance such as scratch resistance although it is excellent in antifogging property.
  • An object of the present invention is to provide an antifogging article having excellent antifogging property, scratch resistance such as scratch resistance and low initial fog value, and a method for producing the same.
  • the present invention provides an antifogging article having the following configurations [1] to [10].
  • An antifogging article having a substrate and a water-absorbing layer containing a water-absorbing crosslinked resin provided on the surface of the substrate, wherein the water-absorbing layer contains 20 to 60% by mass of metal oxide fine particles.
  • An antifogging article characterized by being contained in a proportion and having a haze value of 1% or less.
  • the antifogging according to any one of [1] to [4], wherein an antifogging time is 90 seconds or more in an antifogging test in which a time until a perspective image distortion due to a water film is recognized is measured as an antifogging time. Sex goods.
  • the antifogging article according to any one of [1] to [7], wherein the metal oxide fine particles have an average primary particle diameter of 10 to 50 nm.
  • cross-linked resin is a cured epoxy resin obtained by a reaction between a polyepoxide and a curing agent, or a urethane resin obtained by a reaction between a polyisocyanate and a polyol.
  • the present invention also provides a method for producing an antifogging article having the following configurations [11] to [15].
  • a method for producing an antifogging article comprising a substrate and a water absorbing layer containing a water-absorbing crosslinked resin and metal oxide fine particles provided on the surface of the substrate, Adding a part of the content of the metal oxide fine particles to the liquid composition containing the raw material component of the crosslinked resin (1), A step (2) of proceeding a crosslinking reaction of the liquid composition obtained by the step (1); Adding the remainder of the content of the metal oxide fine particles to the liquid composition obtained by the step (2) (3); and Applying the water-absorbing layer-forming composition obtained in the step (3) to the surface of the substrate and further causing a crosslinking reaction to form a water-absorbing layer;
  • a method for producing an antifogging article wherein the water absorbing layer contains the metal oxide fine particles in a proportion of 20 to 60% by mass.
  • the anti-fogging article of the present invention is excellent in anti-fogging property, scratch resistance such as scratch resistance, and low initial fog value. Moreover, according to the production method of the present invention, an antifogging article having excellent antifogging properties and scratch resistance and having a sufficiently low initial haze value can be obtained.
  • the antifogging article of the present invention is an antifogging article having a base and a water absorbing layer containing a crosslinked resin provided on the surface of the base, wherein the water absorbing layer contains 20 to 60 metal oxide fine particles. It contains in the ratio of the mass%, and a haze is 1% or less, It is characterized by the above-mentioned.
  • the haze value [%] means the haze value [%] measured using a haze meter in accordance with the standard of JIS K-7361 unless otherwise specified.
  • the antifogging article having a substrate and a water-absorbing layer containing a crosslinked resin provided on the surface of the substrate of the present invention a high content ratio of 20 to 60% by mass of metal oxide fine particles in the water-absorbing layer Exists.
  • the metal oxide fine particles present at a high content ratio in the water absorption layer have a low haze value of 1% or less by being uniformly dispersed throughout the water absorption layer. It becomes possible.
  • the water-absorbing layer containing the crosslinked resin provided on the surface of the substrate contains the metal oxide fine particles uniformly at the high content, so that the antifogging article of the present invention has an anti-fogging property as described below. It has excellent fog resistance and scratch resistance such as scratch resistance.
  • the specimen that is, the specimen of the antifogging article
  • the antifogging time is 90 seconds or more in the antifogging test in which the time until the distortion of the fluoroscopic image due to cloudiness or a water film is observed when the sample surface is placed on a 40 ° C. hot water bath is measured as the antifogging time.
  • the material constituting the water absorbing layer preferably has a saturated water absorption amount of 50 mg / cm 3 or more.
  • the film thickness of the water absorbing layer is preferably 7 ⁇ m to 30 ⁇ m.
  • a water absorbing layer as a specimen is provided on a soda lime glass substrate having a size of 3.3 cm ⁇ 10 cm ⁇ 2 mm, and this is left for 1 hour in an environment of 20 ° C. and a relative humidity of 50%.
  • the time until fogging or distortion of a fluoroscopic image due to a water film is observed when the image is hung up is measured, and this time is taken as the antifogging time. Note that the determination of the occurrence of perspective image distortion due to cloudiness or a water film is made visually.
  • the saturated water absorption amount is a 3 cm ⁇ 4 cm ⁇ 2 mm thick soda lime glass substrate provided with a water absorption layer as a specimen, which is immersed in distilled water at 25 ° C. for 10 minutes, so that excessive water cannot be discriminated visually. It wipes off with a Kim towel and measures the moisture content (I) of the whole base
  • a value obtained by dividing a value obtained by subtracting the amount of water (II) from the amount of water (I) by the volume of the water-absorbing layer is defined as a saturated water-absorbing amount of the material constituting the water-absorbing layer.
  • the water content is measured with a trace moisture meter FM-300 (manufactured by Kett Science Laboratory) as follows. The measurement sample is heated at 120 ° C., the moisture released from the sample is adsorbed to the molecular sieve in the micro moisture meter, and the mass change of the molecular sieve is measured as the moisture content. The measurement is performed for the same time as the blank measurement, and the maximum value during that time is adopted as the moisture content.
  • the anti-fogging time is an index indicating the anti-fogging property of the water-absorbing layer itself depending on the material constituting the water-absorbing layer and the layer thickness, but the saturated water absorption is an index indicating the anti-fogging property of the material constituting the water-absorbing layer.
  • the antifogging property of the water absorbing layer is evaluated together with the thickness of the layer.
  • the anti-fogging time in the water-absorbing layer of the anti-fogging article of the present invention is 90 seconds or more, the anti-fogging property of the water-absorbing layer can be said to be sufficient, but the anti-fogging time of the water-absorbing layer is preferably 100 seconds or more. .
  • the upper limit of the antifogging time is not particularly set, in a water absorbing layer having an antifogging time exceeding 200 seconds, there is a possibility that the mechanical strength is not sufficient at the time of water absorption due to containing a large amount of water.
  • the saturated water absorption amount of the material constituting the water absorption layer is 50 mg / cm 3 or more, and if the water absorption layer has a film thickness of 7 ⁇ m to 30 ⁇ m, the water absorption layer is sufficient. Although it can be said that it has a good anti-fogging property, it is preferable that the saturated water absorption is 60 mg / cm 3 or more under the same film thickness conditions.
  • the upper limit of the saturated water absorption amount is not particularly set as in the anti-fogging time. However, in the water absorption layer containing a crosslinked resin having a saturated water absorption amount exceeding 150 mg / cm 3 , the machine absorbs a large amount of water. Strength may be insufficient.
  • the film thickness range of the water absorbing layer is preferably 7 to 25 ⁇ m and more preferably 7 to 20 ⁇ m from the viewpoint of securing adhesion.
  • the antifogging article of the present invention may be evaluated by any antifogging index of the antifogging time or a combination of saturated water absorption and film thickness.
  • the use of antifogging articles is diverse, and the antifogging performance required varies depending on the use, but within the range of antifogging properties of the antifogging article of the present invention, it is required for antifogging articles for each use.
  • the design can be changed as appropriate according to the performance.
  • the water absorption layer containing a crosslinked resin provided on the surface of the substrate has, in addition to the above water absorption and antifogging properties, the surface mechanical strength, particularly scratch resistance,
  • the Martens Hardness measured under the following measurement conditions is preferably 20 N / mm 2 or more.
  • the “hardness” of a thin film such as a water absorption layer containing a crosslinked resin provided on the surface of the substrate of the antifogging article of the present invention, that is, when determining the mechanical strength such as scratch resistance
  • a microhardness measurement test for measuring the Martens hardness corresponding to the scratch resistance for calculating the hardness from the penetration depth of the indenter under a constant load condition on the measurement surface is used.
  • the Martens hardness in the water absorption layer of the antifogging article of the present invention if the value in the above measurement condition is 20 N / mm 2 or more, it can be said that the scratch resistance of the water absorption layer is sufficient, but the water absorption layer in the same measurement condition.
  • the Martens hardness is preferably 30 N / mm 2 or more.
  • the upper limit of the Martens hardness is not particularly set, but in a water absorbing layer having a Martens hardness exceeding 200 N / mm 2 or more, there is a risk of deterioration in appearance such as cracking or whitening.
  • Martens hardness means the Martens hardness in the said measurement conditions unless there is particular notice.
  • the antifogging article of the present invention has excellent antifogging properties and scratch resistance as described above in a water-absorbing layer containing a crosslinked resin provided on the substrate surface. Furthermore, the antifogging article of the present invention is allowed to stand for 1 hour in an environment of 20 ° C. and 50% relative humidity, which is an index indicating hydrophobicity, on the surface of the water-absorbing layer containing a crosslinked resin provided on the surface of the substrate.
  • the water contact angle immediately after dropping 2 ⁇ L of water droplets is preferably 40 to 100 °, and within this range, it is advantageous in terms of the recovery speed of visibility.
  • the water absorption layer of the antifogging article of the present invention is measured in the DFM mode using a scanning probe microscope (SPM, SPA-400, SII Nanotechnology Co., Ltd.) that exhibits surface flatness.
  • SPM scanning probe microscope
  • SPA-400 SII Nanotechnology Co., Ltd.
  • a smaller surface roughness (Ra) is preferable in terms of ensuring transparency.
  • the water absorption layer has a specific configuration, specifically, the water absorption layer contains metal oxide fine particles together with a crosslinked resin, and the content of the metal oxide fine particles in the water absorption layer is By setting the ratio to 20 to 60% by mass, the water absorption layer can have the above characteristics.
  • members constituting the antifogging article of the present invention will be described.
  • Substrate The substrate used in the antifogging article of the present invention is not particularly limited as long as it is a substrate made of a material that is generally required to be imparted with antifogging properties, but is preferably glass, plastic, or metal. , Ceramics, or a substrate made of a combination thereof (for example, composite material, laminated material, etc.), more preferably, a transparent substrate made of glass or plastic, a mirror, and the like.
  • the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable.
  • plastic examples include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET). Among these, polyethylene terephthalate (PET) ) And polyphenylene carbonate are preferred.
  • acrylic resins such as polymethyl methacrylate
  • aromatic polycarbonate resins such as polyphenylene carbonate
  • aromatic polyester resins such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • PET polyphenylene carbonate
  • the shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature.
  • the thickness of the substrate can be appropriately selected depending on the use of the antifogging article, but is generally preferably 1 to 10 mm.
  • the water-absorbing layer formed on at least a part of the surface of the base contains metal oxide fine particles together with the crosslinked resin.
  • the content is 20 to 60% by mass of the entire water-absorbing layer.
  • the cross-linked resin contained in the water-absorbing layer is a water-absorbing cross-linked resin, and the water-absorbing layer obtained in combination with the metal oxide fine particles blended in the above proportion together with the water-absorbing layer is the anti-fogging article of the present invention.
  • crosslinked resin Specific examples of the water absorbent crosslinked resin contained in the water absorbing layer include a cured epoxy resin obtained by a reaction between a polyepoxide and a curing agent, and a urethane resin obtained by a reaction between a polyisocyanate and a polyol. Can be mentioned.
  • polyepoxide refers to a compound having two or more epoxy groups in one molecule.
  • Polyepoxide includes low molecular weight compounds, oligomers, and polymers.
  • the polyepoxide component is a component composed of at least one polyepoxide, and may be hereinafter referred to as a main agent as necessary.
  • the curing agent is a compound having two or more reactive groups in one molecule that react with the epoxy group of the polyepoxide, and is a polyaddition type curing agent that polyadds to the polyepoxide by reaction, and the polyepoxide by reaction.
  • the catalyst-type curing agent includes a thermosetting type and a photo-curing type, and these are collectively referred to as a catalyst-type curing agent.
  • the cured epoxy resin refers to a cured product obtained by a crosslinking reaction between the main agent and the curing agent.
  • the cured epoxy resin has a structure in which polyepoxide is cross-linked by a polyaddition type curing agent or the like to form a three-dimensional structure and / or a structure in which polyepoxides are linearly or three-dimensionally polymerized.
  • polyisocyanate means a compound having two or more isocyanate groups in one molecule.
  • Polyisocyanates include low molecular compounds, oligomers, and polymers.
  • Polyol refers to a polymer compound having an active hydrogen group such as two or more alcoholic hydroxyl groups in one molecule and a molecular weight of approximately 200 or more.
  • the urethane resin refers to a cured product obtained by crosslinking reaction of the polyisocyanate and the polyol.
  • the urethane resin has a structure in which a polyol is cross-linked with a polyisocyanate to form a three-dimensional structure.
  • the cured epoxy resin is not particularly limited as long as the antifogging property and scratch resistance of the present invention can be obtained.
  • the antifogging property of the water absorption layer according to the present invention is substantially determined by the water absorption performance of the cured epoxy resin used. Therefore, the cured epoxy resin used for the water absorption layer is selected to have a water absorption performance that is high enough to achieve the antifogging property.
  • the water absorption performance of the cured epoxy resin is preferably such that the saturated water absorption measured by the above method is 120 mg / cm 3 or more, and more preferably 150 mg / cm 3 or more.
  • the saturated water absorption amount of the cured epoxy resin takes the above value, the antifogging article of the present invention can ensure sufficient antifogging properties in the water absorbing layer.
  • the saturated water absorption amount of the cured epoxy resin is preferably 900 mg / cm 3 or less, and more preferably 500 mg / cm 3 or less.
  • the cured epoxy resin having such a high water absorption performance is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 800 and a high molecular weight polyepoxide having a molecular weight of 900 to 2000.
  • the low molecular weight polyepoxide is represented by the high molecular weight polyepoxide.
  • a first polyepoxide component having a mass ratio of 30:70 to 70:30 (hereinafter, this polyepoxide component is referred to as a first polyepoxide component) and a curing agent that reacts with the first first polyepoxide component (
  • a cured epoxy resin hereinafter, this cured polyepoxy resin is referred to as a first cured epoxy resin obtained by reacting a composition for forming a water-absorbing layer containing this curing agent with a first curing agent). It is done.
  • the water absorption evaluated by, for example, the saturated water absorption of the cured epoxy resin mainly depends on the abundance of hydrophilic groups such as hydroxyl groups and hydrophilic chains (for example, polyoxyethylene groups) derived from the main agent.
  • the water absorption also depends on the degree of crosslinking in the cured epoxy resin. If the number of cross-linking points contained in the cured epoxy resin per unit amount is large, the cured epoxy resin has a dense three-dimensional network structure, and it is considered that the water absorption becomes low because the space for water retention becomes small. On the other hand, if the number of cross-linking points contained per unit amount is small, it is considered that the space for water retention becomes large and the water absorption becomes high.
  • the glass transition point of the cured epoxy resin is closely related to the number of crosslinking points in the cured epoxy resin. In general, a resin having a high glass transition point is considered to have a large number of crosslinking points per unit amount.
  • the glass transition point of the cured epoxy resin is preferably ⁇ 20 to 60 ° C., although it depends on the type of the cured epoxy resin. More preferably, it is 40 degreeC.
  • the glass transition point is a value measured according to JIS K7121. Specifically, it is a value measured using a differential scanning calorimeter after providing a resin layer as a specimen on a substrate and leaving it in an environment of 20 ° C. and 50% relative humidity for 1 hour. However, the heating rate at the time of measurement shall be 10 degrees C / min.
  • curing agent which mainly comprise a water absorption layer react will be demonstrated.
  • the first polyepoxide component which is a raw material component of the first cured epoxy resin is composed of a low molecular weight polyepoxide having a molecular weight of 200 to 800 and a high molecular weight polyepoxide having a molecular weight of 900 to 2000, and a mass represented by low molecular weight polyepoxide: high molecular weight polyepoxide.
  • the ratio is 30:70 to 70:30.
  • the molecular weight of the high molecular weight polyepoxide used in the present invention is 900 to 2000, preferably 900 to 1500, and more preferably 900 to 1450.
  • the high molecular weight polyepoxide is considered to impart high water absorption and abrasion resistance such as abrasion resistance to the first cured epoxy resin obtained as described above.
  • the first cured epoxy resin has sufficient wear resistance when the molecular weight of the high molecular weight polyepoxide is within the above range. It is possible to ensure scratch resistance such as property.
  • high molecular weight polyepoxide may be used individually by 1 type, or may use 2 or more types together.
  • the molecular weight of the low molecular weight polyepoxide used in the present invention is 200 to 800, preferably 300 to 700, more preferably 300 to 650.
  • the low molecular weight polyepoxide has a role of favorably maintaining the appearance of the first cured epoxy resin obtained by using in combination with the high molecular weight polyepoxide.
  • the first cured epoxy resin is applied by solution by setting the molecular weight of the low molecular weight polyepoxide within the above range. A good appearance can be ensured without insufficient wetting and spreading of the coating liquid and unevenness of the coating film.
  • low molecular weight polyepoxide may be used individually by 1 type, or may use 2 or more types together.
  • the molecular weight means a mass average molecular weight (Mw) unless otherwise specified.
  • the mass average molecular weight (Mw) in this specification means the mass average molecular weight which uses polystyrene as a standard measured by gel permeation chromatography (GPC).
  • the high molecular weight polyepoxide and the low molecular weight polyepoxide constituting the first polyepoxide component compounds of the same class can be used except for the difference in molecular weight.
  • specific compounds used as the high molecular weight polyepoxide and the low molecular weight polyepoxide will be described.
  • the glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine polyepoxide, cycloaliphatic polyepoxide, etc. which are used as raw material components of ordinary cured epoxy resins, have the molecular weight described above. It can adjust and use so that it may become a range.
  • the number of epoxy groups per molecule of the polyepoxide in the first polyepoxide component is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, and in the high molecular weight polyepoxide, 3 to 8 is more preferable, 3 to 7 is more preferable, and in the low molecular weight polyepoxide, 2 to 8 is more preferable, and 2 to 5 is more preferable.
  • the glycidyl ether-based polyepoxide is a polyepoxide having a structure in which a glycidyloxy group is substituted for a phenolic hydroxyl group of a polyphenol having two or more phenolic hydroxyl groups or an alcoholic hydroxyl group of a polyol having two or more alcoholic hydroxyl groups.
  • Polyepoxide oligomer ).
  • the glycidyl ester polyepoxide has a structure in which the carboxyl group of a polycarboxylic acid having two or more carboxyl groups is substituted with a glycidyloxycarbonyl group, and the glycidylamine polyepoxide has two or more hydrogen atoms bonded to a nitrogen atom. It is a polyepoxide having a structure in which a hydrogen atom bonded to a nitrogen atom of an amine is substituted with a glycidyl group.
  • the cycloaliphatic polyepoxide is a polyepoxide having an alicyclic hydrocarbon group (such as a 2,3-epoxycyclohexyl group) in which an oxygen atom is bonded between adjacent carbon atoms of the ring.
  • an alicyclic hydrocarbon group such as a 2,3-epoxycyclohexyl group
  • a polyepoxide having no aromatic nucleus is preferable in terms of obtaining high water absorption in the obtained cured epoxy resin.
  • a cured epoxy resin obtained using a polyepoxide having an aromatic nucleus for example, a glycidyl ether-based polyepoxide derived from polyphenols, is difficult to incorporate moisture into the three-dimensional network structure due to the hard aromatic nucleus, It is thought that water absorption is low.
  • polyepoxide having no aromatic nucleus examples include glycidyl ether polyepoxides derived from polyols, glycidyl ester polyepoxides, glycidylamine polyepoxides, and polyepoxides having no aromatic nucleus among cyclic aliphatic polyepoxides. Of these, glycidyl ether polyepoxides derived from polyols having no aromatic nucleus are particularly preferred in the invention.
  • polyols having no aromatic nucleus such as aliphatic polyols and alicyclic polyols, and the number of hydroxyl groups per molecule is 2 to 10
  • the number of hydroxyl groups is more preferable, and the more preferable number of hydroxyl groups is the number listed as the number of preferable epoxy groups in the high molecular weight polyepoxide and the low molecular weight polyepoxide.
  • aliphatic / alicyclic polyol such a polyol having no aromatic nucleus is referred to as “aliphatic / alicyclic polyol”.
  • Examples of the aliphatic / alicyclic polyol include alkane polyol, etheric oxygen atom-containing polyol, sugar alcohol, polyoxyalkylene polyol, and polyester polyol.
  • the polyoxyalkylene polyol is obtained by ring-opening addition polymerization of a monoepoxide such as propylene oxide or ethylene oxide to a relatively low molecular weight polyol such as an alkane polyol, an etheric oxygen atom-containing polyol or a sugar alcohol.
  • the polyester polyol includes a compound having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are condensed, a compound having a structure in which a cyclic ester is ring-opening polymerized, and the like.
  • glycidyl ether-based polyepoxide derived from aliphatic / alicyclic polyols preferably used in the present invention include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol.
  • the glycidyl ether-based polyepoxide derived from aliphatic / alicyclic polyols that is preferably used preferably has an average number of glycidyloxy groups of 2 to 10 per molecule, and more preferably In the molecular weight polyepoxide and the low molecular weight polyepoxide, the number of polyepoxides listed as the preferred number of epoxy groups.
  • Such polyepoxides include, for example, triol triglycidyl ether, tetraol tetraglycidyl ether, a mixture of triol triglycidyl ether and the same triol diglycidyl ether, tetraol tetraglycidyl ether, triglycidyl ether and diol.
  • triol triglycidyl ether tetraol tetraglycidyl ether
  • a mixture of triol triglycidyl ether and the same triol diglycidyl ether tetraol tetraglycidyl ether
  • triglycidyl ether and diol examples thereof include a mixture of glycidyl ether, a mixture of triglycidyl ether of triol and diglycidyl ether of diol, and the like.
  • the average number of glycidyloxy groups per molecule is preferably 2 to 10, more preferably the number of epoxy groups preferably mentioned in the high molecular weight polyepoxide and the low molecular weight polyepoxide.
  • polyepoxides having no aromatic nucleus other than the glycidyl ether-based polyepoxides derived from the above aliphatic / alicyclic polyols are cycloaliphatic polyepoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-.
  • glycerin polyglycidyl ether As the low molecular weight polyepoxide, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether and the like, which are glycidyl ether-based polyepoxides derived from aliphatic / alicyclic polyols, are particularly preferable in the present invention. Used. Further, the average number of glycidyloxy groups per molecule in the low molecular weight polyepoxide is preferably 2 to 8, and more preferably 2 to 4.
  • the epoxy equivalent of the low molecular weight polyepoxide showing the relationship between the preferred molecular weight as the low molecular weight polyepoxide and the average number of epoxy groups per molecule (grams of resin containing 1 gram equivalent of epoxy groups [g / eq]) It is preferably 120 to 200 g / eq, more preferably 120 to 180 g / eq.
  • polyethylene glycol polyglycidyl ether, polyglycerin polyglycidyl ether, polyethylene glycol sorbitol polyglycidyl ether and the like which are glycidyl ether polyepoxides derived from aliphatic / alicyclic polyols, are particularly preferably used in the present invention. It is done. Furthermore, the average number of glycidyloxy groups per molecule in the high molecular weight polyepoxide is preferably 3 to 8, and more preferably 3 to 6.
  • the epoxy equivalent of the high molecular weight polyepoxide calculated in the same manner as the low molecular weight polyepoxide is preferably 140 to 200 g / eq, more preferably 150 to 190 g / eq.
  • the first polyepoxide component which is a raw material component of the first cured epoxy resin used in the present invention, is composed of at least one of the high molecular weight polyepoxides and at least one of the low molecular weight polyepoxides.
  • the mass ratio of low molecular weight polyepoxide: high molecular weight polyepoxide in the first polyepoxide component is preferably 30:70 to 70:30. More preferably, it is 40:60 to 70:30, and particularly preferably 40:60 to 60:40.
  • the low molecular weight polyepoxide has a molecular weight of 200 to 800, and the average epoxy per molecule At least one selected from the group consisting of glycerol polyglycidyl ether, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether having an epoxy equivalent of 120 to 180 g / eq, having 2 to 4 groups, and a high molecular weight polyepoxide having a molecular weight of 900 Polyethylene glycol polyglycidyl ether, polyglycerin polyglycidyl ether having an epoxy equivalent of 150 to 190 g / eq, having an average number of epoxy groups of 3 to 6 per molecule, A combination of at least one selected from the group consisting of Chi glycol sorbitol
  • both low molecular weight polyepoxide and high molecular weight polyepoxide constituting the first polyepoxide component can be commercially available products.
  • a commercially available product specifically, any of those manufactured by Nagase ChemteX Corporation is a trade name, and as a low molecular weight polyepoxide, Denacol EX-313 (Mw: 383, average number of epoxy groups: 2) is glycerin polyglycidyl ether.
  • Denacol EX-314 (Mw: 454, average number of epoxy groups: 2.3 / molecule), and polyglycerin polyglycidyl ether, Denacol EX-512 (Mw: 630, average number of epoxy groups: 4.1 pieces / molecule).
  • Denacol EX-1410 (Mw: 988, average number of epoxy groups: 3.5 / molecule), which is also an aliphatic polyglycidyl ether, also under the trade name, also manufactured by Nagase ChemteX Corporation, Denacol EX-1610 (Mw: 1130, average number of epoxy groups: 4.5 / molecule), Denacol EX-610U (Mw: 1408, average number of epoxy groups: 4.5 / molecule), and polyglycerin polyglycidyl ether , Denacol EX-521 (Mw: 1294, average number of epoxy groups: 6.3 / molecule) and the like.
  • Examples of sorbitol polyglycidyl ether include Denacol EX-622 (Mw: 930, average number of epoxy groups: 4.9 / molecule).
  • the first cured epoxy resin contained in the water absorbing layer is a first cured epoxy resin obtained by reacting the first polyepoxide component with a first curing agent.
  • curing agent it is a compound which has two or more reactive groups which react with the epoxy group which polyepoxide has, Comprising: It is preferable to use the polyaddition type hardening
  • Some catalyst-type curing agents have the effect of accelerating the crosslinking progress of polyaddition-type curing agents, and are expected to reduce defects at the cross-linking sites formed by some polyaddition-type curing agents. It is to be done.
  • An example of a defect is color change of a cured epoxy resin due to alteration of a cross-linked site due to heat load.
  • the reactive group that reacts with the epoxy group in the polyaddition type curing agent examples include an amino group having active hydrogen, a carboxyl group, and a thiol group. That is, the polyaddition type curing agent is preferably an amino compound having two or more amino groups having active hydrogen, a compound having two or more carboxyl groups, or a compound having two or more thiol groups, more preferably The amino compound having the active hydrogen is used.
  • Specific examples of such a compound having two or more reactive groups include polyamines, polycarboxylic acid anhydrides, polyamides, polythiols and the like. In the present invention, polyamines and polycarboxylic acid anhydrides are exemplified. The product is preferably used.
  • the first polyepoxide component used in the first cured epoxy resin contained in the water-absorbing layer in the present invention is the above-mentioned two kinds of molecular weight polyepoxides having no aromatic nucleus from the viewpoint of obtaining high water absorption. It is preferable to become.
  • the polyaddition type curing agent which is one of the reactive raw materials of the first cured epoxy resin is also a compound having no aromatic nucleus. That is, even if the first polyepoxide component is composed of a compound having no aromatic nucleus, if the polyaddition curing agent used has an aromatic nucleus, the first curing comprising the polyaddition curing agent is used.
  • the cured epoxy resin obtained from the combination with the agent becomes a cured epoxy resin having a relatively large number of aromatic nuclei, which may result in insufficient water absorption.
  • the polyaddition type curing agent used as the first curing agent is preferably a polyamine or polycarboxylic acid anhydride having no aromatic nucleus, and particularly preferably a polyamine having no aromatic nucleus.
  • the polyamines are preferably polyamines having 2 to 4 amino groups having active hydrogen
  • the polycarboxylic acid anhydrides are preferably dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and tetracarboxylic acid anhydrides.
  • polyamines having no aromatic nucleus examples include aliphatic polyamine compounds and alicyclic polyamine compounds. Specific examples of these polyamines include ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, mensendiamine, 3,9-bis (3-amino Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like.
  • the polyoxyalkylene polyamine is a polyamine having a structure in which the hydroxyl group of the polyoxyalkylene polyol is substituted with an amino group.
  • the hydroxyl group of the polyoxypropylene polyol having 2 to 4 hydroxyl groups is replaced with an amino group having active hydrogen.
  • the molecular weight per amino group is preferably 1000 or less, and particularly preferably 500 or less.
  • Examples of the polycarboxylic acid anhydride having no aromatic nucleus include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like.
  • catalyst-type curing agent that is preferably used together with the polyaddition-type curing agent in the first curing agent, tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, phosphine And other curing catalysts.
  • a catalyst-type curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluoro. Examples include phosphate, triphenylsulfonium hexafluorophosphate, and the like.
  • the catalyst-type curing agent contained in the first curing agent is a cured epoxy obtained even if it is a compound having an aromatic nucleus due to a small amount of use relative to the first polyepoxide component. Since there is almost no influence on the water absorption of the resin, a compound having an aromatic nucleus may be used.
  • onium salts such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate exemplified as the catalyst-type curing agent are catalyst-type curing agents that decompose with light such as ultraviolet rays to generate a Lewis acid catalyst. Usually, it is used as a catalyst-type curing agent that gives a photocurable cured epoxy resin.
  • the catalyst type curing agent used together with the polyaddition type curing agent preferably polyamines having no aromatic nucleus in the present invention, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole are used. Compounds are preferred.
  • the blending ratio of the first polyepoxide component, which is a raw material component of the first cured epoxy resin used in the present invention, and the first curing agent is as follows when a polyaddition type curing agent is used as the first curing agent.
  • the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is preferably a ratio of about 0.8 to 1.2, more preferably about 1.0 to 1.1. . If the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group is within the above range, a three-dimensional network that is appropriately crosslinked so as to have the above water absorption without decreasing the abrasion resistance such as abrasion resistance. A cured epoxy resin having a structure is obtained.
  • the equivalent ratio of amine active hydrogen to epoxy group derived from the first polyepoxide component is 0.00. It is preferably used so that the ratio becomes 5 to 1.5, and more preferably used so that the ratio becomes 0.6 to 0.8.
  • the equivalent ratio of the amine active hydrogen to the epoxy group is in the above range, a cured epoxy resin having a three-dimensional network structure that is appropriately cross-linked so as to have the above-mentioned water absorption without significant yellowing can be obtained.
  • the mass ratio of the polyaddition type curing agent used as the first curing agent with respect to the first polyepoxide component is too large, the physical properties of the obtained first cured epoxy resin may be insufficient.
  • the ratio of the polyaddition type curing agent to the first polyepoxide component is preferably 40% by mass or less.
  • the amount of the catalyst type curing agent used is 1.0 to 20% by mass relative to the first polyepoxide component. It is preferably 1 to 10% by mass, more preferably 1 to 5% by mass. If the amount of the catalyst-type curing agent used for the first polyepoxide component is 1.0% by mass or more, the reaction proceeds sufficiently, and sufficient water absorption and scratch resistance are realized in the obtained first cured epoxy resin. it can.
  • curing agent with respect to a 1st polyepoxide component is 20 mass% or less, the residue of a catalyst-type hardening
  • curing agent is the above-mentioned ratio of a catalyst type hardening
  • the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group may be reduced by about 10 to 50% from the above 0.5 to 1.0.
  • a commercially available product can be used as the first curing agent as described above.
  • a commercial product of the first curing agent specifically, as a polyoxyalkylene triamine which is a polyaddition type curing agent, Jeffamine T403 (trade name, manufactured by Huntsman) and the like can be mentioned.
  • Examples of the triarylsulfonium salt that is a photocurable catalyst-type curing agent include Adekaoptomer SP152 (trade name, manufactured by Adeka).
  • (1-2) Urethane resin When a urethane resin is used as the water-absorbing crosslinked resin contained in the water-absorbing layer, the present invention is obtained when the urethane resin and the metal oxide fine particles described later are combined in the above ratio to form a water-absorbing layer.
  • the urethane resin is not particularly limited as long as the antifogging property and scratch resistance can be obtained.
  • the antifogging property of the water absorption layer according to the present invention is substantially determined by the water absorption performance of the urethane resin used. Therefore, the urethane resin used for the water absorption layer is selected to have a water absorption performance that is high enough to achieve the antifogging property.
  • the water absorption performance of the urethane resin is such that the saturated water absorption measured by the above method is preferably 120 mg / cm 3 or more, and more preferably 150 mg / cm 3 or more.
  • the saturated water absorption amount of the urethane resin takes the above value, the antifogging article of the present invention can ensure sufficient antifogging properties in the water absorbing layer.
  • the saturated water absorption amount of the urethane resin is preferably 900 mg / cm 3 or less, and more preferably 500 mg / cm 3 or less.
  • urethane resins having high water absorption performance examples include urethane resins obtained by reaction of polyisocyanates and polyols, more specifically, acrylic polyols having an average molecular weight of 1000 to 4000 and polyoxyalkylenes having an average molecular weight of 400 to 5000. Examples thereof include a urethane resin obtained by reacting a polyol containing a polyol with a polyisocyanate.
  • the above polyoxyalkylene-based polyol is used as a polyol for causing the water absorption layer to exhibit an antifogging function.
  • a polyol having an oxyethylene chain, an oxypropylene chain, or the like can be used as the polyoxyalkylene polyol.
  • the oxyethylene chain is excellent in the function of absorbing water as bound water, and thus is advantageous for forming a water-absorbing layer having reversible absorption and dehydration that has a high dehydration rate during dehydration. Therefore, it is preferable to use a polyol having an oxyethylene chain in consideration of the antifogging property in a low temperature environment such as winter when the ambient temperature is 5 ° C. or lower.
  • the average molecular weight of the polyoxyalkylene polyol is preferably 400 to 5,000.
  • the average molecular weight is less than 400, the ability to absorb water as bound water is low, and when the average molecular weight exceeds 5000, problems such as poor curing and a decrease in film strength are likely to occur.
  • the average molecular weight is more preferably 400 to 4500.
  • the material used for the urethane resin and the average molecular weight of the obtained urethane resin refer to the number average molecular weight (Mn).
  • the number average molecular weight (Mn) refers to the number average molecular weight based on polystyrene measured by gel permeation chromatography (GPC).
  • the average molecular weight is preferably 400 to 2000 in consideration of the ability to absorb water, poor curing and mechanical strength of the water absorption layer.
  • the average molecular weight is preferably 1500 to 5000.
  • polystyrene-based polyol multiple types may be used as the polyoxyalkylene-based polyol.
  • the polyol to be used includes polyethylene glycol having an average molecular weight of 400 to 2000, which is particularly excellent in the ability to absorb water as bound water. It is preferable. Since polyethylene glycol is particularly excellent in the ability to absorb water as bound water, all polyoxyalkylene polyols may be polyethylene glycol.
  • the above-mentioned acrylic polyol mainly exerts an effect of lowering the wear resistance, water resistance, and surface friction coefficient of the water absorption layer, that is, exhibits the slip property on the surface of the water absorption layer.
  • this acrylic polyol has the effect of shortening the leveling step of uniforming the film thickness deviation when the water-absorbing layer-forming composition for forming the water-absorbing layer is applied to the substrate.
  • the acrylic polyol preferably has an average molecular weight of 1000 to 4000. If it is less than 1000, the wear resistance of the water-absorbing layer tends to decrease, and if it exceeds 4000, the applicability of the water-absorbing layer-forming composition at the time of forming the water-absorbing layer tends to be poor, and the water-absorbing layer formation tends to be difficult. .
  • the number of hydroxyl groups of the acrylic polyol is preferably 3 or 4.
  • the chain in the urethane resin obtained by reacting the polyoxyalkylene polyol and the polyol containing the acrylic polyol with the polyisocyanate has the effect of increasing the dehydration rate of the water absorbed in the water absorption layer. It has gained. Since this effect tends to improve as the molecular weight of the acrylic polyol increases, the average molecular weight of the acrylic polyol is preferably 2000 or more.
  • the acrylic polyol contributes to improving the durability of the water absorption layer and increasing the water dehydration rate as described above. Considering only the improvement of the durability of the water absorbing layer, a hydrophobic polyol other than the above acrylic polyol can be used, but it does not contribute to increasing the water dehydration rate. Therefore, although it is preferable that an acrylic polyol is included as a polyol for obtaining a urethane resin, it may not be an essential component depending on the design of the antifogging article.
  • the polyisocyanate for forming a urethane resin by crosslinking reaction with the polyol is an organic polyisocyanate such as an organic diisocyanate, preferably a trifunctional having a biuret and / or isocyanurate structure starting from hexamethylene diisocyanate.
  • the polyisocyanate can be used.
  • Such polyisocyanates have weather resistance, chemical resistance, and heat resistance, and are particularly effective for weather resistance.
  • diisophorone diisocyanate, diphenylmethane diisocyanate, bis (methylcyclohexyl) diisocyanate, toluene diisocyanate and the like can be used in addition to the above.
  • the blending ratio of the polyisocyanate and the polyol is such that the number of isocyanate groups as the whole polyisocyanate is 1 to 2 times, more preferably 1.4 to 1 times the number of hydroxyl groups as the whole polyol. It is preferable to adjust so that it may become 8 times amount. When the amount is less than 1 times, the curability deteriorates and the formed water-absorbing layer is soft, and durability such as weather resistance, solvent resistance, and chemical resistance may be lowered. On the other hand, when the amount exceeds 2 times, the antifogging property is deteriorated because the water absorption and dehydration is inhibited by excessive curing.
  • the ratio of the polyoxyalkylene-based polyol and the acrylic polyol is adjusted so that the water absorption performance of the obtained urethane resin becomes the saturated water absorption amount.
  • the water absorption layer contains metal oxide fine particles.
  • the metal oxide fine particles By including the metal oxide fine particles, the mechanical strength such as abrasion resistance and scratch resistance and heat resistance of the formed water absorption layer can be increased, and the curing shrinkage of the resin during the curing reaction can be reduced.
  • the metal oxide of such metal oxide fine particles include silica, alumina, titania, zirconia, and composite oxides thereof, and among these, silica is preferable.
  • ITO Indium Tin Oxide
  • metal oxide fine particles can also be used as the metal oxide fine particles. Since ITO has infrared absorptivity, heat absorption can be imparted to the water absorption layer. Therefore, if ITO fine particles are used, provision of an antifogging article having heat absorption in addition to water absorption can be expected.
  • the metal oxide fine particles contained in the water absorption layer preferably have an average primary particle size of 10 to 50 nm, and more preferably 10 to 30 nm. If the average primary particle diameter of the metal oxide fine particles is within this range, it is advantageous for ensuring transparency. In the present specification, the average primary particle diameter refers to that measured by the BET method.
  • the content of the metal oxide fine particles in the water absorption layer is 20 to 60% by mass with respect to the total amount of the water absorption layer, and preferably 30 to 50% by mass. By setting the content of the metal oxide fine particles in the water absorption layer to 20% by mass or more, the scratch resistance of the water absorption layer can be within the range of the present invention. Moreover, by setting it as 60 mass% or less, anti-fogging property can fully be ensured, maintaining a haze value low.
  • Silica fine particles which are preferably used as the metal oxide fine particles, are formed into water-absorbing layer-forming compositions as water or colloidal silica dispersed in an organic solvent such as methanol, ethanol, isobutanol, propylene glycol monomethyl ether, butyl acetate or the like. Can be blended. A method of blending the metal oxide fine particles into the water absorbing layer forming composition will be described later.
  • colloidal silica include silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent.
  • the organic solvent preferably used for this composition It is preferable to use an organosilica sol using the same organic solvent as the dispersion medium.
  • organosilica sol a commercially available product can be used.
  • organosilica sol IPA-ST trade name, Nissan Chemical Industries, Ltd.
  • silica fine particles having a particle diameter of 10 to 20 nm are dispersed in isopropanol at a ratio of 30% by mass as SiO 2 content with respect to the total amount of organosilica sol.
  • the amount of the solvent to be blended in the water absorbing layer forming composition is appropriately adjusted in consideration of the amount of solvent contained in the colloidal silica.
  • the water absorption layer in the antifogging article of the present invention is mainly composed of a crosslinked resin and metal oxide fine particles.
  • the content of the metal oxide fine particles in the water absorbing layer is such that the metal oxide fine particles are 20 to 60% by mass, preferably 30 to 50% by mass, based on the total amount of the water absorbing layer.
  • the content of the cross-linked resin in the water-absorbing layer is such that the cross-linked resin is 40 to 80% by mass, preferably 50 to 70% by mass with respect to the total amount of the water-absorbing layer.
  • the crosslinked resin is obtained by reacting a water-absorbing layer-forming composition containing the first polyepoxide component and the first curing agent.
  • curing agent which the composition for water absorption layer formation contains it is as above including preferable aspects, such as a compound used and the ratio at the time of combining.
  • the composition for forming a water absorption layer usually contains a solvent in addition to the first polyepoxide component and the first curing agent. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.
  • the reaction of the first polyepoxide component and the first curing agent for obtaining the first cured epoxy resin is carried out after coating on the coated surface of the substrate as a water absorbing layer forming composition.
  • these components may be reacted in advance in the composition before being applied to the application surface, then applied to the application surface, then dried, and further reacted.
  • a method of reacting to some extent in advance is taken as described above. A method in which the water absorbing layer forming composition is charged before and after the reaction is taken.
  • the reaction temperature when the reaction is performed in advance should be 30 ° C. or higher. This is preferable because the curing reaction proceeds reliably.
  • the solvent used in the water-absorbing layer forming composition is a solvent having good solubility with respect to the blending component including the first polyepoxide component, the first curing agent, and other optional components, and with respect to these blending components.
  • the solvent is not particularly limited as long as it is an inert solvent, and specific examples include alcohols, acetates, ethers, ketones, and water.
  • a solvent and an epoxy group may react and it may be hard to form a cured epoxy resin. Accordingly, when a protic solvent is used, it is preferable to select a solvent that does not easily react with the first polyepoxide component.
  • protic solvents examples include ethanol and isopropanol.
  • acetone, methyl ethyl ketone, butyl acetate, propylene carbonate, diethylene glycol dimethyl ether, diacetone alcohol, propylene glycol monomethyl ether and the like are preferable.
  • solvents may be used alone or in combination of two or more.
  • compounding components such as a 1st polyepoxide component and a 1st hardening
  • the solvent contained in the mixture may be used as it is as the solvent in the water-absorbing layer-forming composition, and the water-absorbing layer-forming composition may be the same or other solvent. May be added.
  • the amount of the solvent in the water-absorbing layer forming composition is 100 to 100 parts by mass with respect to a total mass of 100 parts by mass of the total solid content in the first polyepoxide component, the first curing agent, and other various blending components optionally blended.
  • the amount is preferably 500 parts by mass, and more preferably 200 to 350 parts by mass.
  • the blending amount of the first polyepoxide component and the first curing agent in the water-absorbing layer forming composition is preferably 15 to 30% by mass with respect to the total amount of the composition for the first polyepoxide component.
  • the first curing agent is preferably 3 to 20% by mass with respect to the total amount of the composition.
  • the total amount is preferably 3 to 16% by mass with respect to the total amount of the composition.
  • the blending ratio of the polyaddition type curing agent and the catalyst type curing agent in the first curing agent depends on the type of curing agent used. For example, when an amine compound having active hydrogen (polyaddition type curing agent) and an imidazole compound (catalytic type curing agent) are used in combination as the first curing agent, the total amount of the water absorbing layer forming composition
  • the amine compound having active hydrogen is preferably blended at a ratio of 3 to 15% by mass and the imidazole compound at a ratio of 0.1 to 1.0% by mass.
  • the reactive additive includes a compound having one reactive group reactive with an epoxy group such as alkyl monoamine, a coupling having an epoxy group or an amino group Agents and the like.
  • the coupling agent has an adhesive property between the substrate and the water-absorbing layer, an adhesive property between the water-absorbing layer and the underlayer, or a water-absorbing layer and a functional layer described later laminated on the layer as necessary. It is a component that is blended for the purpose of improving the adhesiveness to and is one of the components that are preferably blended.
  • an organometallic coupling agent or a polyfunctional organic compound is preferable.
  • organometallic coupling agents include silane coupling agents (hereinafter referred to as silane coupling agents), titanium coupling agents, and aluminum coupling agents, with silane coupling agents being preferred.
  • These coupling agents preferably have a reactive group that can react with the reactive group that the first polyepoxide component or the first curing agent has and the reactive group that remains on the surface of the underlayer described later.
  • the coupling agent is preferably a compound having one or more (preferably one or two) bonds between a metal atom and a carbon atom.
  • a silane coupling agent is particularly preferable.
  • a silane coupling agent is a compound in which one or more hydrolyzable groups and one or more monovalent organic groups (however, the terminal bonded to the silicon atom is a carbon atom) are bonded to the silicon atom.
  • One of the monovalent organic groups is a functional organic group (an organic group having a reactive group or an organic group exhibiting characteristics such as hydrophobicity).
  • a functional organic group an organic group having a reactive group or an organic group exhibiting characteristics such as hydrophobicity.
  • an alkyl group having 4 or less carbon atoms is preferable.
  • the number of hydrolyzable groups bonded to the silicon atom is preferably 2 or 3.
  • the silane coupling agent is preferably a compound represented by the following formula (1).
  • R 3 represents a monovalent functional organic group
  • R 4 represents an alkyl group having 4 or less carbon atoms
  • c represents an integer of 0 or 1.
  • R 4 is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • X 2 is a hydrolyzable group such as a chlorine atom, an alkoxy group, an acyl group, or an amino group, and an alkoxy group having 4 or less carbon atoms is particularly preferable.
  • the functional organic group may be a hydrophobic organic group such as a polyfluoroalkyl group or a long-chain alkyl group having 6 to 22 carbon atoms.
  • it is an alkenyl group having an addition polymerizable unsaturated group or an alkyl group having a reactive group.
  • the alkyl group having a reactive group may be an alkyl group substituted with an organic group having a reactive group.
  • Such an alkyl group preferably has 1 to 4 carbon atoms.
  • the reactive group include an epoxy group, amino group, mercapto group, ureido group, hydroxyl group, carboxyl group, acryloyloxy group, methacryloyloxy group, and isocyanate group.
  • Examples of the organic group having such a reactive group include a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted amino group.
  • a silane coupling agent whose reactive group is an epoxy group, an amino group, a mercapto group, or a ureido group is preferable.
  • silane coupling agents examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidyl Sidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxys
  • a silane coupling agent having an amino group such as ethyl) -3-aminopropyltrimethoxysilane is preferably used.
  • the blending amount of the coupling agent in the water absorbing layer forming composition is not an essential component, so there is no lower limit.
  • the mass ratio of the coupling agent is 5 with respect to the total mass of the first polyepoxide component and the first curing agent in the water absorbing layer forming composition. It is preferably ⁇ 40% by mass, more preferably 10 to 30% by mass.
  • the upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent.
  • the mass ratio of the coupling agent to the total mass of the first polyepoxide component and the first curing agent is 40 mass.
  • % Or less is preferable, and 30% by mass or less is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the water-absorbing resin mainly composed of the first cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.
  • the blending amount of the coupling agent relative to the total amount of the water-absorbing layer forming composition is preferably 2 to 10% by mass, for example, when using a silane coupling agent, and is 3 to 7% by mass. It is more preferable.
  • a particularly preferable composition in the composition for forming a water absorbing layer containing a silane coupling agent an amine having 15 to 30% by mass of the first polyepoxide component and active hydrogen with respect to the total amount of the composition. Examples thereof include a composition containing 3 to 15% by mass of the compound, 0.1 to 1.0% by mass of the imidazole compound, 2 to 10% by mass of the silane coupling agent, and 50 to 75% by mass of the solvent.
  • the equivalent ratio of amine active hydrogen to the epoxy group is the amine activity in the first curing agent.
  • the equivalent ratio with the epoxy group of the first polyepoxide component is calculated so as to be within the preferred range.
  • the equivalent ratio of amine active hydrogen to the epoxy group is the epoxy contained in the first polyepoxide component.
  • the equivalent ratio of amine active hydrogen in the first curing agent is calculated so as to be in the preferred range.
  • the water-absorbing layer-forming composition preferably further contains an antioxidant as an optional component in order to improve the weather resistance of the water-absorbing layer obtained.
  • an antioxidant as an optional component in order to improve the weather resistance of the water-absorbing layer obtained.
  • Antioxidants include phenolic antioxidants that suppress the oxidation of resins by capturing and decomposing peroxy radicals, and phosphorus antioxidants that suppress the oxidation of resins by decomposing peroxides. In the present invention, a phenolic antioxidant is preferably used.
  • the following phenolic antioxidants usually blended in a cured epoxy resin can be used without particular limitation. One of these may be used alone, or two of them may be used in combination.
  • Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ′′, 5,5 ′, 5 ′′ -hexa-tert-butyl-a, a ′
  • phenolic antioxidants examples include IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135 (trade name, manufactured by Ciba Japan), Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90 (trade name, manufactured by ADEKA), Sumilizer GA-80, Sumizer MDP-S, Sumizer BBM-S, Sumizer GM, Sumizer GS (F), Sumil Chemical Industries, Sumitomo G Etc.).
  • the amount of the antioxidant blended in the water-absorbing layer forming composition is preferably 0.5 to 2% by mass with respect to the total mass of the first polyepoxide component and the first curing agent, and preferably 1 to 2 mass% is more preferable.
  • a leveling agent, an antifoamer, a viscosity modifier, a light stabilizer, etc. can be further added to the composition for forming a water absorbing layer as necessary.
  • the leveling agent include polydimethylsiloxane-based surface conditioners, acrylic copolymer surface conditioners, fluorine-modified polymer-based surface conditioners, and antifoaming agents include silicone-based antifoaming agents, surfactants, Organic antifoaming agents such as ethers and higher alcohols, acrylic copolymers, polycarboxylic acid amides, modified urea compounds, etc.
  • each component may be used in combination of two or more of the exemplified compounds.
  • the content of various components in the water-absorbing layer-forming composition may be 0.001 to 10% by mass with respect to the total mass of the first polyepoxide component and the first curing agent for each component. it can.
  • the crosslinked resin used in the water-absorbing layer in the antifogging article of the present invention is, for example, a urethane resin
  • the crosslinked resin is obtained by reacting the water-absorbing layer-forming composition containing the polyol and the polyisocyanate. .
  • the composition for forming a water absorption layer usually contains a solvent in addition to the polyol and the polyisocyanate. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.
  • the reaction of the polyol and the polyisocyanate for obtaining the urethane resin is carried out after coating on the coated surface of the substrate as a water-absorbing layer forming composition.
  • the composition contains a solvent, the coated surface
  • These components may be allowed to react to some extent in the composition before being applied to the surface, then applied to the coated surface, dried, and further reacted.
  • the above-described method of reacting to some extent is taken, and the metal oxide fine particles are put before and after this reaction.
  • a method of separately charging the water absorbing layer forming composition is employed.
  • the curing reaction can be ensured by setting the reaction temperature to 30 ° C. or higher in advance. This is preferable because it proceeds.
  • the solvent used in the water-absorbing layer-forming composition is a solvent having good solubility with respect to the above-mentioned polyol, polyisocyanate, and other optional ingredients, and an inert solvent for these ingredients. If it is, it will not specifically limit, Specifically, it is preferable to use an acetate ester solvent, ketones, and diacetone alcohol.
  • solvents may be used alone or in combination of two or more.
  • compounding components such as the said polyol and the said polyisocyanate, may be prepared as a mixture with a solvent.
  • the solvent contained in the mixture may be used as it is as a solvent in the water-absorbing layer-forming composition, and the water-absorbing layer-forming composition may contain the same or other solvents. May be added.
  • the amount of the solvent in the water-absorbing layer forming composition is 100 to 500 parts by mass with respect to 100 parts by mass as a total mass of the total solids in the above-mentioned polyol, polyisocyanate, and other various blending components optionally blended. It is preferably 200 to 350 parts by mass.
  • an organic tin compound that is a curing catalyst may be added as another component in order to increase the curing rate of the polyol and the polyisocyanate.
  • Examples of the compound include dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin markabutide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin makercarboxylate, dioctyltin thiocarboxylate Etc. can be used.
  • the blending amount is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polyol and polyisocyanate.
  • organic A coupling agent comprising a metal-based coupling agent or a polyfunctional organic compound, an antioxidant, a leveling agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer and the like can be added.
  • the water absorbing layer in the antifogging article of the present invention is obtained by reacting the first polyepoxide component and the first curing agent contained in the water absorbing layer forming composition or the polyol and polyisocyanate.
  • a first crosslinked epoxy resin or urethane resin having a three-dimensional network structure, and the predetermined amount of metal oxide fine particles uniformly in the three-dimensional network structure of the crosslinked resin. It is a resin layer having a composition that is dispersed and included, and thus has both excellent anti-fogging properties and abrasion resistance such as abrasion resistance and scratch resistance. The reaction conditions will be described in the production method described later.
  • a reactive additive such as a silane coupling agent that is optionally added is present in the water absorption layer in a form that is bonded to a part of the three-dimensional network structure of the crosslinked resin, and is optionally added in addition to that.
  • the non-reactive additive is, as in the case of the metal oxide fine particles, present in the water-absorbing layer by being uniformly dispersed and included in the three-dimensional network structure of the crosslinked resin.
  • the antifogging article of the present invention may have a functional layer such as an undercoat layer or an adhesion layer between the substrate and the water absorbing layer as long as the effects of the present invention are not impaired.
  • a functional layer such as an undercoat layer or an adhesion layer between the substrate and the water absorbing layer
  • the antifogging index is more antifogging than the water absorbing layer in order to prevent peeling of the substrate and the water absorbing layer.
  • You may have a low base layer. Since antifogging properties are relative, “high antifogging properties” and “low antifogging properties” do not mean high or low with a threshold.
  • the underlayer is a layer formed between the substrate and the water absorbing layer, and is obtained by reacting a composition for forming an underlayer containing a second polyepoxide component and a second curing agent. It is a layer having lower water absorption than the water absorption layer mainly composed of the second cured epoxy resin.
  • the resin mainly composed of the second cured epoxy resin in the underlayer is also referred to as a low water absorption resin.
  • the base layer and the water absorption layer are collectively referred to as an antifogging film.
  • the water absorption layer formed on the base surface without an underlayer may be referred to as an antifogging film.
  • the saturated water absorption measured by the method demonstrated with the said water absorption layer is 30 mg / cm ⁇ 3 > or less. And is more preferably 20 mg / cm 3 or less.
  • the saturated water absorption amount of the low water absorbent resin constituting the underlayer is 1 mg / cm 3 or more. It is preferably 3 mg / cm 3 or more.
  • the antifogging property can be 10 seconds or less, In a more preferred embodiment, it can be 7 seconds or less, and in a particularly preferred embodiment, it can be 3 seconds or less.
  • the antifogging property is preferably 1 second or more from the viewpoint of reducing the degree of expansion / contraction between the base layer and the water absorption layer in the antifogging film, preferably 2 seconds or more. More preferably.
  • the film thickness of the foundation layer according to the antifogging article of the present invention is preferably 1 ⁇ m or more, More preferably, it is 3 ⁇ m or more, and further preferably 5 ⁇ m or more. If the film thickness of the underlayer is 1 ⁇ m or more, it becomes possible to prevent the antifogging film from peeling from the substrate, and as a result, an antifogging article having excellent acid resistance and alkali resistance is obtained.
  • the thickness of the underlayer is more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more, for the reason of relieving the stress generated at the interface due to the expansion / contraction of the water absorption layer.
  • the thickness of the underlayer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 8 ⁇ m or less, from the viewpoint of reducing material costs and improving the yield rate.
  • the peel resistance required for the undercoat layer varies depending on the use, and therefore the design may be appropriately changed in accordance with the required performance.
  • the cured epoxy resin mainly constituting the foundation layer is a second cured epoxy resin obtained by reacting the second polyepoxide component and the second curing agent, and is used for designing the foundation layer to have the above water absorption.
  • the main component is a second cured epoxy resin obtained by reacting the second polyepoxide component and the second curing agent, and is used for designing the foundation layer to have the above water absorption.
  • the glass transition point of the cured epoxy resin low, and to increase the scratch resistance, it is preferable to control the glass transition point of the cured epoxy resin high.
  • the glass transition point of the second cured epoxy resin mainly constituting the low water-absorbing resin is preferably 40 to 150 ° C., preferably 40 to 120 ° C., although it depends on the type of the cured epoxy resin. More preferably.
  • the glass transition point of the first water-absorbing layer mainly comprising the water-absorbing layer is in the above range ( ⁇ 20 to 60 ° C., preferably ⁇ 5 to 40 ° C.), and the water-absorbing layer mainly comprises the underlayer. If the glass transition point of the second cured epoxy resin is within the above range and higher than the glass transition point of the first cured epoxy resin, the antifogging performance and the scratch resistance are compatible at a high level. Easy to do.
  • the difference in glass transition point between the second cured epoxy resin in the underlayer and the first cured epoxy resin in the water-absorbent resin is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher.
  • the second cured epoxy resin obtained by reacting the second polyepoxide component mainly constituting the base layer with the second curing agent will be described.
  • the second polyepoxide component which is a raw material component of the second cured epoxy resin the first polyepoxide component which is usually used as the raw material component of the cured epoxy resin has been described so that the water absorption is in the preferred range.
  • a polyepoxide appropriately selected from glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine polyepoxide, cyclic aliphatic polyepoxide, and the like can be used.
  • the molecular weight of the polyepoxide used as the second polyepoxide component is not particularly limited, but from the viewpoint of avoiding poor appearance such as insufficient wetting and spreading of the coating solution during coating and unevenness of the coating film, about 500 to 1000 Polyepoxides with a molecular weight of The number of epoxy groups per molecule of polyepoxide in the second polyepoxide component is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, more preferably 2 to 8 2 to 4 are more preferable.
  • the second polyepoxide component for example, by selecting a polyepoxide having an aromatic nucleus that is not selected as a preferred polyepoxide in the first polyepoxide component, the water absorption of the resulting cured epoxy resin can be lowered. Is possible.
  • the polyepoxide having an aromatic nucleus that can be used as the second polyepoxide component is preferably a polyepoxide having a structure in which a phenolic hydroxyl group is substituted with a glycidyloxy group.
  • bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are preferably used as the second polyepoxide component.
  • the resulting cured epoxy resin has a dense three-dimensional network structure, and the space for water retention is reduced, resulting in a decrease in water absorption. It is done.
  • a polyepoxide preferable as the first polyepoxide component is also preferably used as the second polyepoxide component.
  • Particularly preferred polyepoxides as the second polyepoxide component are sorbitol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers and the like classified into glycidyl ether-based polyepoxides derived from aliphatic / alicyclic polyols. It is.
  • the second polyepoxide component in order to increase the number of crosslinking points of the obtained second cured epoxy resin and control the water absorption low, for example, the second polyepoxide component is aliphatic / alicyclic.
  • the epoxy equivalent is preferably 100 to 200 g / eq, and more preferably 100 to 150 g / eq.
  • a commercially available product can be used in the same manner as the polyepoxide constituting the first polyepoxide component.
  • jER828 (trade name, manufactured by Mitsubishi Chemical Corporation) as bisphenol A diglycidyl ether
  • Adeka Resin EP4901 product as bisphenol F diglycidyl ether Name, manufactured by Adeka).
  • the second cured epoxy resin that mainly constitutes the underlayer is a second cured epoxy resin obtained by reacting the second polyepoxide component with a second curing agent.
  • curing agent it is preferable to use a polyaddition type hardening
  • the type of polyaddition type curing agent that can be used is the same as that of the first curing agent. That is, the polyaddition type curing agent is preferably an amino compound having two or more amino groups having active hydrogen, a compound having two or more carboxyl groups, or a compound having two or more thiol groups, more preferably The amino compound having the active hydrogen is used.
  • the second curing agent for example, a cured epoxy resin obtained by selecting a polyaddition curing agent having an aromatic nucleus that is not selected as a preferable curing agent in the first curing agent. It is possible to reduce the water absorption. Depending on the degree of water absorption required for the underlayer, if a compound having an aromatic nucleus is used in at least one of the second polyepoxide component and the second curing agent, the water absorption of the second cured epoxy resin obtained is obtained. The property can be in the desired range.
  • the same curing agent as the polyaddition type curing agent having no aromatic nucleus described in the first curing agent can be used.
  • the polyaddition type curing agent having an aromatic nucleus include polyamines having an aromatic nucleus and aromatic polycarboxylic acid anhydrides. Specific examples of the polyamine having an aromatic nucleus include phenylenediamine, xylylenediamine, diaminodiphenylmethane, and the like, and examples of the aromatic polycarboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, and pyrophilic anhydride. And merit acid.
  • the catalyst-type curing agent that can be used as necessary in the second curing agent the same curing agent as the catalyst-type curing agent described in the first curing agent can be used.
  • the blending ratio of the second polyepoxide component, which is a raw material component of the second cured epoxy resin used in the present invention, and the second curing agent is the second when a polyaddition curing agent is used as the second curing agent.
  • the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group derived from the polyepoxide component is preferably about 0.8 to 1.5, more preferably about 1.0 to 1.5. If the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group is in the above range, the reaction temperature is raised and the polyaddition reaction is accelerated to crosslink at a sufficient number of crosslinking points at room temperature. Thus, a second cured epoxy resin having a low water absorption as compared with the first cured epoxy resin having a three-dimensional network structure is obtained.
  • the equivalent ratio of amine active hydrogen to epoxy group derived from the second polyepoxide component is 0.00. It is preferably used so that the ratio becomes 5 to 1.5, and more preferably used so that the ratio becomes 1.2 to 1.5.
  • the equivalent ratio of amine active hydrogen to epoxy group is in the above range, a dense three-dimensional network structure can be formed by crosslinking at a sufficient number of crosslinking points without increasing the reaction temperature and accelerating the polyaddition reaction.
  • a second cured epoxy resin having a low water absorption as compared with the first cured epoxy resin having the above is obtained.
  • the mass ratio of the polyaddition type curing agent used as the second curing agent with respect to the second polyepoxide component is too large, the physical properties of the obtained second cured epoxy resin may be insufficient.
  • the ratio of the polyaddition type curing agent to the polyepoxide component is preferably 40% by mass or less.
  • the underlayer in the antifogging film of the antifogging article of the present invention comprises a second cured epoxy resin obtained by reacting the underlayer forming composition containing the second polyepoxide component and the second curing agent. This is the underlying layer.
  • curing agent which the composition for base layer formation contains it is as above including preferable aspects, such as a compound used and the ratio at the time of combining.
  • the underlayer-forming composition usually contains a solvent in addition to the second polyepoxide component and the second curing agent. Moreover, the reactive additive other than these and a non-reactive additive are contained as needed.
  • the composition for forming the underlayer is the second polyepoxide component and the second curing agent in the composition before being applied to the coating surface as a composition containing a solvent, like the composition for forming the water absorption layer. May be reacted in advance to some extent, then applied to the coated surface, dried, and further reacted.
  • the conditions for the reaction in advance can be the same as those in the case of the water absorbing layer forming composition.
  • the solvent used in the composition for forming the underlayer is a solvent having good solubility with respect to the blending component including the second polyepoxide component, the second curing agent, and other optional components, and with respect to these blending components.
  • the solvent is not particularly limited as long as it is an inert solvent, and specific examples thereof include the same solvents as the water absorbing layer forming composition.
  • the preferred embodiment of the solvent is the same as that of the water absorbing layer forming composition.
  • the amount of the solvent in the composition for forming the underlayer is 200 to 200 parts by mass with respect to 100 parts by mass as a total mass of the total solid content in the second polyepoxide component, the second curing agent, and other various blending components optionally blended.
  • the amount is preferably 950 parts by mass, and more preferably 400 to 950 parts by mass.
  • the blending amount of the second polyepoxide component and the second curing agent in the underlayer-forming composition is preferably 4 to 10% by mass with respect to the total amount of the composition for the second polyepoxide component.
  • the second curing agent is preferably 0.1 to 4.0% by mass with respect to the total amount of the composition.
  • the total amount is preferably 0.1 to 4.0% by mass with respect to the total amount of the composition.
  • the reactive additive optionally contained in the underlayer-forming composition examples include the same additives as the reactive additive optionally contained in the water-absorbing layer-forming composition.
  • the coupling agent is a component that is blended for the purpose of improving the adhesion between the foundation layer and the substrate and the adhesion between the foundation layer and the water absorbing layer in the composition for forming the foundation layer. It is one of the preferred components.
  • the amount of the coupling agent blended in the underlayer-forming composition is such that the mass ratio of the coupling agent is 5 to 50% by mass with respect to the total mass of the second polyepoxide component and the second curing agent. It is preferably 10 to 40% by mass.
  • the upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent.
  • the mass ratio of the coupling agent to the total mass of the second polyepoxide component and the second curing agent is 50 mass. % Or less is preferable, and 40% by mass or less is more preferable.
  • the second polyepoxide component when adjusting physical properties such as water absorption of the resin of the base layer mainly composed of the second cured epoxy resin by the coupling agent or by the second curing agent and the coupling agent, the second polyepoxide component
  • the mass ratio of the coupling agent to the total mass of the second curing agent is preferably 40% by mass or less, and more preferably 20% by mass or less. If the amount of the coupling agent used is not excessive, it is possible to prevent the resin of the base layer mainly composed of the second cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.
  • the blending amount of the coupling agent with respect to the total amount of the underlayer-forming composition is, for example, preferably 0.1 to 4.0% by mass when a silane coupling agent is used, and 0.1 to 3.
  • the content is more preferably 0% by mass, and particularly preferably 1 to 2% by mass.
  • a particularly preferable composition in the above-mentioned composition for forming an underlayer containing a silane coupling agent the amine having 4 to 10% by mass of the second polyepoxide component and active hydrogen with respect to the total amount of the composition.
  • examples include a composition containing 0.1 to 4.0% by mass of a compound, 0.1 to 4.0% by mass of a silane coupling agent, and 70 to 95% by mass of a solvent.
  • the equivalent ratio of the amine active hydrogen to the epoxy group is determined as follows. It is preferable to adjust the blending amount of each component so that this is within the above range.
  • the underlayer forming composition preferably further contains tetraalkoxysilane and / or an oligomer thereof (that is, a partially hydrolyzed condensate thereof) as an optional component.
  • tetraalkoxysilane and / or an oligomer thereof that is, a partially hydrolyzed condensate thereof
  • the viscosity of the underlayer-forming composition is lowered, and a crosslinking reaction between the second polyepoxide component and the second curing agent. Is performed uniformly.
  • substrate and a water absorption layer increases, and adhesiveness improves further. Thereby, the weather resistance of the base layer obtained can be improved.
  • tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and tetra n-butoxysilane.
  • tetramethoxysilane and tetraethoxysilane are preferable.
  • One of these may be used alone, or two of them may be used in combination.
  • the above tetraalkoxysilane may be blended into the underlayer forming composition as an oligomer obtained by partial hydrolysis (co) condensation of about 2 to 3 of the tetraalkoxysilane, and as a mixture of the tetraalkoxysilane and the oligomer. You may mix
  • the amount of tetraalkoxysilane and / or oligomer thereof blended in the underlayer-forming composition is preferably 10 to 40% by mass with respect to the total mass of the second polyepoxide component and the second curing agent, 25 More preferable is 35 mass%.
  • the composition for forming the underlayer further contains an antioxidant as an optional component in order to improve the weather resistance of the obtained underlayer, for the same reason as the composition for forming the water absorbing layer.
  • an antioxidant as an optional component in order to improve the weather resistance of the obtained underlayer, for the same reason as the composition for forming the water absorbing layer.
  • blended with the composition for base layer formation it can be made to be the same as that of the antioxidant used for the said composition for water absorption layer formation including the compound used and a preferable aspect.
  • the amount of the antioxidant blended in the underlayer-forming composition is preferably 0.5 to 3% by mass with respect to the total mass of the second polyepoxide component and the second curing agent. It is more preferably 1 to 2% by mass.
  • the same leveling agent, antifoaming agent, viscosity adjusting agent, light stabilizer, etc. as those contained in the water absorbing layer forming composition are contained.
  • Metal oxide fine particles may be added, but the blending amount is preferably 0.5 to 5% by mass based on the total mass of the second polyepoxide component and the second curing agent. The mass% is more preferable.
  • the underlayer in the antifogging article of the present invention is a second layer having a three-dimensional network structure obtained by reacting the second polyepoxide component and the second curing agent contained in the underlayer forming composition. Consisting of a cured epoxy resin, the properties of the second cured epoxy resin described above have a water absorption lower than that of the water absorbing layer, and sufficiently secure the adhesion to the substrate and the water absorbing layer. It is a resin layer excellent in peelability. The reaction conditions will be described in the production method described later.
  • the antifogging article of the present invention has a configuration in which a water absorption layer is provided on a substrate. Furthermore, when it has a base layer as needed, it has the structure by which the base layer and the water absorption layer were laminated
  • Such an antifogging article can be specifically manufactured by the following method (A) or (B), taking as an example the case of having a foundation layer. When the base layer is not provided, the method is limited to the method (A). By eliminating the step of forming the base layer by the method (A), an antifogging article having a water absorption layer directly formed on the substrate surface is obtained.
  • the film (water-absorbing layer) is bonded by using a composition for forming an underlayer as an adhesive and forming an underlayer that is an adhesive layer between the two, so that the underlayer and the water-absorbing layer are formed from the substrate surface side.
  • a water-absorbing layer made of a film-like water-absorbing resin is formed on a releasable support, and this is separated from the support to form an underlayer-forming composition on the substrate surface.
  • a method in which a water-absorbing layer made of a film-like water-absorbing resin is bonded to the substrate surface together with the support using the underlayer-forming composition as an adhesive is preferred.
  • the support to be used is not particularly limited as long as it does not impair the effects of the present invention, but an acrylic resin film such as polymethyl methacrylate is preferably used.
  • the method (A) is capable of maintaining a good appearance when a base layer or a water absorption layer is provided on the surface of a large-area substrate or during industrial mass production. More preferred.
  • a method for producing the antifogging article of the present invention by the method (A) will be described.
  • the method for producing an antifogging article of the present invention is for forming an underlayer containing a second polyepoxide component and a second curing agent as the step (a).
  • the antifogging article does not have a base layer, the same operation may be performed with the “surface of the base layer” in the step (b) as the “substrate surface”.
  • the step (b) may be a method including the following steps (1) to (4).
  • the liquid composition containing the raw material component of the crosslinked resin for the water absorbing layer contains the metal oxide fine particles, that is, the metal oxide fine particles are 20 to 60% by mass with respect to the total amount of the water absorbing layer to be obtained.
  • a step (2) of proceeding a crosslinking reaction of the liquid composition obtained in the step (1) A step (3) of adding the remainder of the content of the metal oxide fine particles to the liquid composition obtained by the step (2), -And the process (4) which apply
  • Each process of the above method is classified into a process for preparing a water-absorbing layer forming composition and a process for forming a water-absorbing layer from the obtained composition.
  • a method for preparing the water absorbing layer forming composition a method including the above step (1), step (2), and step (3) can be used. That is, the composition obtained through the steps (1), (2) and (3) is the water absorbing layer forming composition.
  • the method containing the said process (4) can be used as a method of forming a water absorption layer from the composition for water absorption layer formation.
  • the content of the metal oxide fine particles in the water absorbing layer can have both excellent antifogging property and abrasion resistance, scratch resistance and other scratch resistance in the water absorbing layer obtained. Therefore, the content of the metal oxide fine particles is 20 to 60% by mass with respect to the total amount of the water absorption layer, and the content is more preferably 30 to 50% by mass.
  • the addition amount of the metal oxide fine particles in the step (1) is a metal content relative to the content of the metal oxide fine particles in the water absorption layer, that is, the total amount of the water absorption layer to be obtained.
  • the content of oxide fine particles is preferably 20 to 50% by mass of the content of 20 to 60% by mass, and more preferably 5 to 40% by mass.
  • the crosslinking reaction of the liquid composition is allowed to proceed to about 50 to 70% assuming that the crosslinking reaction when the water-absorbing layer is finally formed is 100% crosslinking. It is preferable to advance, and it is more preferable to advance the crosslinking to about 50 to 60%.
  • the amount added in the step (1) is subtracted from the content of the metal oxide fine particles in the water absorption layer to the liquid composition in which the crosslinking reaction has progressed to the above degree in the step (2). Add the remainder.
  • the amount of the metal oxide fine particles to be added in the step (3) is converted from the amount to be added in the step (1), the content of the metal oxide fine particles in the water absorption layer, that is, the total amount of the water absorption layer to be obtained.
  • the content of the metal oxide fine particles is preferably from 20 to 60% by mass, more preferably from 60 to 95% by mass, based on the content of 20 to 60% by mass.
  • the underlayer-forming composition and the water-absorbing-layer-forming composition are as described above, and the underlayer-forming composition is prepared by mixing these components in a normal manner. .
  • the method for applying the underlayer-forming composition obtained above to the application surface of the substrate is not particularly limited. Known methods such as a dip coating method, a spin coating method, a spray coating method, a flexographic printing method, a screen printing method, a gravure printing method, a roll coating method, a meniscus coating method, a die coating method, and a wiping method may be mentioned.
  • the coating thickness of the composition for forming the underlayer is set such that the thickness of the underlayer finally obtained by reaction of the reaction components in the composition falls within the above range.
  • the solvent is removed by drying as necessary, and a curing treatment is performed under conditions suitable for the reaction components used, and the base layer mainly composed of the second cured epoxy resin.
  • conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes.
  • the reaction component in the underlayer forming composition that is, the reaction condition of the second polyepoxide component and the second curing agent, specifically includes heat treatment at 70 to 150 ° C. for about 1 to 60 minutes. It is done.
  • a treatment such as performing UV irradiation at 100 to 500 mJ / cm 2 for 1 to 5 seconds with a UV curing device or the like can be given.
  • the reaction of the composition for forming an underlayer is performed under a constant humidification condition.
  • the reaction time can be shortened in the reaction performed under the same temperature conditions as compared with the case where no humidification is performed.
  • the reaction time is the same, the reaction can be sufficiently performed even if the reaction temperature is set low by humidification.
  • the reaction can be performed uniformly throughout the entire layer, and quality variations in the underlayer can be suppressed.
  • humidifying conditions include 40 to 80% RH, but 50 to 80% RH is more preferable. If more preferable reaction conditions are shown together with the temperature conditions, reaction conditions of 50 to 80% RH, 70 to 100 ° C., and 5 to 30 minutes can be mentioned. More preferable conditions include reaction conditions of 50 to 80% RH, 80 to 100 ° C., and 10 to 30 minutes.
  • step (4) of step (b) including steps (1) to (4) a water-absorbing layer-forming composition is applied to the surface of the base layer formed on the substrate in step (a).
  • the method can be the same as the coating method of the underlayer forming composition.
  • the coating thickness of the water-absorbing layer forming composition is such that the thickness of the water-absorbing layer finally obtained by reaction of the reaction components in the composition falls within the above range.
  • step (4) After applying the water-absorbing layer-forming composition on the underlayer, subsequently, in step (4), if necessary, the solvent is removed by drying, and a curing treatment is performed under conditions suitable for the reaction components to be used.
  • a water-absorbing layer containing oxide fine particles in the above proportion is used.
  • specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes.
  • a reaction condition of the reaction component in the water-absorbing layer forming composition that is, the first polyepoxide component and the first curing agent
  • heat treatment at 50 to 120 ° C. for about 10 to 60 minutes can be mentioned. It is done.
  • a UV curable photocurable resin a treatment such as performing UV irradiation of 50 to 1000 mJ / cm 2 for 5 to 10 seconds with a UV curing device or the like can be given.
  • reaction conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes.
  • reaction conditions of the polyol and polyisocyanate specifically include heat treatment at 50 to 200 ° C. for about 1 to 60 minutes.
  • the reaction is performed by using the composition for forming the underlayer.
  • a constant humidifying condition in that the scratch resistance such as scratch resistance and the like can be remarkably improved.
  • Specific examples of the humidification condition include 40 to 80% RH, but a condition of 50 to 80% RH is more preferable. If more preferable reaction conditions are shown together with the temperature conditions, reaction conditions of 50 to 80% RH, 70 to 100 ° C., and 5 to 30 minutes can be mentioned. More preferable conditions include reaction conditions of 50 to 80% RH, 80 to 100 ° C., and 10 to 30 minutes.
  • the antifogging article of the present invention in which the antifogging film is formed on the substrate is obtained through the step (b) or the steps (a) and (b).
  • the step (c) is obtained after the step (b).
  • the base layer and the water absorbing layer are preferably formed on the interior substrate surface when applied to a building window glass, and formed on the interior substrate surface when applied to a vehicle window glass. preferable.
  • Examples 1 to 7 are examples, and examples 8 and 9 are comparative examples.
  • Denacol is a trade name of Nagase ChemteX Corporation.
  • Low molecular weight polyepoxide (first polyepoxide component) Glycerin polyglycidyl ether: Denacol EX-313 (Mw: 383, average number of epoxy groups: 2.0 / molecule),
  • Evaluation of the anti-fogging article in each example was performed as follows. [Measurement of film thickness] A cross-sectional image of the antifogging article was taken with a scanning electron microscope (manufactured by Hitachi, Ltd., S4300), and the film thickness of the water absorption layer was measured. [Measurement of haze value] In accordance with the standard of JIS K-7361, the haze value [%] (shown as “Haze” in Table 1 to be described later) of the antifogging article is measured using a haze meter (Hazeguard Plus, manufactured by Gardner). did.
  • Anti-fogging time Anti-fogging until a specimen is left in an environment of 20 ° C. and a relative humidity of 50% for 1 hour and then the specimen surface is put on a hot water bath at 40 ° C. until cloudiness or distortion of a fluoroscopic image due to a water film is observed. Time (seconds) was measured. A normal soda-lime glass that has not been subjected to anti-fogging processing was fogged or a fluoroscopic image was distorted by a water film in 1 to 2 seconds. The required anti-fogging performance varies depending on the application. In this example, antifogging property of 90 seconds or more is necessary for practical use, and 100 seconds or more is preferable.
  • the moisture content was measured with a trace moisture meter FM-300 (Kett Science Laboratory Co., Ltd.) as follows. The measurement sample was heated at 120 ° C. for the same time as the blank measurement, the amount of water released from the sample was measured, and the maximum value during that time was adopted as the amount of water.
  • the water content (II) of soda lime glass not subjected to normal antifogging processing was 0.11 mg.
  • organosilica sol (10.81 g, MEK-ST (trade name)
  • 8.81 g, neoethanol PIP (product) Name manufactured by Daishin Chemical Co., Ltd.
  • a leveling agent 0.02 g, BYK307 (trade name), manufactured by Big Chemie
  • Production Example B-1 33% by mass (1/3) of the total amount of silica fine particles contained in the water-absorbing layer in the above-described step (1) in the production method of the present invention is added to the liquid composition.
  • 67% by mass (2/3) of the total amount of silica fine particles contained in the water absorption layer was added to the liquid composition.
  • Table 1 the case where it added by said each addition amount in process (1) and process (3) is shown as "A1B2" in the column of the addition method.
  • organosilica sol 15.26 g, MEK-ST (trade name)
  • a leveling agent 0.02 g, BYK307 (trade name), manufactured by Big Chemie
  • Production Example B-2 as in Production Example B-1, an amount of 33% by mass (1/3) of the total amount of silica fine particles contained in the water absorbing layer in Step (1) is added to the liquid composition.
  • the addition method is “A1B2”.
  • Production Example B-4 25% by mass (1/4) of the total amount of silica fine particles contained in the water-absorbing layer in the above-described step (1) in the production method of the present invention is added to the liquid composition.
  • 75% by mass (3/4) of the total amount of silica fine particles contained in the water absorption layer was added to the liquid composition.
  • Table 1 the case where it added by said each addition amount in process (1) and process (3) is shown as "A1B3" in the column of the addition method.
  • Glycol (60.00 g, average hydroxyl value: 113 mg KOH / g, average molecular weight 1000, manufactured by Lion) hexamethylene diisocyanate type polyisocyanate (36.00 g, NCO%: 23%, Desmodur N3200 (trade name), Bayer AG Co., Ltd.), organosilica sol (52.27 g, MEK-ST-L (trade name), manufactured by Nissan Chemical Industries, Ltd., SiO 2 content 30 mass%) were added with stirring, and the mixture was stirred at 25 ° C. for 1 hour. .
  • organosilica sol (156.82 g, MEK-ST-L (trade name)), isobutyl acetate (165.53 g, manufactured by Junsei Kagaku), leveling agent (0.05 g, BYK307 (trade name), manufactured by Big Chemie) was added with stirring to obtain a water-absorbing layer-forming composition (B-5).
  • Production Example B-5 as in Production Example B-4, an amount of 25% by mass (1/4) of the total amount of silica fine particles contained in the water absorption layer in Step (1) is added to the liquid composition. Then, 75% by mass (3/4) of the total amount of silica fine particles contained in the water absorbing layer in step (3) was added to the liquid composition.
  • the addition method is “A1B3”.
  • Examples 1 to 3 A clean soda-lime glass substrate (water contact angle 3 °, 200 mm ⁇ 200 mm ⁇ thickness 2 mm), which was polished and cleaned with cerium oxide, was used as a substrate, and a manufacturing example (A- The underlayer-forming composition (A-1) obtained in 1) was applied by flow coating, held in an electric furnace at 90 ° C. for 10 minutes, and then held in a constant temperature and humidity chamber at 90 ° C. and 70% RH for 20 minutes. Then, an underlayer was formed. Then, on the surface of the formed underlayer, as shown in Table 1 for each example, the water-absorbing layer forming compositions (B-1) to (B-) obtained in Production Examples (B-1) to (B-3) were used.
  • Example 4 As a substrate, a clean soda lime glass substrate (water contact angle 3 °, 200 mm ⁇ 200 mm ⁇ thickness 2 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the glass substrate was shown for each example. As shown in FIG. 1, either the foundation layer forming composition (A-1) or the adhesion layer forming composition (A-2) obtained in Production Example (A-1) was applied by flow coating, and 100 The substrate was kept in an electric furnace at 0 ° C. for 30 minutes to form a base layer or an adhesion layer.
  • the water-absorbing layer forming composition obtained in Production Examples (B-1) and (B-4) to (B-6) was formed on the surface of the formed underlayer or adhesion layer as shown in Table 1 for each example. Any one of the products (B-1), (B-4) to (B-6) is applied by flow coating and held in an electric furnace at 100 ° C. for 30 minutes to form a water absorption layer, and the underlayer and water absorption An antifogging article having an antifogging film composed of two layers was obtained.
  • Example 5 As the substrate, a clean soda lime glass substrate (water contact angle 3 °, 200 mm ⁇ 200 mm ⁇ thickness 2 mm), the surface of which was polished and washed with cerium oxide, was used.
  • the water-absorbing layer-forming composition (B-1) obtained in 1) is applied by flow coating and held in an electric furnace at 100 ° C. for 30 minutes to form a water-absorbing layer and have a single layer of anti-fogging film An antifogging article was obtained.
  • the symbols shown in the column of the method for adding metal oxide fine particles indicate the addition time and amount of the metal oxide fine particles when preparing the water absorbing layer forming composition.
  • “A1B2” indicates that 33% of the total amount of fine particles is added in the step (1) and the remaining 67% is added in the step (3).
  • “A1B3” represents that 25% of the total amount of fine particles is added in the step (1) and the remaining 75% is added in the step (3).
  • “A” indicates that the total amount of fine particles is added in the step (1).
  • the content of the metal fine particles indicates the content of the metal fine particles in the obtained water absorption layer in mass%.
  • the antifogging articles obtained in Examples 1 to 7 as examples have excellent antifogging properties and scratch resistance, and the haze value is sufficiently low. It can be seen that the antifogging articles obtained in Comparative Examples 8 and 9 are insufficient in antifogging property, scratch resistance or low haze value.
  • the antifogging article of the present invention is useful as an antifogging glass for automobiles and buildings because it has excellent antifogging properties and scratch resistance such as scratch resistance. It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2011-118413 filed on May 26, 2011 are incorporated herein as the disclosure of the present invention.

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Abstract

L'invention porte sur un article antibuée qui présente d'excellentes propriétés antibuée, qui est excellent en termes de résistance à la rayure telle que la résistance aux éraflures et qui présente un faible voile initial et sur un procédé pour la production de l'article antibuée. L'article antibuée comprend une base et une couche absorbant l'eau qui a été disposée sur une surface de la base et qui contient une résine réticulée ayant des propriétés d'absorption de l'eau et il est caractérisé en ce que la couche absorbant l'eau contient de fines particules d'oxyde métallique à hauteur de 20-60 % en masse par rapport à la quantité totale et en ce qu'il présente un voile inférieur ou égal à 1 %. Le procédé, qui sert à produire un article antibuée qui comprend une base et, disposée sur une surface de la base, une couche absorbant l'eau comprenant une résine réticulée absorbant l'eau et de fines particules d'oxyde métallique, la quantité des particules étant de 20-60 % en masse par rapport à la quantité de la couche totale, comprend : l'ajout d'une partie de la quantité des fines particules d'oxyde métallique devant être contenues à une composition liquide qui contient des matières de départ pour la résine réticulée ce qui de cette manière amène une réaction de réticulation à avoir lieu ; après cela, l'ajout du reste des fines particules d'oxyde métallique pour de cette manière amener la réaction de réticulation à se poursuivre ; l'application de la composition liquide sur une surface de la base ; et le fait d'amener encore la réaction de réticulation à avoir lieu, ce qui forme de cette manière une couche absorbant l'eau.
PCT/JP2012/063553 2011-05-26 2012-05-25 Article antibuée et son procédé de production WO2012161330A1 (fr)

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WO2015152047A1 (fr) * 2014-04-01 2015-10-08 旭硝子株式会社 Composition d'agent antibuée, et article antibuée ainsi que procédé de fabrication de celui-ci
CN105593443A (zh) * 2014-07-18 2016-05-18 三井金属爱科特株式会社 车辆用门锁装置
WO2017159564A1 (fr) 2016-03-14 2017-09-21 旭化成株式会社 Film de revêtement et composition de revêtement antibuée hautement durable
WO2019163918A1 (fr) 2018-02-23 2019-08-29 旭化成株式会社 Film de revêtement antibuée hautement durable, et composition de revêtement

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JP6578479B2 (ja) * 2015-07-08 2019-09-25 セントラル硝子株式会社 防曇性被膜形成用塗布剤、防曇性被膜形成物品及び防曇性被膜形成物品の製造方法
WO2017006707A1 (fr) * 2015-07-08 2017-01-12 セントラル硝子株式会社 Agent de revêtement pour former un film de revêtement antibuée, article recouvert d'un film antibuée et procédé de production d'un article recouvert d'un film antibuée
WO2017033532A1 (fr) * 2015-08-21 2017-03-02 セントラル硝子株式会社 Revêtement anti-buée, article à revêtement anti-buée, et procédé de production dudit article à revêtement anti-buée
JP2020011404A (ja) * 2018-07-13 2020-01-23 清水建設株式会社 コンクリート成形用型枠およびその製造方法

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JP2008273067A (ja) * 2007-04-27 2008-11-13 Asahi Glass Co Ltd 防曇性物品および該防曇性物品の製造方法

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WO2015152047A1 (fr) * 2014-04-01 2015-10-08 旭硝子株式会社 Composition d'agent antibuée, et article antibuée ainsi que procédé de fabrication de celui-ci
CN105593443A (zh) * 2014-07-18 2016-05-18 三井金属爱科特株式会社 车辆用门锁装置
CN105593443B (zh) * 2014-07-18 2017-08-04 三井金属爱科特株式会社 车辆用门锁装置
US10407950B2 (en) 2014-07-18 2019-09-10 Mitsui Kinzoku Act Corporation Vehicle door latch device
WO2017159564A1 (fr) 2016-03-14 2017-09-21 旭化成株式会社 Film de revêtement et composition de revêtement antibuée hautement durable
KR20180093065A (ko) 2016-03-14 2018-08-20 아사히 가세이 가부시키가이샤 고내구 방담 도막 및 코팅 조성물
KR20210022782A (ko) 2016-03-14 2021-03-03 아사히 가세이 가부시키가이샤 고내구 방담 도막 및 코팅 조성물
US11041076B2 (en) 2016-03-14 2021-06-22 Asahi Kasei Kabushiki Kaisha Highly durable antifogging coating film and coating composition
WO2019163918A1 (fr) 2018-02-23 2019-08-29 旭化成株式会社 Film de revêtement antibuée hautement durable, et composition de revêtement
JPWO2019163918A1 (ja) * 2018-02-23 2020-12-17 旭化成株式会社 高耐久防曇塗膜およびコーティング組成物
JP7087059B2 (ja) 2018-02-23 2022-06-20 旭化成株式会社 高耐久防曇塗膜およびコーティング組成物
US11781037B2 (en) 2018-02-23 2023-10-10 Asahi Kasei Kabushiki Kaisha High-durability antifogging coating film and coating composition

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