WO2017104612A1 - Stratifié anti-opalescence et anti-tâches, produit et son procédé de fabrication - Google Patents

Stratifié anti-opalescence et anti-tâches, produit et son procédé de fabrication Download PDF

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Publication number
WO2017104612A1
WO2017104612A1 PCT/JP2016/086913 JP2016086913W WO2017104612A1 WO 2017104612 A1 WO2017104612 A1 WO 2017104612A1 JP 2016086913 W JP2016086913 W JP 2016086913W WO 2017104612 A1 WO2017104612 A1 WO 2017104612A1
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Prior art keywords
layer
fogging
antifogging
antifouling laminate
antifouling
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PCT/JP2016/086913
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English (en)
Japanese (ja)
Inventor
水野　幹久
祥吾 坂本
忍 原
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デクセリアルズ株式会社
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Priority claimed from JP2016089429A external-priority patent/JP7161836B2/ja
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Publication of WO2017104612A1 publication Critical patent/WO2017104612A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents

Definitions

  • the present invention has an antifogging and antifouling property, and further has an antireflection function, can be used in a wide range of applications such as automobiles and optical applications, and is easy to form and process.
  • the present invention relates to an article using an anti-fogging laminate and a method for producing the same.
  • a resin film, glass, or the like is attached to the surface.
  • the visibility and aesthetics of the article may deteriorate due to fogging and soiling of resin films, glass, etc. that decorate and protect the surface of the article. Therefore, in order to prevent the visibility and aesthetics of such articles from deteriorating, the resin film and glass are subjected to antifogging treatment and antifouling treatment.
  • Patent Document 1 a resin molded product provided with an antifogging organic hard coat layer has been proposed (see, for example, Patent Document 1). Further, for example, an antifogging coating film composed of an antifogging coating composition containing a random copolymer formed from a plurality of monomers and a polyfunctional blocked isocyanate compound has been proposed (for example, Patent Documents). 2). Further, for example, a molding hard coat film having antifouling properties has been proposed (see, for example, Patent Document 3). Moreover, for example, an optical article having antifogging properties and antifouling properties has been proposed (see, for example, Patent Document 4). For example, a hard coat sheet in which a coating layer having antifogging properties, antifouling properties, and hard coat properties is formed has been proposed (see, for example, Patent Document 5).
  • an antireflection function as an optical function may be required for a film attached to the surface of an article.
  • an antireflection film including a specific cured film as a low refractive index layer has been proposed (see, for example, Patent Document 6).
  • the present invention provides an antifogging and antifouling laminate having excellent antifogging and antifouling properties and excellent antireflection function, an article using the antifogging and antifouling laminate, and a method for producing the same.
  • the purpose is to provide.
  • Means for solving the problems are as follows. That is, ⁇ 1> A first layer and a second layer on at least one surface of the base material and the base material, The first layer contains a hydrophilic molecular structure; The second layer contains a low refractive index filler; The antifogging and antifouling laminate is characterized in that the contact angle of pure water on the surface of the second layer is 90 ° or more. ⁇ 2> The antifogging and antifouling laminate according to ⁇ 1>, wherein the first layer and the second layer have a third layer different from the first layer and the second layer. Is the body.
  • ⁇ 3> The anti-fogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 2>, wherein the dynamic friction coefficient of the second layer is 0.4 or less.
  • ⁇ 4> The antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the luminous reflectance is 3.0% or less.
  • ⁇ 5> The antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the second layer contains a water repellent molecular structure.
  • ⁇ 6> The antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the second layer contains a hydrophilic molecular structure.
  • ⁇ 7> The antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the hydrophilic molecular structure contained in the first layer is a polyoxyalkylene chain.
  • ⁇ 8> An article having the antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 7> on a surface thereof.
  • ⁇ 9> The method for producing an article according to ⁇ 8>, A heating step of heating the antifogging and antifouling laminate, An anti-fogging and antifouling laminate forming step for forming the heated antifogging and antifouling laminate into a desired shape; and And an injection molding step of molding the molding material by injecting a molding material onto the base material side of the anti-fogging and antifouling laminate molded into a desired shape.
  • the heating in the heating step is performed by infrared heating.
  • the conventional problems can be solved, the object can be achieved, the antifogging and antifouling laminate has excellent antifogging and antifouling properties, and is excellent in antireflection function.
  • An article using the anti-fogging and antifouling laminate and a method for producing the same can be provided.
  • FIG. 1 is a schematic sectional view of an example of the anti-fogging and antifouling laminate of the present invention.
  • FIG. 2 is a schematic cross-sectional view of another example of the anti-fogging and antifouling laminate of the present invention.
  • FIG. 3 is a schematic cross-sectional view of another example of the anti-fogging and antifouling laminate of the present invention.
  • FIG. 4A is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 4B is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 4C is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 4A is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 4B is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 4D is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 4E is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 4F is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 5 is a schematic sectional drawing of an example of the articles
  • FIG. 6 is a schematic sectional drawing of an example of the articles
  • FIG. 7: is a schematic sectional drawing of an example of the articles
  • FIG. 8 is a schematic sectional drawing of an example of the articles
  • the anti-fogging and antifouling laminate of the present invention has at least a substrate, a first layer, and a second layer, and further includes other members as necessary.
  • the first layer of the first layer and the second layer is arranged at a position close to the base material.
  • Base material> There is no restriction
  • a triacetyl cellulose TAC
  • polyester TPE
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PE polyacrylate
  • PMMA acrylic resin
  • PC Polycarbonate
  • epoxy resin epoxy resin, urea resin, urethane resin, melamine resin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (CO ), PC / PMMA laminate, such as rubber additives PMMA and the like.
  • the resin substrate may be a triacetyl cellulose (TAC), polyester (TPEE), a polyethylene terephthalate (PET), a polyethylene naphthalate ( PEN), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyether sulfone, polysul
  • Examples of the material for the inorganic base material include metal oxides (eg, quartz, sapphire, glass, etc.), metals (eg, iron, chromium, nickel, molybdenum, niobium, copper, titanium, aluminum, zinc, silicon, magnesium). , Manganese, etc.), alloys (for example, combinations of the above metals), and the like.
  • the substrate has transparency.
  • the average thickness of the resin substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m to 1,000 ⁇ m, and preferably 50 ⁇ m to 500 ⁇ m. Is more preferable.
  • the average thickness of the inorganic substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 mm to 100 mm.
  • the numerical range defined using “to” in this specification is a range including a lower limit value and an upper limit value. That is, “5 ⁇ m to 1,000 ⁇ m” is synonymous with “5 ⁇ m to 1,000 ⁇ m”.
  • a character, pattern, image or the like may be printed on the surface of the substrate.
  • a binder layer may be provided.
  • various adhesives can be used in addition to various binders such as acrylic, urethane, polyester, polyamide, ethylene butyl alcohol, and ethylene vinyl acetate copolymer systems.
  • Two or more binder layers may be provided.
  • the binder to be used one having heat sensitivity and pressure sensitivity suitable for the molding material can be selected.
  • the surface of the resin base material on the side opposite to the first layer and the second layer side May have a wrinkle pattern.
  • the wrinkle pattern can be formed by wrinkle processing, for example.
  • blocking means that it is difficult to separate each sheet when a plurality of sheets are stacked.
  • the first layer contains a hydrophilic molecular structure.
  • the first layer is preferably a resin layer in terms of easy production. There is no restriction
  • the hydrophilic molecular structure is not particularly limited as long as it is a hydrophilic molecular structure, and can be appropriately selected according to the purpose. Examples thereof include a hydrophilic organic molecular structure. Specifically, , Polyoxyalkyl chain, polyoxyalkylene chain and the like.
  • the hydrophilic molecular structure can be introduced into the first layer, for example, by using a hydrophilic monomer described later when the first layer is produced.
  • the active energy ray-curable resin composition contains at least a hydrophilic monomer having a radical polymerizable unsaturated group (hereinafter sometimes referred to as “hydrophilic monomer”) and a photopolymerization initiator, and is further necessary. Depending on the content, other components are contained.
  • hydrophilic monomer-- examples include (meth) acrylate having a polyoxyalkylene chain, quaternary ammonium salt-containing (meth) acrylate, tertiary amino group-containing (meth) acrylate, and sulfonic acid. Examples thereof include a group-containing monomer, a carboxylic acid group-containing monomer, a phosphoric acid group-containing monomer, and a phosphonic acid group-containing monomer. These may be monofunctional monomers or polyfunctional monomers. Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.
  • (meth) acrylate means acrylate or methacrylate. The same applies to (meth) acryloyl and (meth) acryl.
  • hydrophilic monomer examples include mono- or polyacrylates obtained by a reaction between a polyhydric alcohol (polyol or polyhydroxy-containing compound) and a compound selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof, Alternatively, mono or polymethacrylate can be used.
  • polyhydric alcohol examples include divalent alcohol, trivalent alcohol, and tetravalent or higher alcohol.
  • divalent alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a number average molecular weight of 300 to 1,000, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedi For example, methanol.
  • trivalent alcohol examples include trimethylolethane, trimethylolpropane, pentaglycerol, glycerol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like.
  • tetravalent or higher alcohol examples include pentaerythritol, diglycerol, and dipentaerythritol.
  • Examples of the (meth) acrylate having a polyoxyalkylene chain include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, ethoxylated glycerin (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate. It is done.
  • Examples of the polyethylene glycol (meth) acrylate include methoxypolyethylene glycol (meth) acrylate.
  • a commercial item can be used as said methoxypolyethyleneglycol (meth) acrylate.
  • the commercially available product include MEPM-1000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • MEPM-1000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • ethoxylated glycerin (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate are preferable from the viewpoint that both the appropriate hardness and hydrophilicity of the first layer can be achieved.
  • Examples of the quaternary ammonium salt-containing (meth) acrylate include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethyldimethylglycidylammonium chloride, (meth) Acryloyloxyethyltrimethylammonium methyl sulfate, (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidopropyldimethyl Benzyl ammonium chloride, (meth) acrylamide Pills dimethyl glycidyl chloride, (
  • Examples of the tertiary amino group-containing (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, 1,2, Examples include 2,6,6-pentamethylpiperidyl (meth) acrylate and 2,2,6,6-tetramethylpiperidyl (meth) acrylate.
  • Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, and sulfonic acid group-containing (meth) acrylate.
  • Examples of the sulfonic acid group-containing (meth) acrylate include, for example, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and terminal sulfonic acid-modified polyethylene glycol mono (meth) Examples include chlorate. These may form a salt. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like.
  • Examples of the carboxylic acid group-containing monomer include acrylic acid and methacrylic acid.
  • Examples of the phosphate group-containing monomer include (meth) acrylate having a phosphate ester.
  • the hydrophilic monomer is preferably a polyfunctional hydrophilic monomer.
  • the molecular weight of the hydrophilic monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 200 or more.
  • the hydrophilic monomer may be a commercially available product.
  • examples of the commercially available product include SR9035 (manufactured by Sartomer, ethoxylated trimethylolpropane trimethacrylate).
  • photopolymerization initiator examples include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxyglycolyl.
  • the radical photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,6-dimethylbenzoyl).
  • the content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 10% by mass, 0.5% by mass to 8% by mass is more preferable, and 1% by mass to 5% by mass is particularly preferable.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition.
  • urethane (meth) acrylate isocyanuric acid group containing (meth) acrylate, a filler, etc. are mentioned. These may be used to adjust the elongation rate, hardness, etc. of the first layer.
  • the urethane (meth) acrylate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate. Among these, aliphatic urethane (meth) acrylate is preferable.
  • the content of the urethane (meth) acrylate in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass to 45% by mass, More preferred is 40% by weight, and especially preferred is 20% to 35% by weight.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition.
  • the active energy ray-curable resin composition may further contain a leveling agent for improving smoothness.
  • the content of the leveling agent in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.0001% by mass to 5% by mass.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition.
  • the active energy ray-curable resin composition can be diluted with an organic solvent when used.
  • organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl
  • organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl
  • formamide dimethyl sulfoxide, dimethylacetamide, and the like.
  • the active energy ray-curable resin composition is cured when irradiated with active energy rays.
  • active energy ray There is no restriction
  • the average thickness of the first layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 ⁇ m to 100 ⁇ m, more preferably 4 ⁇ m to 50 ⁇ m, and particularly preferably 10 ⁇ m to 30 ⁇ m.
  • the average thickness is within a preferable range, it is advantageous in that the antifogging property is excellent, the interference unevenness is reduced, and the productivity is excellent.
  • interference unevenness can be further reduced.
  • the pure water contact angle on the surface of the second layer is 90 ° or more.
  • the second layer contains at least a low refractive index filler, and further contains other components as necessary.
  • the second layer is, for example, a cured product of an active energy ray curable resin composition.
  • the second layer preferably contains a water repellent molecular structure.
  • the water-repellent molecular structure contributes to increasing the pure water contact angle and also contributes to improving the antireflection function.
  • the second layer preferably contains a hydrophilic molecular structure. When the second layer has the hydrophilic molecular structure, the antifogging property is improved.
  • the water-repellent molecular structure is not particularly limited as long as it is a water-repellent molecular structure, and can be appropriately selected according to the purpose. Examples thereof include a water-repellent organic molecular structure. , Fluoroalkyl group, fluoroalkyl ether group, dimethylsiloxane group and the like.
  • the water-repellent molecular structure uses, for example, a water-repellent monomer having a radical polymerizable unsaturated group described later (hereinafter sometimes referred to as “water-repellent monomer”) when the second layer is formed. Can be introduced into the second layer.
  • the hydrophilic molecular structure is not particularly limited as long as it is a hydrophilic molecular structure, and can be appropriately selected according to the purpose. Examples thereof include a hydrophilic organic molecular structure. Specifically, , Polyoxyalkyl chain, polyoxyalkylene chain and the like.
  • the hydrophilic molecular structure can be introduced into the second layer by using the hydrophilic monomer when the second layer is produced, for example.
  • the surface of the second layer is preferably smooth.
  • that the surface is smooth means that there are no intentionally formed convex portions or concave portions on the surface.
  • fine convex portions or concave portions by physical processing are not formed on the surface. It is preferable. Since the second layer does not have fine convex portions or concave portions on the surface, aqueous stains and / or oily stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) are difficult to adhere. Moreover, even if those stains are adhered, it can be easily removed with a tissue or the like, and an article having excellent anti-fogging properties can be obtained.
  • the pure water contact angle on the surface of the second layer is 90 ° or more, preferably 100 ° or more, more preferably 110 ° or more, and particularly preferably 115 ° or more.
  • the pure water contact angle can be measured, for example, using a contact angle meter PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions.
  • -Put distilled water in a plastic syringe attach a stainless steel needle to the tip, and drop it onto the evaluation surface.
  • ⁇ Drip amount of water 2 ⁇ L
  • Measurement temperature 25 °C
  • the contact angle after 5 seconds from dropping water is measured at any 10 locations on the surface of the second layer, and the average value is defined as the pure water contact angle.
  • the hexadecane contact angle on the surface of the second layer is preferably 30 ° or more, more preferably 60 ° or more, still more preferably 70 ° or more, and particularly preferably 80 ° or more.
  • the hexadecane contact angle is within the preferred range, even when fingerprints, sebum, sweat, tears, cosmetics, etc. adhere to the surface, it can be easily wiped away, and excellent antifogging properties can be maintained. It is advantageous.
  • the hexadecane contact angle can be measured, for example, using a contact angle meter PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions.
  • -Put hexadecane in a plastic syringe attach a Teflon-coated stainless steel needle to the tip, and drop it onto the evaluation surface.
  • ⁇ Drop amount of hexadecane 1 ⁇ L
  • Measurement temperature 25 °C
  • the contact angle after 20 seconds from the dropping of hexadecane is measured at any 10 locations on the surface of the second layer, and the average value is defined as the hexadecane contact angle.
  • the pure water contact angle is within the above range and the hexadecane contact angle is within the above range, water-based stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) and / or oily stains are adhered. Even in those cases, the dirt is prevented from penetrating the first layer. Therefore, the dirt can be easily wiped off by wiping with a tissue or the like, and the antifogging property returns to the state before the dirt is adhered.
  • water-based stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) and / or oily stains are adhered. Even in those cases, the dirt is prevented from penetrating the first layer. Therefore, the dirt can be easily wiped off by wiping with a tissue or the like, and the antifogging property returns to the state before the dirt is adhered.
  • the dynamic friction coefficient of the second layer is preferably 0.4 or less. By doing so, the physical pressure by wiping can be kept low, and scratch resistance is improved. In addition, the ability to wipe off dirt with a tissue or the like is improved.
  • the dynamic friction coefficient can be measured, for example, by the following method. Measurement is performed using Triboster TS501 (trade name; manufactured by Kyowa Interface Science Co., Ltd.). BEMCOT (registered trademark) M-3II (trade name, manufactured by Asahi Kasei Co., Ltd.) is attached to the surface contactor with a double-sided tape, measuring load 50 g / cm 2 , measuring speed 1.7 mm / s, measuring distance 20 mm, 12 times. Measure and obtain the average value. This is repeated at five arbitrary locations, and the average value of the five values obtained is taken as the dynamic friction coefficient.
  • the low refractive index filler is not particularly limited as long as it is a low refractive index filler, and can be appropriately selected according to the purpose.
  • “low refractive index” means a refractive index lower than the refractive index of 1.50 to 1.70 of a general plastic.
  • Examples of the refractive index of the low refractive index filler include 1.10 to 1.40.
  • Examples of the material for the low refractive index filler include magnesium fluoride, lithium fluoride, calcium fluoride, aluminum fluoride, and silica.
  • Examples of the structure of the low refractive index filler include solid particles, hollow particles, and porous particles. Among these, as the low refractive index filler, hollow silica and porous silica are preferable.
  • the average particle size of the low refractive index filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm to 200 nm, and more preferably 10 nm to 100 nm.
  • the surface of the low refractive index filler is preferably surface-treated with an organic dispersant having a (meth) acryl group, a vinyl group, or an epoxy group at the terminal.
  • the organic dispersant is copolymerized with surrounding monomers in the curing step of the active energy ray-curable resin composition containing the low refractive index filler, and the resulting cured product contains the low refractive index filler and is entirely contained. Since they are integrated, the coating strength and flexibility are improved.
  • the content of the low refractive index filler in the second layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 80% by mass. When the content is less than 5% by mass, a sufficient antireflection function may not be obtained, and when it exceeds 80% by mass, scratch resistance and workability may be deteriorated.
  • the active energy ray curable resin composition comprises the low refractive index filler, a water repellent monomer, and a polymerization initiator. Containing, preferably containing a hydrophilic monomer, and further containing other components as required.
  • hydrophilic monomer examples include the hydrophilic monomer in the description of the first layer.
  • the preferred embodiment is also the same.
  • polymerization initiator the said polymerization initiator in description of the said 1st layer is mentioned, for example.
  • the preferred embodiment is also the same.
  • the other components include the other components in the description of the first layer. The preferred embodiment is also the same.
  • Water repellent monomer- Examples of the water repellent monomer having a radical polymerizable unsaturated group include a monomer having a radical polymerizable unsaturated group and at least one of fluorine and silicon.
  • Examples of such water-repellent monomers include (meth) acrylates having at least one of fluorine and silicon, and further examples include fluorinated (meth) acrylates, silicone (meth) acrylates, and the like. More specifically, (meth) acrylate having a fluoroalkyl group, (meth) acrylate having a fluoroalkyl ether group, (meth) acrylate having a dimethylsiloxane group, and the like can be given.
  • Examples of the water repellent monomer further include water repellent monomers classified into the following (1) to (5).
  • Fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, chlorotrifluoroethylene;
  • alkyl perfluoro vinyl ethers or alkoxyalkyl perfluoro vinyl ethers such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether);
  • Perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether);
  • Fluorine-containing (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (
  • the water repellent monomer may be a commercially available product.
  • commercially available products of the fluorinated (meth) acrylate include KY-1200 series manufactured by Shin-Etsu Chemical Co., Ltd., MegaFac RS series manufactured by DIC Corporation, and OPTOOL DAC manufactured by Daikin Industries, Ltd.
  • Examples of commercially available silicone (meth) acrylates include X-22-164 series manufactured by Shin-Etsu Chemical Co., Ltd., and TEGO Rad series manufactured by Evonik.
  • 0.018 mass% is preferable, 0.018 mass % To less than 5.0% by mass, more preferably 0.075% by mass to 3.0% by mass, and particularly preferably 0.18% by mass to 1.5% by mass.
  • the content is 5.0% by mass or more, although the water repellency of the cured product is excellent, the glass transition temperature becomes low, so that it becomes too soft and wear resistance may be lowered.
  • the breath antifogging property may be lowered.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition.
  • the average thickness of the second layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is 10 nm to 200 nm from the viewpoint that the luminous reflectance can be reduced and the antireflection function can be enhanced. 10 nm to 100 nm is more preferable.
  • the third layer is not particularly limited as long as it is disposed between the first layer and the second layer and is different from the first layer and the second layer. It can be selected as appropriate according to the conditions. By providing the third layer, scratch resistance is improved.
  • examples of the layer different from the first layer and the second layer include a layer thinner than the first layer and thicker than the second layer.
  • the pure water contact angle on the surface of the third layer is preferably 65 ° or less.
  • the third layer is preferably a resin layer in terms of easy manufacture.
  • the third layer preferably contains a hydrophilic molecular structure.
  • the hydrophilic molecular structure in the third layer preferably has a molecular weight of 1000 or less.
  • the adhesion between the first layer and the third layer is improved.
  • limiting in particular as said 3rd layer Although it can select suitably according to the objective, It is preferable to contain the hardened
  • the active energy ray-curable resin composition contains, for example, at least a hydrophilic monomer having a radical polymerizable unsaturated group (hereinafter sometimes referred to as “hydrophilic monomer”) and a photopolymerization initiator, Furthermore, other components are contained as necessary.
  • hydrophilic monomer examples include the hydrophilic monomer in the description of the first layer.
  • the preferred embodiment is also the same.
  • polymerization initiator the said polymerization initiator in description of the said 1st layer is mentioned, for example.
  • the preferred embodiment is also the same.
  • the other components include the other components in the description of the first layer. The preferred embodiment is also the same.
  • the average thickness of the third layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m, and more preferably 0.5 ⁇ m to 2 ⁇ m. Is particularly preferred.
  • the fourth layer is not particularly limited as long as it is a layer that is disposed between the first layer and the second layer and contains a high refractive index filler, and is appropriately selected according to the purpose. be able to. It is preferable that the anti-fogging and antifouling laminate has the fourth layer in that the luminous reflectance can be reduced and the antireflection function can be enhanced.
  • the high refractive index filler is not particularly limited as long as it is a filler having a higher refractive index than the low refractive index filler, and can be appropriately selected according to the purpose.
  • the refractive index of the high refractive index filler is preferably 1.60 or more, and preferably 1.70 to 2.50.
  • the material of the high refractive index filler is not particularly limited and may be appropriately selected depending on the intended purpose. However, titania, zirconia, tin oxide, indium tin oxide, antimony-doped tin oxide, antimony pentoxide, alumina, oxide Examples include zinc.
  • the high refractive index filler is preferably solid particles.
  • the average particle size of the high refractive index filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm to 200 nm, and more preferably 10 nm to 100 nm.
  • the surface of the high refractive index filler is preferably surface-treated with an organic dispersant having a (meth) acryl group, a vinyl group, or an epoxy group at the terminal.
  • the organic dispersant is copolymerized with surrounding monomers in the curing step of the active energy ray-curable resin composition containing the high refractive index filler, and the resulting cured product contains the high refractive index filler and the whole Since they are integrated, the coating strength and flexibility are improved.
  • the content of the high refractive index filler in the fourth layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 80% by mass. When the content is less than 5% by mass, a sufficient antireflection function may not be obtained, and when it exceeds 80% by mass, scratch resistance and workability may be deteriorated.
  • the fourth layer preferably contains a hydrophilic molecular structure in terms of improving antifogging properties.
  • the hydrophilic molecular structure is not particularly limited as long as it is a hydrophilic molecular structure, and can be appropriately selected according to the purpose. Examples thereof include a hydrophilic organic molecular structure. Specifically, , Polyoxyalkyl chain, polyoxyalkylene chain and the like.
  • the hydrophilic molecular structure can be introduced into the fourth layer, for example, by using the hydrophilic monomer described above when the fourth layer is produced.
  • the said 4th layer contains the said high refractive index filler and a polymerization initiator at least, Preferably, it is hydrophilic Formed by applying an active energy ray-curable resin composition containing a monomer and further containing other components as necessary onto the first layer, and then irradiating and curing the active energy ray. The method of doing is mentioned.
  • hydrophilic monomer examples include the hydrophilic monomer in the description of the first layer.
  • the preferred embodiment is also the same.
  • polymerization initiator the said polymerization initiator in description of the said 1st layer is mentioned, for example.
  • the preferred embodiment is also the same.
  • the other components include the other components in the description of the first layer. The preferred embodiment is also the same.
  • the average thickness of the fourth layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 10 nm to 200 nm from the viewpoint that the luminous reflectance can be reduced and the antireflection function can be enhanced. 10 nm to 100 nm is more preferable.
  • the anchor layer is a layer disposed between the base material and the first layer. By disposing the anchor layer, the adhesion between the base material and the first layer can be improved.
  • the anchor layer preferably has a refractive index close to that of the first layer. Therefore, the refractive index of the anchor layer is preferably within ⁇ 0.10 of the refractive index of the first layer, and more preferably within ⁇ 0.05. Alternatively, the refractive index of the anchor layer is preferably between the refractive index of the first layer and the refractive index of the substrate.
  • the anchor layer can be formed, for example, by applying an active energy ray-curable resin composition. That is, the anchor layer is, for example, a cured product obtained by curing an active energy ray-curable resin composition with active energy rays.
  • the active energy ray-curable resin composition for example, an active energy ray-curable resin composition containing at least urethane (meth) acrylate and a photopolymerization initiator, and further containing other components as necessary.
  • the urethane (meth) acrylate and the photopolymerization initiator include the urethane (meth) acrylate and the photopolymerization initiator exemplified in the description of the first layer.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • examples of the material of the anchor layer include a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. These preferably have a radically polymerizable unsaturated group.
  • a method for forming the anchor layer when the substrate is an inorganic substrate for example, a solution in which the material is dissolved is applied onto the inorganic substrate, the solvent is dried, and then heat treatment is performed for a predetermined time. The method etc. are mentioned.
  • a solvent used for the solution a solvent that dissolves the material is selected.
  • water for example, water, alcohol (eg, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, etc.), anone (eg, cyclohexanone, cyclopentanone), amide
  • At least one selected from for example, N, N-dimethylformamide: DMF), sulfide (for example, dimethylsulfoxide: DMSO) and the like is used.
  • the coating method is not particularly limited, and a known coating method can be used.
  • Known coating methods include, for example, micro gravure coating method, wire bar coating method, direct gravure coating method, die coating method, dip method, spray coating method, reverse roll coating method, curtain coating method, comma coating method, knife coating method. , Spin coating, letterpress printing, offset printing, gravure printing, intaglio printing, rubber printing, screen printing, ink jet printing, and the like.
  • heating temperature it is 80 to 200 degreeC, for example.
  • the heating time is, for example, from 1 minute to 12 hours.
  • the average thickness of the anchor layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.3 ⁇ m to 3 ⁇ m. preferable.
  • the anchor layer may be provided with a function of reducing reflectivity or preventing charging.
  • the protective layer is a layer that protects the surface of the second layer (the surface having a pure water contact angle of 90 ° or more).
  • the said protective layer protects the said surface, when manufacturing the article
  • the protective layer is disposed on the surface of the second layer.
  • Examples of the material of the protective layer include the same material as that of the anchor layer.
  • the elongation percentage of the antifogging and antifouling laminate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% or more, more preferably 10% to 200%, and more preferably 40% to 150%. Is particularly preferred. If the elongation is less than 10%, molding may be difficult. When the elongation percentage is within the particularly preferable range, it is advantageous in that the moldability is excellent.
  • the said elongation rate can be calculated
  • the anti-fogging and antifouling laminate is formed into a strip having a length of 10.5 cm and a width of 2.5 cm to be used as a measurement sample.
  • the measurement temperature varies depending on the type of the resin base material, and the elongation percentage is measured at a temperature near or above the softening point of the resin base material. Specifically, it is between 10 ° C and 250 ° C.
  • the resin substrate is a polycarbonate or PC / PMMA laminate, it is preferable to measure at 150 ° C.
  • the antifogging and antifouling laminate preferably has a smaller difference in heat shrinkage between the X direction and the Y direction in the plane of the antifogging and antifouling laminate.
  • the X direction and the Y direction of the anti-fogging and antifouling laminate correspond to, for example, the longitudinal direction and the width direction of the roll when the antifogging and antifouling laminate is a roll.
  • the difference between the heat shrinkage rate in the X direction and the heat shrinkage rate in the Y direction in the anti-fogging and antifouling laminate is preferably within 5% at the heating temperature used in the heating step during molding. Outside this range, during the molding process, the first layer and the second layer may be peeled or cracked, or the characters, patterns, images, etc. printed on the surface of the resin substrate May be deformed or misaligned, making molding difficult.
  • the luminous reflectance of the antifogging and antifouling laminate is preferably 3.0% or less. If the luminous reflectance exceeds 3.0%, a sufficient antireflection function may not be obtained.
  • the luminous reflectance can be measured by the following method, for example. Black vinyl tape (VT-50 manufactured by Nichiban Co., Ltd.) is pasted on the opposite side of the second layer of the anti-fogging and antifouling laminate, and a 5 ° specular reflectance spectrum is measured from the second layer side. Measured using an absolute reflectance measurement unit with a company-made V-560 to calculate luminous reflectance. This is performed at three arbitrary locations, and the average value is obtained.
  • the anti-fogging and antifouling laminate is particularly suitable for a thermal bending film, an in-mold molding film, an insert molding film, and an overlay molding film.
  • the method for producing the anti-fogging and antifouling laminate is not particularly limited and may be appropriately selected depending on the intended purpose, but the method for producing the antifogging and antifouling laminate described below is preferred.
  • FIG. 1 is a schematic sectional view of an example of the anti-fogging and antifouling laminate of the present invention.
  • the anti-fogging and antifouling laminate of FIG. 1 has a resin substrate 11, a first layer 1 and a second layer 2 that are sequentially laminated on the resin substrate 11.
  • the second layer 2 contains a low refractive index filler 2A. Further, in the second layer 2, low surface energy components are localized on the surface.
  • FIG. 2 is a schematic cross-sectional view of another example of the anti-fogging and antifouling laminate of the present invention.
  • the anti-fogging and antifouling laminate of FIG. 2 includes a resin base material 11, a first layer 1, a third layer 3, and a second layer 2 sequentially laminated on the resin base material 11. Have.
  • the second layer 2 contains a low refractive index filler 2A. Further, in the second layer 2, low surface energy components are localized on the surface.
  • the third layer 3 improves the scratch resistance of the antifogging and antifouling laminate of the present invention.
  • FIG. 3 is a schematic cross-sectional view of another example of the anti-fogging and antifouling laminate of the present invention.
  • the anti-fogging and antifouling laminate of FIG. 3 includes a resin base 11, a first layer 1, a fourth layer 4, and a second layer 2 that are sequentially laminated on the resin base 11. Have.
  • the second layer 2 contains a low refractive index filler 2A. Further, in the second layer 2, low surface energy components are localized on the surface.
  • the fourth layer 4 contains a high refractive index filler 4A.
  • the method for producing the anti-fogging and antifouling laminate includes at least a first uncured layer forming step, a first layer forming step, a second uncured layer forming step, and a second layer forming step. In addition, other steps are included as necessary.
  • the method for producing the anti-fogging and antifouling laminate is a method for producing the antifogging and antifouling laminate of the present invention.
  • the first uncured layer forming step is not particularly limited as long as it is a step of forming the first uncured layer by applying the first active energy ray-curable resin composition on the substrate. It can be appropriately selected according to the purpose.
  • the first uncured layer is formed by applying the first active energy ray-curable resin composition on the substrate and drying it as necessary.
  • the first uncured layer may be a solid film, or a film having fluidity due to a low molecular weight curable component contained in the first active energy ray-curable resin composition. May be.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • the first uncured layer is not cured because it is not irradiated with active energy rays.
  • the first active energy ray-curable resin composition is applied onto the anchor layer of the base material on which the anchor layer is formed, and the first uncured layer is formed. May be formed.
  • the anchor layer There is no restriction
  • the first layer forming step is not particularly limited as long as it is a step of forming the first layer by irradiating the first uncured layer with active energy rays to cure the first uncured layer. And can be appropriately selected according to the purpose.
  • the first active energy curable resin composition has the hydrophilic monomer
  • a hydrophilic component water-absorbing component
  • water vapor is easily trapped in the first layer.
  • better antifogging properties can be obtained.
  • the active energy ray is not particularly limited as long as it is an active energy ray that cures the first uncured layer, and can be appropriately selected according to the purpose.
  • the antifogging and antifouling of the present invention examples thereof include the active energy rays exemplified in the description of the laminate.
  • the second uncured layer forming step is not particularly limited as long as it is a step of forming a second uncured layer by applying the second active energy ray-curable resin composition on the first layer. It can be appropriately selected depending on the purpose.
  • said 2nd active energy ray curable resin composition there is no restriction
  • the said 2nd layer of the said anti-fog antifouling laminated body of this invention examples thereof include the active energy ray-curable resin composition exemplified in the description.
  • the second uncured layer is formed by applying the second active energy ray-curable resin composition on the first layer and drying as necessary.
  • the second uncured layer may be a solid film or a film having fluidity by a low molecular weight curable component contained in the second active energy ray curable resin composition. May be.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • the second uncured layer is not cured because it is not irradiated with active energy rays.
  • the second layer forming step is not particularly limited as long as it is a step of forming the second layer by irradiating the second uncured layer with active energy rays to cure the second uncured layer. And can be appropriately selected according to the purpose.
  • physical processing for forming fine convex portions or concave portions on the surface is usually not performed.
  • the second active energy curable resin composition has the water-repellent monomer and the hydrophilic monomer
  • the low surface energy component is localized on the surface in the second layer obtained.
  • a hydrophilic component water-absorbing component
  • water droplets are water repellent on the surface of the second layer, and water vapor is easily trapped in the second layer.
  • an antireflection function derived from the low refractive index filler is obtained. It is done.
  • the article of the present invention has the anti-fogging and antifouling laminate of the present invention on the surface, and further includes other members as necessary.
  • the article is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include glass windows, refrigerated / frozen showcases, window materials such as automobile windows, bathroom mirrors, automobile side mirrors, and the like. Mirrors, bathroom floors and walls, solar panels, security surveillance cameras, etc.
  • the article may be glasses, goggles, a helmet, a lens, a microlens array, an automobile headlight cover, a front panel, a side panel, a rear panel, and the like. These are preferably formed by in-mold molding, insert molding, or overlay molding.
  • the antifogging and antifouling laminate may be formed on a part of the surface of the article, or may be formed on the entire surface.
  • the method for manufacturing the article is not particularly limited and may be appropriately selected depending on the intended purpose. However, the method for manufacturing the article of the present invention described later is preferable.
  • the method for producing an article of the present invention includes at least a heating step and an anti-fogging and antifouling laminate molding step, and further includes other steps such as an injection molding step and a cast molding step as necessary.
  • the manufacturing method of the article is the manufacturing method of the article of the present invention.
  • the heating step is not particularly limited as long as it is a step for heating the anti-fogging and antifouling laminate, and can be appropriately selected according to the purpose.
  • the antifogging and antifouling laminate is the antifogging and antifouling laminate of the present invention.
  • heating there is no restriction
  • the anti-fogging and antifouling laminate forming step is not particularly limited as long as it is a step for forming the heated antifogging and antifouling laminate into a desired shape, and can be appropriately selected according to the purpose.
  • mold into a desired shape with an air pressure etc. are mentioned.
  • an injection molding step may be performed as necessary.
  • the injection molding process is not particularly limited as long as it is a process for injecting a molding material onto the base side of the anti-fogging and antifouling laminate molded into a desired shape and molding the molding material. It can be appropriately selected depending on the case.
  • Examples of the molding material include resin.
  • Examples of the resin include olefin resins, styrene resins, ABS resins (acrylonitrile-butadiene-styrene copolymers), AS resins (acrylonitrile-styrene copolymers), acrylic resins, urethane resins, unsaturated polyesters.
  • Resin epoxy resin, polyphenylene oxide / polystyrene resin, polycarbonate, polycarbonate-modified polyphenylene ether, polyethylene terephthalate, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyimide, polyamide, liquid crystal polyester, polyallyl heat-resistant resin, various composite resins, Various modified resins are exemplified.
  • the injection method is not particularly limited and can be appropriately selected depending on the purpose.
  • the molten mold is formed on the substrate side of the antifogging and antifouling laminate adhered to a predetermined mold.
  • the method of pouring material is mentioned.
  • a cast forming step may be performed as necessary.
  • the cast molding process is a process in which a resin material dissolved in a solution is poured into the base of the antifogging and antifouling laminate molded into a desired shape, and the resin material is solidified and molded.
  • the manufacturing method of the article is preferably performed using an in-mold molding apparatus, an insert molding apparatus, and an overlay molding apparatus.
  • This manufacturing method is a manufacturing method using an in-mold molding apparatus.
  • the anti-fogging and antifouling laminate 500 is heated.
  • the heating is preferably infrared heating or exposure to a high temperature atmosphere.
  • the heated anti-fogging and antifouling laminate 500 is disposed at a predetermined position between the first mold 501 and the second mold 502.
  • the first mold 501 is a fixed mold
  • the second mold 502 is a movable mold.
  • the first mold 501 and the second mold 502 are clamped. Subsequently, the antifogging / antifouling laminate 500 is sucked into the cavity surface of the second mold 502 by sucking the antifogging / antifouling laminate 500 through the suction hole 504 opened in the cavity surface of the second mold 502. To do. By doing so, the cavity surface is shaped by the anti-fogging and antifouling laminate 500. At this time, the outer periphery of the anti-fogging / anti-stain laminate 500 may be fixed and positioned by a film pressing mechanism (not shown).
  • the molten molding material 506 is injected from the gate 505 of the first mold 501 toward the resin base material of the anti-fogging and antifouling laminate 500, and the first mold 501 and the second mold 502 are molded. Injection into a cavity formed by tightening (FIG. 4C). Thereby, the molten molding material 506 is filled in the cavity (FIG. 4D). Further, after the filling of the molten molding material 506 is completed, the molten molding material 506 is cooled to a predetermined temperature and solidified.
  • the second mold 502 is moved to open the first mold 501 and the second mold 502 (FIG. 4E).
  • an anti-fogging and antifouling laminate 500 is formed on the surface of the molding material 506, and an article 507 in-mold molded into a desired shape is obtained.
  • the protruding pin 508 is pushed out from the first mold 501 and the obtained article 507 is taken out.
  • a manufacturing method in the case of using the overlay molding apparatus is as follows. This is a step of directly decorating the surface of the molding material with the anti-fogging and anti-stain laminate, and an example thereof is a TOM (Threee Dimension Over Method) method.
  • TOM Three Dimension Over Method
  • An example of a method for producing the article of the present invention using the TOM method will be described below.
  • air is sucked by a vacuum pump or the like in both spaces in the apparatus divided by the anti-fogging and antifouling laminate fixed to the fixed frame, and the two spaces are evacuated.
  • a molding material that has been injection molded in advance is placed in a space on one side.
  • the anti-fogging / anti-fouling laminate is firmly attached to the three-dimensional shape of the molding material in a vacuum atmosphere by sending air to the side of the equipment space where there is no molding material. Adhere closely. If necessary, compressed air pressing from the side where the atmosphere is sent may be used in combination. After the anti-fogging and antifouling laminate is in close contact with the molded body, the obtained decorative molded product is removed from the fixed frame. Vacuum forming is usually performed at 80 ° C to 200 ° C, preferably about 110 ° C to 160 ° C.
  • an adhesive layer is provided on the surface opposite to the surface of the second layer of the anti-fogging and antifouling laminate in order to bond the antifogging and antifouling laminate and the molding material.
  • said adhesion layer There is no restriction
  • limiting in particular as a formation method of the said adhesion layer According to the objective, it can select suitably, For example, after forming the said 1st layer and the said 2nd layer on the said base material, the said base material The method of forming the said adhesion layer etc.
  • the coating liquid for adhesion layers on the opposite side to the said 2nd layer side is mentioned.
  • the adhesive layer coating liquid is applied on the release sheet to form the adhesive layer, the substrate and the adhesive layer on the release sheet are laminated, and the adhesive layer is formed on the substrate. Layers may be stacked.
  • FIG. 5 to 8 are schematic cross-sectional views of an example of the article of the present invention.
  • the article in FIG. 5 includes a molding material 506, a resin base material 211, a first layer 212, and a second layer 213, and the resin base material 211 and the first layer 213 are formed on the molding material 506.
  • the layer 212 and the second layer 213 are stacked in this order.
  • This article can be manufactured, for example, by insert molding.
  • the article in FIG. 6 includes a molding material 506, a resin base material 211, a first layer 212, a second layer 213, and a hard coat layer 600, and a resin base material is formed on the molding material 506.
  • the material 211, the first layer 212, and the second layer 213 are stacked in this order.
  • a hard coat layer 600 is formed on the side of the molding material 506 opposite to the resin substrate 211 side.
  • the article is immersed in the hard coat layer 600 on the surface of the molding material 506 and the molding material 506 in the hard coating liquid. Then, it can be formed by drying, curing, etc., and further by peeling off the protective layer.
  • the second layer 213 When the second layer 213 is a smooth surface, the pure water contact angle is in the above range, and the hexadecane contact angle is in the above range, the second layer 213 repels the hard coat liquid. Even if the protective layer is not formed, the hard coat is not formed on the second layer, and the hard coat layer 600 is formed only on the side opposite to the resin base material 211 side of the molding material 506. Excellent.
  • the article in FIG. 7 includes a molding material 506, a resin base material 211, a first layer 212, and a second layer 213. On both sides of the molding material 506, a resin base material 211, The first layer 212 and the second layer 213 are stacked in this order.
  • the article in FIG. 8 includes a molding material 506, a resin base material 211, a first layer 212, a second layer 213, and an optical film 601, and a resin base material on the molding material 506. 211, the first layer 212, and the second layer 213 are stacked in this order.
  • An optical film 601 is formed on the side of the molding material 506 opposite to the resin substrate 211 side. Examples of the optical film 601 include a hard coat film, an antireflection film, an antiglare film, and a polarizing film.
  • the article shown in FIG. 7 or 8 can be manufactured by, for example, double insert molding. Double insert molding is a method of molding a double-sided laminated film integrated product, and can be performed using, for example, the method described in JP-A-03-114718.
  • the antifouling method according to the present invention is a method for preventing soiling of the article by laminating the antifogging and antifouling laminate of the present invention on the surface of the article.
  • the article is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include glass windows, refrigerated / frozen showcases, window materials such as automobile windows, bathroom mirrors, automobile side mirrors, and the like. Mirrors, bathroom floors and walls, solar panels, security surveillance cameras, etc.
  • the article may be glasses, goggles, a helmet, a lens, a microlens array, an automobile headlight cover, a front panel, a side panel, a rear panel, and the like. These are preferably formed by in-mold molding or insert molding.
  • the method for laminating the anti-fogging and antifouling laminate on the surface of the article is not particularly limited and may be appropriately selected depending on the purpose.
  • the antifogging and antifouling laminate is provided on the surface of the article. Examples include a method of pasting. Further, the antifogging and antifouling laminate can be laminated on the surface of the article also by the article manufacturing method of the present invention.
  • the layer thickness was measured by observing the cross section of the anti-fogging and antifouling laminate with a field emission scanning electron microscope S-4700 (trade name; manufactured by Hitachi High-Technologies Corporation). Measurements were made at five arbitrary locations, and the average value was taken as the layer thickness.
  • ⁇ Pure water contact angle> The pure water contact angle was measured under the following conditions using a contact angle meter PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.). -Distilled water was put into a plastic syringe, and a stainless steel needle was attached to the tip thereof and dropped onto the evaluation surface. ⁇ Drip amount of water: 2 ⁇ L ⁇ Measurement temperature: 25 °C The contact angle after 5 seconds from dropping of water was measured at any 10 locations on the surface of the second layer, and the average value was defined as the pure water contact angle.
  • ⁇ Hexadecane contact angle> The hexadecane contact angle was measured under the following conditions using a contact angle meter PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.). -Hexadecane was put in a plastic syringe, and a Teflon-coated stainless steel needle was attached to the tip thereof and dropped onto the evaluation surface. ⁇ Drop amount of hexadecane: 1 ⁇ L ⁇ Measurement temperature: 25 °C Hexadecane was dropped and the contact angle after 20 seconds was measured at any 10 locations on the surface of the second layer, and the average value was taken as the hexadecane contact angle.
  • Black vinyl tape (VT-50 manufactured by Nichiban Co., Ltd.) is pasted on the opposite side of the second layer of the anti-fogging and antifouling laminate, and a 5 ° specular reflectance spectrum is measured from the second layer side. Measurement was made with a company-made V-560 using an absolute reflectance measurement unit, and luminous reflectance was calculated. This was performed at three arbitrary locations, and the average value was obtained.
  • ⁇ Molding process> The produced anti-fogging and antifouling laminate was heated at 130 ° C. for 60 seconds by infrared irradiation, and then molded into a 6-curve lens with a diameter of 80 mm by vacuum / pressure forming so that the concave surface became the second layer. Thereafter, a 6-curve lens-shaped antifogging and antifouling laminate having a diameter of 80 mm was punched with a Thomson blade. This was set in an insert mold, filled with molten polycarbonate, and then cooled until the polycarbonate solidified. Thereafter, the mold was opened to obtain a 6-curve lens whose concave surface was the second layer.
  • Expiration antifogging after molding process >> In an environment of 25 ° C. and 37% RH, the surface of the second layer of the 6-curve lens was visually inspected immediately after exhaling once from a distance of 5 cm in the normal direction from the center of the lens. Were observed and evaluated according to the following evaluation criteria. ⁇ Evaluation criteria ⁇ A: No change in appearance on the surface of the second layer. ⁇ : Appearance changes such as white cloudiness and water film formation were confirmed on part of the surface of the second layer. X: On the entire surface of the second layer, changes in appearance such as white cloudiness and water film formation were confirmed.
  • Example 1 Preparation of anti-fogging and antifouling laminate>
  • FE-2000 PC base material, average thickness 180 ⁇ m
  • Mitsubishi Gas Chemical Co., Ltd. was used as a resin base material.
  • the active energy ray-curable resin composition having the following composition was applied onto the resin substrate so that the thickness after drying and curing was 10 ⁇ m. After coating, it was dried in an oven at 60 ° C. for 2 minutes. A metal halide lamp was used to cure by irradiating with ultraviolet rays at a dose of 600 mJ / cm 2 in a nitrogen atmosphere to obtain a first layer.
  • first layer- SR9035 (Sartomer) 34.5 parts by mass EBECRYL 40 (Daicel Ornex Co., Ltd.) 14.8 parts by mass Irgacure 184D (BASF) 1.5 parts by mass Isopropyl alcohol (Kanto Chemical Co., Ltd.) 49.2 parts by mass
  • an active energy ray-curable resin composition having the following composition was applied on the first layer so that the thickness after drying and curing was 100 nm. After coating, it was dried in an oven at 60 ° C. for 2 minutes. Using a metal halide lamp, ultraviolet rays were irradiated and cured in a nitrogen atmosphere at an irradiation amount of 600 mJ / cm 2 to obtain an antifogging and antifouling laminate having an antireflection function.
  • Example 1 (Comparative Example 1) In Example 1, a laminate was produced in the same manner as in Example 1 except that the second layer was not formed.
  • Example 1 Evaluation similar to Example 1 was performed about the obtained laminated body. The evaluation results are shown in Table 1. In the evaluation of Comparative Example 1, “second layer” in the evaluation items is read as “first layer”. In addition, “anti-fogging and anti-fouling laminate” is read as “laminate”.
  • Example 2 An antifogging and antifouling laminate was obtained in the same manner as in Example 1 except that the second layer was formed using an active energy ray-curable resin composition having the following composition. About the obtained anti-fogging antifouling laminated body, evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1.
  • Opstar TU2205 MIBK dispersion containing fluoropolymer and low refractive index filler, solid content concentration 10% by mass
  • Example 2 In Example 1, the laminate was used in the same manner as in Example 1 except that the following first layer active energy ray-curable resin composition was used as the first layer active energy ray-curable resin composition. Was made. In the laminate of Comparative Example 2, the first layer does not contain a hydrophilic molecular structure.
  • Example 2 Evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. In the evaluation of Comparative Example 2, “anti-fogging / anti-fouling laminate” in the above evaluation items is read as “laminate”.
  • A-TMMT Pentaerythritol tetraacrylate
  • the antifogging and antifouling laminates of Example 1 and Example 2 also had an antireflection function. Since the laminate of Comparative Example 1 did not have the second layer, the antifouling property and the antireflection function were insufficient. The laminate of Comparative Example 2 had insufficient antifogging properties because the first layer did not contain a hydrophilic molecular structure.
  • Example 3 ⁇ Preparation of anti-fogging and antifouling laminate>
  • FE-2000 PC base material, average thickness 180 ⁇ m
  • Mitsubishi Gas Chemical Co., Ltd. was used as a resin base material.
  • the active energy ray-curable resin composition having the following composition was applied onto the resin substrate so that the thickness after drying and curing was 10 ⁇ m. After coating, it was dried in an oven at 60 ° C. for 2 minutes. A metal halide lamp was used to cure by irradiating with ultraviolet rays at a dose of 600 mJ / cm 2 in a nitrogen atmosphere to obtain a first layer.
  • an active energy ray-curable resin composition having the following composition was applied on the first layer so that the thickness after drying and curing was 1 ⁇ m. After coating, it was dried in an oven at 60 ° C. for 2 minutes. Using a metal halide lamp, ultraviolet rays were irradiated and cured in a nitrogen atmosphere at an irradiation amount of 600 mJ / cm 2 to obtain a third layer.
  • an active energy ray-curable resin composition having the following composition was applied on the third layer so that the thickness after drying and curing was 100 nm. After coating, it was dried in an oven at 60 ° C. for 2 minutes. Using a metal halide lamp, ultraviolet rays were irradiated and cured in a nitrogen atmosphere at an irradiation amount of 600 mJ / cm 2 to obtain an antifogging and antifouling laminate having an antireflection function.
  • Example 4 An antifogging and antifouling laminate was obtained in the same manner as in Example 3 except that the second layer was formed using an active energy ray-curable resin composition having the following composition. About the obtained anti-fogging antifouling laminated body, evaluation similar to Example 3 was performed. The evaluation results are shown in Table 2.
  • Example 3 (Comparative Example 3) In Example 3, a laminate was produced in the same manner as in Example 3 except that the first layer was not formed.
  • Example 3 Evaluation similar to Example 3 was performed about the obtained laminated body. The evaluation results are shown in Table 2. In the evaluation of Comparative Example 3, “antifogging / antifouling laminate” in the above evaluation items is read as “laminate”.
  • Example 4 (Comparative Example 4) In Example 3, except that the first active energy ray-curable resin composition for the first layer described below was used as the active energy ray-curable resin composition for the first layer, and the first layer of 5 ⁇ m was formed. In the same manner as in Example 3, a laminate was produced. In the laminate of Comparative Example 4, the first layer does not contain a hydrophilic molecular structure.
  • A-DPH Dipentaerythritol hexaacrylate
  • Biscoat # 300 Condensate of pentaerythritol and acrylic acid
  • Example 5 (Comparative Example 5) In Example 3, a laminate was produced in the same manner as Example 3 except that the second layer was not formed.
  • the antifogging and antifouling laminates of Example 3 and Example 4 also had an antireflection function. Further, by providing the third layer between the first layer and the second layer, the scratch resistance was more excellent as compared with Example 1 and Example 2. Since the laminate of Comparative Example 3 did not have the first layer, the antifogging property was insufficient. The laminate of Comparative Example 4 had insufficient antifogging properties because the first layer did not contain a hydrophilic molecular structure. Since the laminate of Comparative Example 5 did not have the second layer, the antifouling property and the antireflection function were insufficient.
  • the anti-fogging and antifouling laminate of the present invention includes glass windows, refrigerated / frozen showcases, window materials such as automobile windows, mirrors in bathrooms, mirrors such as automobile side mirrors, bathroom floors and walls, solar panel surfaces It can be attached to a security surveillance camera.
  • the anti-fogging and antifouling laminate of the present invention is easy to be molded, glasses, goggles, helmets, lenses, microlens arrays, automobile headlight covers are used by using in-mold molding and insert molding. It can be used for front panels, side panels, rear panels and the like.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

Cette invention concerne un stratifié anti-opalescence et anti-tâches possédant un matériau de base, ainsi qu'une première couche et une seconde couche sur au moins une surface du matériau de base. La première couche contient une structure polymère hydrophile, la seconde couche contient une charge présentant un faible indice de réfraction, et l'angle de raccordement d'une goutte d'eau pure sur la surface de la seconde couche est supérieur ou égal à 90 %.
PCT/JP2016/086913 2015-12-18 2016-12-12 Stratifié anti-opalescence et anti-tâches, produit et son procédé de fabrication WO2017104612A1 (fr)

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JP2015-246864 2015-12-18
JP2015246864 2015-12-18
JP2016-089429 2016-04-27
JP2016089429A JP7161836B2 (ja) 2015-12-18 2016-04-27 防曇防汚積層体、物品、及びその製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3858610A4 (fr) * 2018-09-27 2022-07-20 Daiwa Can Company Pellicule ou feuille hydrofuge et matériau d'emballage l'utilisant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02175784A (ja) * 1988-12-28 1990-07-09 Toray Ind Inc 防曇性物品
WO2004070436A1 (fr) * 2003-02-06 2004-08-19 Sdc Technologies-Asia Ltd. Procede de production d'un article ayant ete soumis a un traitement antireflet, solution pour former une couche antireflet et article ayant ete soumis a un traitement antireflet
JP2006044195A (ja) * 2004-08-09 2006-02-16 Mitsubishi Rayon Co Ltd 光硬化性シートおよびそれを用いた成形品
JP2011213002A (ja) * 2010-03-31 2011-10-27 Dainippon Printing Co Ltd 化粧シート
WO2013005710A1 (fr) * 2011-07-06 2013-01-10 東海光学株式会社 Article optique anti-voile et procédé pour sa production
JP2014159154A (ja) * 2013-01-23 2014-09-04 Dexerials Corp 親水性積層体、及びその製造方法、防汚用積層体、物品、及びその製造方法、並びに防汚方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02175784A (ja) * 1988-12-28 1990-07-09 Toray Ind Inc 防曇性物品
WO2004070436A1 (fr) * 2003-02-06 2004-08-19 Sdc Technologies-Asia Ltd. Procede de production d'un article ayant ete soumis a un traitement antireflet, solution pour former une couche antireflet et article ayant ete soumis a un traitement antireflet
JP2006044195A (ja) * 2004-08-09 2006-02-16 Mitsubishi Rayon Co Ltd 光硬化性シートおよびそれを用いた成形品
JP2011213002A (ja) * 2010-03-31 2011-10-27 Dainippon Printing Co Ltd 化粧シート
WO2013005710A1 (fr) * 2011-07-06 2013-01-10 東海光学株式会社 Article optique anti-voile et procédé pour sa production
JP2014159154A (ja) * 2013-01-23 2014-09-04 Dexerials Corp 親水性積層体、及びその製造方法、防汚用積層体、物品、及びその製造方法、並びに防汚方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3858610A4 (fr) * 2018-09-27 2022-07-20 Daiwa Can Company Pellicule ou feuille hydrofuge et matériau d'emballage l'utilisant
US11591148B2 (en) 2018-09-27 2023-02-28 Daiwa Can Company Liquid repellent film or sheet, and packaging matertal, using same

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