WO2014192709A1 - Stratifié, et procédé de production associé - Google Patents

Stratifié, et procédé de production associé Download PDF

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Publication number
WO2014192709A1
WO2014192709A1 PCT/JP2014/063899 JP2014063899W WO2014192709A1 WO 2014192709 A1 WO2014192709 A1 WO 2014192709A1 JP 2014063899 W JP2014063899 W JP 2014063899W WO 2014192709 A1 WO2014192709 A1 WO 2014192709A1
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Prior art keywords
intermediate layer
active energy
energy ray
resin composition
meth
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PCT/JP2014/063899
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English (en)
Japanese (ja)
Inventor
毅 瀧原
誠一朗 守
英子 岡本
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三菱レイヨン株式会社
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Priority to JP2014527389A priority Critical patent/JPWO2014192709A1/ja
Publication of WO2014192709A1 publication Critical patent/WO2014192709A1/fr

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    • 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

Definitions

  • the present invention relates to a laminate and a method for producing the same.
  • a fine concavo-convex structure having a fine concavo-convex structure on the surface exhibits antireflection performance due to a continuous change in refractive index.
  • the fine concavo-convex structure can also exhibit super water-repellent performance due to the lotus effect.
  • Examples of a method for forming a fine concavo-convex structure include, for example, a method of injection molding or press molding using a stamper having an inverted structure of a fine concavo-convex structure, an active energy ray curable resin composition between a stamper and a transparent substrate.
  • An article hereinafter also referred to as a “resin composition”
  • curing the resin composition by irradiation with active energy rays curing the resin composition by irradiation with active energy rays, transferring the stamper irregular shape, and then removing the stamper, the stamper irregularities on the resin composition
  • a method has been proposed in which the stamper is peeled off after the shape is transferred, and then the resin composition is cured by irradiation with active energy rays.
  • a method of transferring the fine concavo-convex structure by curing the resin composition by irradiation with active energy rays is preferable. This method is particularly preferable when a belt-shaped or roll-shaped stamper capable of continuous production is used, and is a method with excellent productivity.
  • the distance between adjacent convex portions or concave portions needs to be a size equal to or smaller than the wavelength of visible light.
  • Such a fine concavo-convex structure has lower scratch resistance than a molded body such as a hard coat having a smooth surface produced using the same resin composition, and has a problem in durability during use.
  • the resin composition used for the production of the fine concavo-convex structure is not sufficiently robust, a phenomenon in which the protrusions come close to each other easily due to release from the mold or heating.
  • such a fine concavo-convex structure has a problem in antifouling properties as compared with a molded body such as a hard coat having a smooth surface produced using the same resin composition.
  • fingerprints saliva dirt
  • Patent Document 2 discloses that dirt can be scraped off by dry wiping by using a curable resin having hydrophobicity and appropriate flexibility.
  • a fine concavo-convex structure using a soft and hydrophobic cured resin is excellent in terms of antifouling properties, but has a problem in scratch resistance because of its flexible composition.
  • a soft substrate such as a urethane film
  • pencil hardness is ensured by providing a flexible resin that forms a fine concavo-convex structure with a thickness of 60 ⁇ m or more.
  • a manufacturing method in which a resin is uniformly applied to a substrate with a thickness of 60 ⁇ m or more and a mold for forming a fine concavo-convex structure is applied.
  • middle layer is provided between the base film and the resin composition which forms an uneven structure.
  • a soft intermediate layer is provided with a predetermined thickness on a hard substrate such as a PET film, and the surface layer having a fine concavo-convex structure has a hard composition.
  • the intermediate layer acts as a stress relaxation layer, it provides scratch resistance, but it is difficult to apply if it has a flexible composition so that the fine uneven structure of the surface layer has antifouling properties, and further improvement can be made desired.
  • the fine concavo-convex structure disclosed in Patent Documents 1 to 3 does not necessarily have both antifouling properties and scratch resistance.
  • the present invention has been made in view of the circumstances described above. That is, an object of the present invention is to provide a laminate having both scratch resistance and antifouling properties.
  • the present invention relates to the following [1] to [19].
  • a display comprising the laminate according to any one of [1] to [9].
  • An active energy ray-curable resin composition is disposed between a stamper having an inverted structure of a fine concavo-convex structure and the intermediate layer, and the active energy ray-curable resin composition is cured by irradiation with active energy rays, and the stamper Forming a surface layer having a fine concavo-convex structure by peeling off the substrate.
  • [14] A method for producing a laminate according to any one of [1] to [9], Applying an active energy ray-curable resin composition on a stamper having an inverted structure of a fine concavo-convex structure; Supplying an intermediate layer material onto the substrate; Covering the stamper coated with the active energy ray curable resin composition so that the surface coated with the active energy ray curable resin composition is in contact with the intermediate layer material supplied on the substrate; A step of simultaneously curing the active energy ray-curable resin composition and the intermediate layer raw material by active energy ray irradiation; And a step of peeling the stamper.
  • [15] A method for producing a laminate according to any one of [1] to [9], Applying an active energy ray-curable resin composition on a stamper having an inverted structure of a fine concavo-convex structure, and curing the active energy ray-curable resin composition by active energy ray irradiation; Supplying an intermediate layer material onto the substrate; The stamper on which the cured active energy ray-curable resin composition is present is covered so that the surface on which the cured active energy ray-curable resin composition is present is in contact with the intermediate layer material supplied on the substrate. Process, Curing the intermediate layer material by irradiation with active energy rays; And a step of peeling the stamper.
  • the active energy ray-curable resin composition coating is not completely cured by irradiation with active energy rays in the presence of oxygen.
  • a laminate having both scratch resistance and antifouling properties can be provided.
  • the laminate according to the present invention is a laminate comprising a substrate, an intermediate layer laminated on the substrate, and a surface layer laminated on the intermediate layer, and is 100 mN with respect to the laminate.
  • the elastic modulus when the Vickers indenter is pushed in is 1.30 times or more of the elastic modulus when the Vickers indenter is pushed at 100 mN with respect to the substrate alone.
  • the elastic modulus of the base material and the elastic modulus of the laminate including the surface layer and the intermediate layer are a specific ratio, so that the base material is not subjected to indentation scratches or dent scratches, and A laminate having both scratch resistance and antifouling properties, in which no scratches remain on the surface layer, is obtained.
  • the surface layer When a pressing force is applied to the surface layer of the laminate, the surface layer is made of a flexible resin to impart antifouling properties, and therefore, the base material and the intermediate layer substantially receive the pressing force.
  • the intermediate layer does not exist and is composed of a hard base material and a flexible surface layer, the surface layer is scratched.
  • it when it consists of a flexible base material and a flexible surface layer, it depends on the thickness ratio and the adhesion between the base material and the surface layer, but the surface layer or the base material is damaged. Moreover, peeling may occur at the interface between the base material and the surface layer. Therefore, the presence of an intermediate layer that is harder than the base material prevents the base material from being scratched, and the surface layer is also prevented from being scratched by being distributed to the base material while receiving the pushing force throughout the intermediate layer. it can.
  • the elastic modulus when the Vickers indenter is pushed into the surface layer of the laminate at 100 mN is the elastic modulus of the substrate alone. 1.30 times or more.
  • the elastic modulus ratio is preferably 1.35 times or more, more preferably 1.45 times or more, and further preferably 1.50 times or more. If the elastic modulus ratio is less than 1.30 times, sufficient scratch resistance and antifouling properties cannot be obtained.
  • the upper limit of the elastic modulus ratio is not particularly limited, but can be 2.00 times or less.
  • the elastic modulus is a value measured using a microindenter (product name: Fischerscope HM2000, manufactured by Fischer Instruments).
  • Martens hardness when pushed Vickers indenter at 100mN in the laminate is 140 N / mm 2 or more, more preferably 150 N / mm 2 or more, still be at 160 N / mm 2 or more preferable.
  • the upper limit of the Martens hardness is not particularly limited, but can be 200 N / mm 2 or less.
  • the Martens hardness is a value measured using a microindenter (product name: Fischerscope HM2000, manufactured by Fischer Instruments).
  • a base material will not be specifically limited if it is a molded object, It is preferable to permeate
  • the material constituting a transparent substrate that transmits light include synthetic polymers such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, Semi-synthetic polymers such as cellulose triacetate and cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polylactic acid, polyamide, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, poly Examples include ether ketone, polyurethane, composites of these polymers (for example, composites of polymethyl methacrylate and polylactic acid, composites of polymethyl methacrylate and polyvinyl chloride), and
  • the manufacturing method and shape of the substrate are not particularly limited.
  • the substrate for example, an injection molded body, an extrusion molded body, a cast molded body, or the like can be used.
  • the shape of the substrate may be a sheet shape or a film shape.
  • the surface of the substrate may be coated or corona treated for the purpose of improving properties such as adhesion, antistatic properties, scratch resistance, and weather resistance.
  • the thickness of the substrate is not particularly limited. However, in the case of selecting a manufacturing method in which an intermediate layer is provided on a substrate and a surface layer is subsequently provided, a process is performed so that the curl of the substrate accompanying the curing shrinkage of the intermediate layer does not occur when the intermediate layer is provided. From the viewpoint of passability, the substrate preferably has an appropriate thickness.
  • the thickness of the substrate is preferably 38 ⁇ m or more, more preferably 80 ⁇ m or more, further preferably 125 ⁇ m or more, and particularly preferably 400 ⁇ m or more.
  • the upper limit of the thickness of a base material is not specifically limited, For example, it can be 3 mm or less. In addition, the thickness of a base material is the value measured using the micrometer.
  • the elastic modulus when the Vickers indenter is pushed into the substrate alone at 100 mN is preferably 2.5 GPa or less, more preferably 2.3 GPa or less, and 1.0 to 2.1 GPa. Is more preferable.
  • the elastic modulus is 2.5 GPa or less, it has moderate flexibility, so that stress can be released moderately when a force to push into the laminate is applied, and the intermediate layer, surface layer, substrate and intermediate Stress is not concentrated at the interface with the layer and the interface between the intermediate layer and the surface layer, and scratches are hardly formed.
  • middle layer can be formed using the intermediate
  • the thickness of the intermediate layer is preferably 20 to 100 ⁇ m, more preferably 20 to 80 ⁇ m, further preferably 25 to 60 ⁇ m, and particularly preferably 30 to 50 ⁇ m.
  • the thickness accuracy of the intermediate layer is preferably within ⁇ 5 ⁇ m, and more preferably within ⁇ 2 ⁇ m.
  • the thickness of the intermediate layer is a value measured using a micrometer. The thickness of the intermediate layer can be obtained by subtracting the thickness of the base material measured in advance from the thickness after the intermediate layer is laminated.
  • each layer it is also possible to measure the thickness of each layer by immersing the laminate in liquid nitrogen or the like, cleaving it in a frozen state, staining the cross section as appropriate, and using a general optical microscope.
  • the thickness when there is no clear interface between each layer is calculated by measuring the intermediate position of the mixed portion between the intermediate layer and the surface layer and the base material and the intermediate layer as the interface.
  • the elastic modulus when the Vickers indenter is pushed into the intermediate layer alone at 100 mN is preferably 2.5 GPa or more, more preferably 3.0 GPa or more from the viewpoint of improving the pencil hardness of the laminate. More preferably, it is 2 GPa or more.
  • the upper limit of the elastic modulus is not particularly limited, but can be 4.0 GPa or less, for example.
  • the elastic modulus when the Vickers indenter is pushed in at 100 mN with respect to the intermediate layer alone is preferably 1.30 times or more, more preferably 1.50 times or more of the base material.
  • the intermediate layer is preferably in the relationship of the following formula (1) from the viewpoint of improving the pencil hardness of the laminate.
  • the elastic modulus of the intermediate layer alone indicates the elastic modulus when the Vickers indenter is pushed in at 100 mN with respect to the intermediate layer alone.
  • the product of the thickness ( ⁇ m) of the intermediate layer and the elastic modulus (GPa) of the intermediate layer alone in the formula (1) is more preferably 105 or more, and further preferably 120 or more.
  • the product is preferably 500 or less.
  • the elastic modulus of the laminate when the intermediate layer is thin, the elastic modulus of the laminate is affected by the base material, but when the intermediate layer is sufficiently thick, it is hardly affected by the base material.
  • the thickness of the intermediate layer in which the elastic modulus of the laminate is affected by the base material varies depending on the hardness of the intermediate layer. For example, when an intermediate layer having an elastic modulus of 3.3 GPa is provided on a base material having an elastic modulus of 2.0 GPa, the elastic modulus of the laminate reaches 2.7 GPa if the thickness of the intermediate layer is 25 ⁇ m.
  • the elastic modulus of the laminated body becomes almost constant at 3 to 3.2 GPa.
  • the elastic modulus of the laminate when an intermediate layer having an elastic modulus higher than 3.3 GPa is provided, the elastic modulus of the laminate can reach 2.7 GPa even if the thickness of the intermediate layer is less than 25 ⁇ m.
  • the elastic modulus of the laminate when an intermediate layer having an elastic modulus lower than 3.2 GPa is provided, the elastic modulus of the laminate can be set to 2.7 GPa by making the intermediate layer thicker than 25 ⁇ m. Therefore, the thickness of the intermediate layer can be appropriately designed according to the hardness of the intermediate layer.
  • the method for measuring the elastic modulus does not necessarily have to be the indentation elastic modulus of the Vickers indenter at 100 mN. Even if a general tensile modulus or flexural modulus is used, the digits of the modulus of elasticity do not change significantly and can be correlated.
  • the curable resin raw material for forming the surface layer is photocured, or the polymer dissolved in a solvent is applied and the solvent is dried and removed, and the thickness is 200 ⁇ m. It can also be measured by forming it into a thin plate, punching it into the shape of a dumbbell test piece as defined in JIS standards, and pulling it at a pulling speed of 1 mm / min.
  • the instrument used for the measurement is not a problem as long as it is a general tensile tester, and for example, a Tensilon universal material tester manufactured by A & D Corporation can be used.
  • Martens hardness is preferably 140 N / mm 2 or more when pushed Vickers indenter at 100 mN, more preferably 150 N / mm 2 or more, further preferably 160 N / mm 2 or more.
  • the upper limit of the Martens hardness is not particularly limited, but can be, for example, 200 N / mm 2 or less.
  • the polymerization reactive monomer component is not particularly limited as long as the laminate can have the elastic modulus ratio.
  • polyfunctional monomer examples include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Specific examples include the following monomers.
  • trifunctional monomer examples include trimethylolpropane tri (meth) acrylate and its ethoxy modified product, propoxy modified product, ethoxy propoxy modified product and butoxy modified product; pentaerythritol tri (meth) acrylate, and its ethoxy modified product, propoxy Modified product, ethoxy propoxy modified product and butoxy modified product; pentaerythritol tetra (meth) acrylate, and ethoxy modified product, propoxy modified product, ethoxy propoxy modified product and butoxy modified product; isocyanuric acid tri (meth) acrylate, and Ethoxy modified, propoxy modified, ethoxy propoxy modified and butoxy modified; glycerin triacrylate, and ethoxy modified, propoxy modified, ethoxy propoxy modified Fine butoxy modified products thereof.
  • tetrafunctional monomers include pentaerythritol tetra (meth) acrylate and its ethoxy modified products, propoxy modified products, ethoxy propoxy modified products and butoxy modified products; ditrimethylolpropane tetra (meth) acrylate, and ethoxy modified products thereof, propoxy Examples include modified products, ethoxy propoxy modified products and butoxy modified products.
  • Examples of the polyfunctional monomer having five or more functional groups include dipentaerythritol penta (meth) acrylate, ethoxy-modified products thereof, propoxy-modified products, ethoxy-propoxy-modified products and butoxy-modified products, dipentaerythritol hexa (meth) acrylate, and its Examples include ethoxy modified products, propoxy modified products, ethoxy propoxy modified products, and butoxy modified products.
  • (meth) acrylate shows a methacrylate and / or an acrylate.
  • urethane (meth) acrylate obtained by reacting a polyol or an isocyanate compound with (meth) acrylate having a hydroxyl group
  • examples of such commercially available urethane (meth) acrylates include “NK Oligo” series U-4HA, U-6HA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), “EBECRYL” series 220, 1290, 5129, 8210, 8200 of the “KRM” series (trade name, manufactured by Daicel Cytec Co., Ltd.), “UA-306H” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), R of the “New Frontier” series -1901, R-1150, R-1403, GX8662V (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like. From the viewpoint of obtaining an intermediate layer exhibiting a high elastic modulus, it is preferable to use polyfunctional urethane (meth) acrylate obtained
  • a compound in which the value obtained by dividing the molecular weight of the monomer by the number of reactive groups in the monomer by appropriate ethoxy modification or caprolactone modification exceeds 110 is preferable.
  • ethoxy modification of trimethylolpropane tri (meth) acrylate ethoxy modification of pentaerythritol tri (meth) acrylate, ethoxy modification of pentaerythritol tetra (meth) acrylate, ethoxy modification of ditrimethylolpropane tetra (meth) acrylate
  • an ethoxy-modified product of dipentaerythritol hexa (meth) acrylate is preferable.
  • NK Ester series ATM-4E, A-TMPT-3EO (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), “EBECRYL40” (trade name, manufactured by Daicel Cytec Co., Ltd.), “ It is preferable to use “New Frontier TMP-2” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and “Light Acrylate TMP-6EO-A” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). These may use 1 type and may use 2 or more types together.
  • the polymerization-reactive monomer component preferably contains 40 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the total amount of the polymerization-reactive monomer component. More preferably, 80 parts by mass is included.
  • the intermediate layer becomes sufficiently rigid with respect to the base material, and is damaged by being pushed into the laminate. Easier to avoid.
  • 80 mass parts or less it becomes easy to suppress the curvature after intermediate
  • the intermediate layer material preferably contains 50% by mass or more, more preferably 60% by mass or more, and more than 70% by mass of tetrafunctional or higher (meth) acrylate. More preferably.
  • middle layer raw material contains 95 mass% or less of (meth) acrylates more than tetrafunctional.
  • the curable component having a bulky main chain or side chain, a main chain or side chain with low mobility or restricted mobility has isobornyl (meth) acrylate, adamantyl (meth) acrylate, or fluorene skeleton (meta ) Acrylate, (meth) acrylate having a bisphenol skeleton, (meth) acrylate having a heterocyclic structure, molecular skeleton that forms a strong interaction such as a hydrogen bond between adjacent molecules, for example, an oligomer having many urethane bonds Etc. These may use 1 type and may use 2 or more types together.
  • a monomer having a polar site capable of forming a hydrogen bond is preferable.
  • the polar site include a carboxyl group, a hydroxyl group, and a urethane bond.
  • Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, and succinic acid.
  • Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, N-methylol ( And (meth) acrylamide.
  • lactone modified (meth) acrylate is also mentioned, and "Placcel" series (trade name, manufactured by Daicel Corporation) is given as a commercial product.
  • polyfunctional monomer include monomers having a plurality of polymerizable double bonds and a hydroxyl group such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.
  • monomer having a urethane bond include polyfunctional urethane (meth) acrylate.
  • a compound having a low molecular weight is preferable as a component that contributes to adhesion.
  • urethane (meth) acrylates such as polycaprolactone-modified active energy ray-curable urethane (meth) acrylate having a long-chain alkyl group having 13 to 25 carbon atoms are preferred. These may use 1 type and may use 2 or more types together.
  • a monomer having a highly mobile side chain is preferable.
  • the monomer include alkyl (meth) acrylates having 4 or more carbon atoms in the alkyl group portion, and polyalkylene oxide mono (meth) acrylates having 4 or more carbon atoms in the polyalkylene oxide portion.
  • the monomer whose glass transition temperature of a homopolymer will be 0 degrees C or less is preferable.
  • the said polyalkylene oxide mono (meth) acrylate is preferable.
  • polyethylene glycol mono (meth) acrylate examples include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate. These may use 1 type and may use 2 or more types together. The number of repeating alkylene oxides can be determined as appropriate. Further, the type and amount of this component may be determined according to the physical properties of the intermediate layer finally obtained. The amount of this component used is preferably 3 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymerization reactive monomer components of the intermediate layer material. When it is used in an amount of 3 parts by mass or more, good impact absorbing ability is easily imparted. Moreover, when 20 mass parts or less are used, the strength fall of an intermediate
  • the active energy ray polymerization initiator is not particularly limited as long as it is a compound that generates a radical that is cleaved by irradiating active energy rays and initiates a polymerization reaction of the polymerization reactive monomer component.
  • the “active energy ray” means, for example, an electron beam, ultraviolet rays, visible rays, plasma, infrared rays or other heat rays. In particular, it is preferable to use ultraviolet rays from the viewpoint of apparatus cost and productivity.
  • the type and amount of the active energy ray polymerization initiator are, for example, an environment in which the active layer is irradiated with active energy rays in the presence of oxygen or a nitrogen atmosphere, or the surface of the intermediate layer is completely cured or What is necessary is just to determine suitably according to the request
  • Various known polymerization initiators can be used as the active energy ray polymerization initiator.
  • polymers of various polymerization reactive monomer components listed above can be used.
  • the polymer can be used by dissolving in a solvent.
  • the intermediate layer material may be diluted with a solvent if necessary.
  • it is preferable to adjust the viscosity by appropriately diluting the intermediate layer material with a solvent so as to obtain a viscosity suitable for the coating method.
  • middle layer can also be improved by dissolving the surface of a base material partially with a solvent.
  • a solvent having an appropriate boiling point can be selected according to the drying method and the like.
  • the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, methanol, ethanol, isopropyl alcohol, and other alcohols. . These may be used alone or in combination.
  • the intermediate layer is made of UV absorber, antioxidant, mold release agent, lubricant, plasticizer, antistatic agent, light stabilizer, flame retardant, flame retardant aid, polymerization inhibitor, filler, silane cup as required
  • additives such as a ring agent, a coloring agent, a reinforcement
  • an antistatic agent in the intermediate layer, it is possible to obtain a laminate in which dust and the like are difficult to adhere.
  • the antistatic agent include polythiol-based, polythiophene-based, polyaniline-based conductive polymers, inorganic fine particles such as carbon nanotubes and carbon black, lithium salts, and quaternary ammonium salts. These may use 1 type and may use 2 or more types together. Among these, lithium perfluoroalkyl acid salts that do not impair the transparency of the laminate, are relatively inexpensive, and exhibit stable performance are preferable.
  • the antistatic agent is preferably added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizing reactive monomer component or the polymer in the intermediate layer raw material (that is, 100 parts by mass of the polymer in the intermediate layer). It is more preferable to add 1 to 10 parts by mass.
  • the antistatic agent By adding 0.5 part by mass or more of the antistatic agent, the surface resistance value of the laminate is lowered, and the dust adhesion preventing performance is exhibited. Moreover, it is preferable that it is 20 mass parts or less from a cost surface.
  • the thickness of the surface layer laminated on the intermediate layer is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the intermediate layer contains a near-infrared absorber
  • a near-infrared absorber include, for example, organic compounds such as diimonium dyes, phthalocyanine dyes, dithiol metal complex dyes, substituted benzenedithiol metal complex dyes, cyanine dyes, squalium dyes, and conductive antimony-containing tin oxides.
  • organic compounds such as diimonium dyes, phthalocyanine dyes, dithiol metal complex dyes, substituted benzenedithiol metal complex dyes, cyanine dyes, squalium dyes, and conductive antimony-containing tin oxides.
  • Inorganic compounds such as product fine particles, conductive tin-containing indium oxide fine particles, tungsten oxide fine particles, and composite tungsten oxide fine particles. These may use 1 type and may use 2 or more types together.
  • the viscosity of the polymer dissolved in the intermediate layer material or the solvent can be adjusted to an optimum value according to the coating method.
  • An appropriate coating method can be selected according to the viscosity. For example, when the viscosity is 50 mPa ⁇ s or less, the polymer dissolved in the intermediate layer raw material or the solvent can be uniformly coated on the substrate by gravure coating.
  • the intermediate layer can be formed by applying the intermediate layer material on a substrate and irradiating active energy rays, or by applying the polymer dissolved in a solvent and drying and removing the solvent.
  • active energy rays it is preferable to use ultraviolet rays as the active energy rays.
  • the irradiation amount of the ultraviolet rays can be appropriately determined according to the amount of the active energy ray polymerization initiator contained in the intermediate layer material.
  • the environment for irradiating with ultraviolet rays may be in the presence of oxygen or in a nitrogen atmosphere.
  • the adhesion of the surface layer is improved by curing the coating film of the intermediate layer raw material to a state that does not lead to complete curing by ultraviolet irradiation in the presence of oxygen, and deliberately curing the surface. It is preferable.
  • the integrated light quantity is not particularly limited, but can be, for example, 200 to 4000 mJ / cm 2 .
  • the intermediate layer may be two or more layers, it is preferably one layer from the viewpoint of productivity and cost.
  • the surface layer is a layer laminated on the base material via an intermediate layer.
  • the surface layer preferably has a fine uneven structure.
  • a layer containing a cured resin formed of an active energy ray-curable resin composition can be used.
  • the surface layer is preferably thinner than the intermediate layer. Since the surface layer is a layer that bears antifouling properties and is preferably flexible, if the amount of deformation increases due to the indentation load, the surface layer is easily damaged. For this reason, it is preferable that a surface layer is moderately thin.
  • the thickness of the surface layer is preferably 15 ⁇ m or less, more preferably 2 to 10 ⁇ m. The thickness of the surface layer is a value measured using a micrometer.
  • the surface layer is a surface that receives contact in the process of use and is exposed to various types of dirt. Typical stains include fingerprints (sebum stains), scales and dust caused by human touch. It is preferable that the surface layer is a layer having an antifouling property that makes it difficult for these stains to adhere and easily removes these stains.
  • the surface layer has a fine concavo-convex structure, dirt enters the fine concavo-convex structure and cannot be easily removed. In this case, it is not possible to remove the dirt between the irregularities simply by wiping the surface, and as a result, the antireflection performance due to the fine irregular structure is impaired.
  • the first is a method in which the surface of the surface layer is designed to be familiar with water by using a hydrophilic resin, and the dirt is lifted off from the surface by wiping with water when the dirt adheres.
  • the second is a method of making it easy to scrape dirt by using a hydrophobic resin for the surface layer, making it difficult for dirt to adhere to the surface of the surface layer, and making it moderately flexible.
  • the method for imparting antifouling properties to the surface layer of the laminate according to the present invention is not limited to either the former method using a hydrophilic resin or the latter method using a hydrophobic resin. It is preferable to moderately soften.
  • an important surface property as well as antifouling property is scratch resistance.
  • the surface layer is preferably moderately flexible.
  • the surface layer preferably contains a flexible cured resin.
  • the surface layer contains a cured resin having an elastic modulus of 800 MPa or less when a Vickers indenter is pushed in at 10 mN.
  • the elastic modulus is more preferably 10 to 500 MPa, further preferably 20 to 250 MPa, and particularly preferably 30 to 150 MPa.
  • the elastic modulus of the cured resin of the surface layer is determined by photocuring the curable resin raw material for forming the surface layer, or by applying the polymer dissolved in the solvent and drying / removing the solvent.
  • the plate is formed into a plate shape of 500 ⁇ m or more, and the elastic modulus at the time of pushing 10 mN with a Vickers indenter is used for this plate using a Fisherscope HM2000 manufactured by Fischer Instruments.
  • the attached fingerprint stains can be removed by wiping with water or dry wiping, and since it has appropriate flexibility, it has good scratch resistance. is there. Further, if the elastic modulus is 10 MPa or more, it can be avoided that adjacent protrusions snuggle up to increase the wavelength to scatter light, thereby impairing the appearance.
  • the method for measuring the elastic modulus does not necessarily have to be the indentation elastic modulus of the Vickers indenter at 10 mN. Even if a general tensile modulus or flexural modulus is used, the digits of the modulus of elasticity do not change significantly and can be correlated.
  • the curable resin raw material for forming the surface layer is photocured, or the polymer dissolved in a solvent is applied and the solvent is dried and removed, and the thickness is 200 ⁇ m. It can also be measured by forming it into a thin plate, punching it into the shape of a dumbbell test piece as defined in JIS standards, and pulling it at a pulling speed of 1 mm / min.
  • the instrument used for the measurement is not a problem as long as it is a general tensile tester, and for example, a Tensilon universal material tester manufactured by A & D Corporation can be used.
  • the intermediate layer and the surface layer are sufficiently adhered. If the adhesion between both layers is sufficient, interfacial peeling due to shear deformation is unlikely to occur.
  • the intermediate layer and the surface layer may be in a mixed state where no clear interface exists. By making the surface of the intermediate layer insufficiently cured and allowing the active energy ray-curable resin composition constituting the surface layer to permeate into the intermediate layer, a clear interface does not occur and adhesion is improved.
  • the thickness of both layers when there is no clear interface is measured using the intermediate position of the mixed portion between the intermediate layer and the surface layer as the interface. Further, adhesion can be improved by applying heat when forming the surface layer.
  • FIGS. 1A and 1B are schematic cross-sectional views showing an embodiment of a laminate according to the present invention.
  • FIG. 1 illustrates a laminated body 10 in which an intermediate layer 15 and a surface layer 12 are sequentially laminated on a base material 11.
  • the surface of the surface layer 12 may be smooth, but as shown in FIG. 1, the surface of the surface layer 12 preferably has a fine concavo-convex structure that exhibits functions such as surface antireflection and water repellency.
  • convex portions 13 and concave portions 14 are formed at equal intervals on the surface of the surface layer 12.
  • the shape of the convex part 13 of Fig.1 (a) is a cone shape or a pyramid shape
  • the shape of the convex part 13 of FIG.1 (b) is bell shape.
  • the refractive index continuously increases from the air to the surface of the material, so that the antireflection performance is achieved with both low reflectance and low wavelength dependency.
  • Any shape can be used.
  • the cross-sectional area when cut in a plane perpendicular to the height direction of the convex portion continuously increases from the top to the bottom of the convex portion, even if it is other than a cone shape, a pyramid shape, or a bell shape. Such a shape is preferable.
  • finer convex portions may be united to form a fine concavo-convex structure.
  • the inverted structure and the porous structure may be used instead of the structure in which the protrusions are forested.
  • a structure having a large number of convex portions is preferable to a structure having a large number of concave portions.
  • the interval between adjacent convex portions 13 or concave portions 14 of the fine concavo-convex structure is The size is preferably less than or equal to the wavelength of visible light.
  • visible light refers to light having a wavelength of 380 to 780 nm. If this interval w1 is 400 nm or less, scattering of visible light can be suppressed.
  • the laminate according to the present invention can be suitably used for optical applications such as an antireflection film.
  • the lower limit value of the interval w1 is not particularly limited as long as it can be manufactured.
  • the interval w1 is preferably 20 nm or more, more preferably 40 nm or more, still more preferably 100 to 300 nm, and particularly preferably 150 to 250 nm from the viewpoint of mold manufacturing ease. preferable.
  • the aspect ratio represented by the height / interval w1 in the fine concavo-convex structure is preferably 0.5 or more, and more preferably 1 or more. When the aspect ratio is 0.5 or more, a light reflection reduction effect can be satisfactorily obtained, and incident angle dependency can be reduced.
  • the upper limit of the aspect ratio is not particularly limited as long as it can be produced, but is preferably 2 or less from the viewpoint of antifouling properties.
  • the aspect ratio is preferably 5 or less from the viewpoint of accurate transfer.
  • the height of the convex portion or the depth of the concave portion is preferably 60 nm or more, and 90 nm The above is more preferable, and the thickness is more preferably 150 nm to 300 nm.
  • the active energy ray-curable resin composition is a resin composition that cures by irradiating active energy rays so that a polymerization reaction proceeds.
  • the active energy ray-curable resin composition (hereinafter sometimes simply referred to as “resin composition”) contains a polymerization reactive monomer component, an active energy ray polymerization initiator, and other components as necessary. be able to.
  • the refractive index n1 of the cured product of the active energy ray-curable resin composition is preferably 1.40 or more, more preferably 1.43 or more, and further preferably 1.49 or more. When the refractive index n1 is 1.40 or more, a sufficient reflection reduction effect can be obtained.
  • the refractive index n1 of the cured product is preferably 1.60 or less, and more preferably 1.55 or less.
  • the refractive index n1 is 1.60 or less, transparency is improved and coloring is difficult to occur, and the viscosity of the resin composition before curing is low and is not easily solidified. If the viscosity of the resin composition is too high, transferability may be lowered when a fine concavo-convex structure is formed by a transfer method using a mold, resulting in an increase in reflectance.
  • polymerization reactive monomer component examples include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
  • examples of the monofunctional or polyfunctional monomer component having a radical polymerizable bond include various (meth) acrylates and derivatives thereof.
  • Examples of the monomer component having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is preferable.
  • Monofunctional monomers having a radical polymerizable bond include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acryl
  • polyfunctional monomer having a radical polymerizable bond examples include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, polybutylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane 2,2-bis (4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (me
  • Examples of the oligomer or reactive polymer having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule include unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, poly Ether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, cationic polymerization type epoxy compound, single or copolymer of the monomer having a radical polymerizable bond in the side chain, etc. It is done.
  • unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol
  • the surface layer preferably has antifouling properties and scratch resistance.
  • a monomer having a polyethylene glycol skeleton examples include polyethylene glycol mono (meth) acrylate, terminal methoxylated polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, ethoxy Modified pentaerythritol tri (meth) acrylate, ethoxy modified trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethoxy modified dipentaerystol hexa (meth) acrylate, ethoxy modified dipentaerystol Penta (meth) acrylate, ethoxy-modified ditrimethyl
  • These monomers having a polyethylene glycol skeleton are preferably used in an amount of 20 parts by mass or more, more preferably 30 to 80 parts by mass, out of 100 parts by mass of the curable component.
  • it is used in an amount of 20 parts by mass or more, sufficient hydrophilicity is imparted, and the dirt can be removed by wiping with water. If it is 80 mass parts or less, it has sufficient fastness and can maintain a fine concavo-convex structure.
  • a monomer having a long-chain alkyl group a monomer having a heterocyclic structure, a monomer having a polydimethylsiloxane skeleton, or a monomer having a fluorinated alkyl chain is used. It is preferable.
  • Examples of the monomer having a long-chain alkyl group include (meth) acrylates having an alkyl group having 12 or more carbon atoms. For example, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and the like can be given.
  • Examples of the monomer having a heterocyclic structure include isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
  • Examples of the monomer having a polydimethylsiloxane skeleton include a reactive silicone surfactant.
  • Examples of the monomer having a fluorinated alkyl chain include a compound having a polyfluoroalkyl chain, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1,1,2,2-tetrafluoropropyl (meth) Acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 1,1,2,2,3,3,4,4-octafluoropentyl (meth) acrylate, Examples thereof include (meth) acrylates having a fluorine-containing alkyl group such as 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoroheptyl (meth) acrylate.
  • the fluorinated urethane compound obtained by making the compound which has an isocyanuric group react with fluorinated alcohol can also be used.
  • an acrylate having a hydrogenated polybutadiene structure or the like can be used to exhibit water repellency.
  • polybutadiene acrylate “TEAI-1000” (trade name, manufactured by Nippon Soda Co., Ltd.) can be used. These may use 1 type and may use 2 or more types together.
  • water repellency can be expressed by depositing a fluorine compound or the like on the surface of the fine uneven structure.
  • the surface layer preferably has an appropriate flexibility. Examples of a method for imparting appropriate flexibility to the surface layer include a method of reducing the crosslinking density and a method of using a compound having high molecular mobility. A compound that exhibits high toughness by forming many hydrogen bonds, although it is not a chemical covalent bond like a urethane monomer, is also preferable.
  • active energy ray polymerization initiator a known polymerization initiator can be used, and can be appropriately selected according to the type of active energy ray used when the active energy ray-curable resin composition is cured.
  • photoinitiators when using a photocuring reaction, include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone.
  • ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 Carbonyl compounds such as -one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoic acid Diethoxy phosphine oxide, and the like. These may be used alone or in combination of two or more.
  • polymerization initiators include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoyl benzoate, 4-phenylbenzophenone, t-butylanthraquinone Thioxanthone such as 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinofe ) -Acetophenone such as butanone; benzoin ether such as benzoin ether such as benzo
  • the content of the polymerization initiator in the active energy ray-curable resin composition is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerization reactive monomer component.
  • the polymerization initiator is 0.1 part by mass or more, the polymerization proceeds sufficiently.
  • the polymerization initiator is 10 parts by mass or less, the resin layer (fine concavo-convex structure) is not colored and sufficient mechanical strength is obtained.
  • the resin composition may include a non-reactive polymer and an active energy ray sol-gel reactive composition.
  • the non-reactive polymer include acrylic resin, styrene resin, polyurethane resin, cellulose resin, polyvinyl butyral resin, polyester resin, and thermoplastic elastomer. These may use 1 type and may use 2 or more types together.
  • Examples of the active energy ray sol-gel reactive composition include alkoxysilane compounds and alkylsilicate compounds.
  • alkoxysilane compound include a compound represented by R x Si (OR ′) y .
  • alkyl silicate compound examples include a compound represented by R 1 O [Si (OR 3 ) (OR 4 ) O] z R 2 .
  • R 1 to R 4 each represents an alkyl group having 1 to 5 carbon atoms, and z represents an integer of 3 to 20.
  • Specific examples include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like. These may use 1 type and may use 2 or more types together.
  • Resin composition is UV absorber, antioxidant, mold release agent, lubricant, plasticizer, antistatic agent, light stabilizer, flame retardant, flame retardant auxiliary, polymerization inhibitor, filler, silane as required
  • the viscosity of the resin composition measured by a rotary B-type viscometer at 25 ° C. is 10,000 mPa ⁇ s or less from the viewpoint of workability. Preferably, it is 5000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less. However, even when the viscosity of the resin composition exceeds 10,000 mPa ⁇ s, it can be used without impairing workability if the viscosity can be lowered by preheating the resin composition when pouring into the stamper. it can.
  • the viscosity of the resin composition measured with a rotary B-type viscometer at 70 ° C. is preferably 5000 mPa ⁇ s or less, and more preferably 2000 mPa ⁇ s or less.
  • the viscosity of the resin composition measured by a rotary B-type viscometer at 25 ° C. is 100 mPa ⁇ s or more is preferable, 150 mPa ⁇ s or more is more preferable, and 200 mPa ⁇ s or more is more preferable.
  • the viscosity is within the above range, the resin composition does not easily leak to the side beyond the width of the stamper in the step of pressing the stamper, and the thickness of the cured product can be easily adjusted arbitrarily.
  • the viscosity of the resin composition can be adjusted by adjusting the type and content of the polymerization reactive monomer component. Specifically, when a large amount of a monomer containing a functional group having a molecular interaction such as a hydrogen bond or a chemical structure is used, the viscosity of the resin composition increases. On the other hand, when a large amount of a low molecular weight monomer having a low intermolecular interaction is used, the resin composition has a low viscosity.
  • the elastic modulus of the cured resin composition is preferably 10 MPa or more.
  • the cured resin composition is less than 10 MPa, nano-sized protrusions may snuggle up when peeling from the stamper or after peeling. In the nano region, surface tension that does not become a problem in the macro region is prominent. Therefore, in order to reduce the surface free energy, nano-sized protrusions come close to each other and force to reduce the surface area acts. When this force exceeds the hardness of the resin composition, the protrusions cling to each other. Such a fine concavo-convex structure may not provide desired antireflection performance or water repellency.
  • the elastic modulus is 10 MPa or more, the protrusions can be prevented from snuggling.
  • the surface layer preferably contains a cured resin having an elastic modulus of 800 MPa or less when a Vickers indenter is pushed in at 10 mN.
  • the elastic modulus is more preferably 10 to 500 MPa, further preferably 20 to 400 MPa, and particularly preferably 30 to 250 MPa.
  • the surface layer containing a flexible resin having an elastic modulus of 800 MPa or less is easy to remove attached fingerprint stains by water wiping or dry wiping, and has good flexibility and scratch resistance.
  • the measurement of the elasticity modulus of cured resin is the value measured by the method mentioned later.
  • the method for measuring the elastic modulus does not necessarily have to be the indentation elastic modulus of the Vickers indenter at 10 mN. Even if a general tensile modulus or flexural modulus is used, the digits of the modulus of elasticity do not change significantly and can be correlated.
  • the curable resin raw material for forming the surface layer is photocured, or the polymer dissolved in a solvent is applied and the solvent is dried and removed, and the thickness is 200 ⁇ m. It can also be measured by forming it into a thin plate, punching it into the shape of a dumbbell test piece as defined in JIS standards, and pulling it at a pulling speed of 1 mm / min.
  • the instrument used for the measurement is not a problem as long as it is a general tensile tester, and for example, a Tensilon universal material tester manufactured by A & D Corporation can be used.
  • the water contact angle of the surface layer is preferably 60 ° or more, more preferably 90 to 160 °, 110 More preferably, it is ⁇ 150 °.
  • the water contact angle is 60 ° or more, dirt is difficult to adhere.
  • the water contact angle is 160 ° or less, sufficient adhesion between the surface layer and the intermediate layer can be obtained.
  • the laminate according to the present invention is preferably used as a functional article having a fine uneven structure on the surface layer.
  • a functional article include an antireflection article and a water-repellent article provided with the laminate according to the present invention.
  • a display or an automobile member provided with the laminate according to the present invention is preferable.
  • the antireflection article according to the present invention includes the laminate according to the present invention.
  • the antireflection article has high scratch resistance and good antireflection performance.
  • a laminated body according to the present invention on the surface of an object such as a liquid crystal display device, a plasma display panel, an electroluminescence display or the like, an image display device such as a cathode ray tube display device, a lens, a show window, or a spectacle lens. Can be used.
  • the water-repellent article according to the present invention includes the laminate according to the present invention.
  • the water-repellent article has high scratch resistance and good water repellency, and also has excellent antireflection performance.
  • the laminate according to the present invention can be used by sticking to the surface of automobile members such as window materials, roof tiles, outdoor lighting, curved mirrors, vehicle windows, and vehicle mirrors.
  • the laminate according to the present invention may be affixed to the front plate, not limited to the surface thereof, and the front plate itself may be the laminate according to the present invention. It can also be configured.
  • the laminate according to the present invention can be applied to optical uses such as optical waveguides, relief holograms, lenses, and polarization separation elements, and uses of cell culture sheets in addition to the uses described above.
  • the laminate according to the present invention includes, for example, a step of forming an intermediate layer by supplying an intermediate layer raw material on a base material and curing the film of the intermediate layer raw material by active energy ray irradiation, and on the intermediate layer Disposing an active energy ray-curable resin composition and forming the surface layer by curing the active energy ray-curable resin composition by irradiation with active energy rays.
  • the intermediate layer forming step may include, for example, a step of supplying the intermediate layer raw material to the substrate, a drying step of volatilizing the solvent when the intermediate layer raw material includes a solvent, and a step of curing the intermediate layer raw material. it can.
  • an intermediate layer raw material is supplied onto a base material to form a film of the intermediate layer raw material.
  • the method for supplying the intermediate layer raw material is not particularly limited. An optimum method can be selected from known coating methods in consideration of the flexibility of the substrate and the viscosity of the intermediate layer raw material.
  • the thickness of the film can be appropriately controlled so as to have a desired thickness according to each supply method.
  • the amount of liquid to be supplied is determined according to the depth of the roll or bar groove to be used and the count, and the thickness of the film is determined.
  • the thickness of the obtained film can be predicted by multiplying the thickness of the film by the solid content ratio of the supply liquid.
  • the film formed on the substrate is dried to volatilize and remove the solvent.
  • the drying method an appropriate method can be selected depending on the type and content of the solvent. For example, the volatilization of the solvent may be promoted by heating or reduced pressure. However, the substrate may be deformed by heating. Moreover, when performing rapid drying, the surface side of a film
  • the intermediate layer material film formed on the substrate is cured to form an intermediate layer.
  • the intermediate layer raw material is a raw material containing a polymerization reactive monomer component and an active energy ray polymerization initiator
  • the film can be polymerized and cured by irradiation with active energy rays.
  • ultraviolet rays are preferable.
  • the lamp that irradiates ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, and a fusion lamp. What is necessary is just to determine the irradiation amount of an ultraviolet-ray according to the absorption wavelength and content of a polymerization initiator.
  • integrated light quantity is preferably 200 ⁇ 4000mJ / cm 2, more preferably 400 ⁇ 2000mJ / cm 2.
  • the integrated light quantity is 200 mJ / cm 2 or more, the intermediate layer raw material can be sufficiently cured, and the deterioration of the scratch resistance of the laminate due to insufficient curing can be prevented.
  • the integrated light quantity is 4000 mJ / cm 2 or less, coloring of the intermediate layer and deterioration of the substrate can be prevented.
  • the irradiation intensity is not particularly limited, but is preferably suppressed to an output that does not cause deterioration of the substrate.
  • the adhesion with the surface layer is formed later by curing the film of the intermediate layer raw material to a state that does not completely cure by ultraviolet irradiation in the presence of oxygen.
  • the film of the intermediate layer raw material By polymerizing in the presence of oxygen, the progress of polymerization on the outermost surface is inhibited, a semi-cured state is obtained, and a crosslinked structure is not sufficiently formed, so that the active energy ray-curable resin composition that comes into contact with the latter easily penetrates.
  • the active energy ray-curable resin composition is cured in a state where it penetrates into the intermediate layer, strong adhesion can be obtained between the intermediate layer and the surface layer.
  • a surface layer is formed on the intermediate layer formed as described above.
  • the surface layer preferably has a fine uneven structure.
  • an active energy ray curable resin composition is disposed between a stamper having an inverted structure of the fine concavo-convex structure and an intermediate layer, and the active energy ray curable resin composition is irradiated by active energy ray irradiation. It can be formed by curing the product and peeling off the stamper. That is, it is preferable to form the fine uneven structure by a transfer method using a stamper having an inverted structure of the fine uneven structure.
  • the manufacturing method of the stamper will be described later, by using the stamper, the fine concavo-convex structure can be easily transferred to the molded body in one step.
  • the stamper and the base material on which the intermediate layer is formed are opposed to each other, and the active energy ray-curable resin composition is filled between them. To do. At this time, the surface on which the inversion structure of the stamper is formed, that is, the stamper surface is made to face the intermediate layer.
  • the active energy ray-curable resin composition is cured by irradiating active energy rays to the filled active energy ray-curable resin composition via a base material or a stamper, for example, with a high-pressure mercury lamp or a metal halide lamp, Thereafter, the stamper is peeled off.
  • the active energy ray may be irradiated again after the stamper is peeled off.
  • the irradiation amount of the active energy ray is not particularly limited as long as the curing proceeds, but can be, for example, 100 to 10,000 mJ / cm 2 .
  • the laminate according to the present invention includes a step of applying an active energy ray-curable resin composition on a stamper having an inverted structure of a fine concavo-convex structure, a step of supplying an intermediate layer raw material on a substrate, and the activity A step of covering the stamper coated with the energy beam curable resin composition so that the surface coated with the active energy beam curable resin composition is in contact with the intermediate layer material supplied on the substrate;
  • the active energy ray-curable resin composition and the intermediate layer raw material can be simultaneously cured by beam irradiation, and the method can include a step of peeling the stamper.
  • the active energy ray-curable resin composition is applied on a stamper having an inverted structure of a fine uneven structure, and the active energy ray-curable resin composition is cured by irradiation with active energy rays.
  • a step a step of supplying an intermediate layer raw material on the substrate, a stamper in which the cured active energy ray-curable resin composition is present, a surface on which the cured active energy ray-curable resin composition is present, It can also be manufactured by a method including a step of covering the intermediate layer material supplied on the base material so as to contact, a step of curing the intermediate layer material by active energy ray irradiation, and a step of peeling the stamper. .
  • each step of these methods can be performed in the same manner as the above-described manufacturing method.
  • the active energy ray-curable resin composition coating is not completely cured by irradiation with active energy rays in the presence of oxygen. Curing is preferable from the viewpoint of improving the adhesion with the intermediate layer.
  • the thickness of the film is preferable to control the thickness of the film with an air knife in the step of supplying the intermediate layer raw material in the two methods described above. Furthermore, it is preferable to supply the intermediate layer material by gravure coating, bar coating, curtain coating or reverse coating.
  • ⁇ Stamper manufacturing method> Examples of a method for manufacturing a stamper having an inverted structure of the fine concavo-convex structure include an electron beam lithography method and a laser beam interference method. However, it is preferable to use anodized porous alumina as a stamper from the viewpoint of easily increasing the area of the stamper and easily producing a roll-shaped stamper.
  • an aluminum base material can be used as the base material for the anodized porous alumina.
  • the purity of aluminum in the aluminum substrate is preferably more than 99.0%, more preferably 99.5% or more, and further preferably 99.9% or more. When the aluminum purity exceeds 99.0%, the pores formed by anodization are regularly formed without branching.
  • the aluminum substrate may be anodized, but the pore diameter increases as the anodization is performed at a higher voltage.
  • an acidic electrolytic solution or an alkaline electrolytic solution can be used, but an acidic electrolytic solution is preferable.
  • As the acidic electrolyte sulfuric acid, oxalic acid, phosphoric acid, or a mixture thereof can be used.
  • An anodized porous alumina stamper can be manufactured, for example, through the following steps (a) to (e) (see FIG. 2).
  • the plane or curved surface which gives the inversion structure of a fine uneven structure on an aluminum base material is called a to-be-processed surface.
  • a second oxide film forming step for forming a film on the work surface Step (d): A pore size expansion treatment step of removing a part of the second oxide film and expanding the pore size of the formed pores, Step (e): A step of repeatedly performing the step (c) and the step (d).
  • Reaction conditions are not particularly limited as long as an oxide film having pores and a thickness of 10 ⁇ m or less is formed.
  • concentration of oxalic acid is 6.5 mass. % Or less is preferable.
  • concentration of oxalic acid is 6.5% by mass or less, the current value during anodic oxidation does not increase, and the surface of the oxide film does not become rough.
  • voltage during anodic oxidation it is possible to obtain a stamper having anodized alumina having highly regular pores with a period of about 100 nm formed on the surface.
  • the temperature of the electrolytic solution is preferably 50 ° C. or lower, and more preferably 35 ° C. or lower. When the temperature of the electrolytic solution is 50 ° C. or lower, a phenomenon called “burning” does not occur, and it is possible to prevent the pores from being broken or the surface from melting and the regularity of the pores from being disturbed.
  • a method for removing all of the first oxide film 32 there is a method in which aluminum is not dissolved but is removed with a solution that selectively dissolves alumina. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.
  • anodization may be performed under the same conditions (electrolyte concentration, electrolyte temperature, chemical conversion voltage, etc.) as in step (a). Also in the step (c), deeper pores can be obtained as the anodic oxidation is performed for a longer time.
  • an oxide film having a thickness of about 0.01 to 0.5 ⁇ m may be formed in step (c), and formed in step (a). It is not necessary to form an oxide film as thick as possible.
  • a specific method of the pore diameter expansion treatment a method of immersing in a solution dissolving alumina and expanding the diameter of the pores formed in the step (c) by etching may be mentioned. Examples of such a solution include a phosphoric acid aqueous solution of about 5.0% by mass. The longer the time of step (d), the larger the pore diameter.
  • a smooth taper shape is obtained as the number of times increases, and it is preferable to perform at least three times in total.
  • the conditions of the step (c) and the step (d) for example, the time of the pore size enlargement process, the temperature and concentration of the solution used for the pore size enlargement treatment, various shapes of pores can be formed. . What is necessary is just to set these conditions suitably according to the use etc. of a desired article.
  • the n-th (last) step (c) It is preferable that the diameter of the formed pores is increased by 1.1 to 1.9 times by the n-th step (d).
  • the expansion ratio is more preferably 1.1 to 1.8 times, and further preferably 1.1 to 1.7 times.
  • anodized porous alumina having a desired deep diameter expansion rate can be formed by changing conditions such as etching temperature, concentration, and time, such as shortening the time of the n-th step (d). it can.
  • this as a stamper the convex part of the fine concavo-convex structure formed on the surface of the compact can be sharpened.
  • the tapered surface of the mirror-finished aluminum base material whose diameter gradually decreases in the depth direction from the opening is formed. Holes are formed periodically.
  • the method for removing the oxide film include a method of dipping in a chromic acid / phosphoric acid mixed solution.
  • the anodic porous alumina thus obtained is suitable as a stamper for transferring a fine concavo-convex structure to a resin composition for producing a laminate according to the present invention.
  • a stamper for transferring a fine concavo-convex structure to a resin composition for producing a laminate according to the present invention.
  • a flat plate may be sufficient and a roll shape may be sufficient.
  • the surface of the stamper on which the inverted structure of the fine concavo-convex structure is formed may be subjected to a release treatment so that the release is easy.
  • Examples of the release treatment method include a method of coating a silicone-based polymer or a fluorine polymer, a method of depositing a fluorine compound, a method of coating a fluorine-based or fluorine-silicone-based silane coupling agent, and the like.
  • a master is produced by a method such as lithography, laser light interference, aluminum anodization, etc.
  • a replica is obtained from the master, and the replica is used as a stamper, or a replica further copied from the replica is used as a stamper.
  • a reverse structure is transferred from a roll-shaped master to a long film, a belt-shaped stamper can be obtained.
  • the inverted structure of the fine concavo-convex structure of the stamper is transferred onto the surface in a relationship between the key and the keyhole.
  • stamper pores A vertical section of a part of a stamper made of anodized porous alumina was deposited by Pt for 1 minute, and an acceleration voltage of 3.00 kV with a field emission scanning electron microscope (product name: “JSM-7400F”, manufactured by JEOL Ltd.) Observed, the interval (period) between adjacent pores and the depth of the pores were measured. Each of these measurements was performed at 10 points, and the average value was taken as the measured value.
  • Martens hardness measurement of laminate The Martens hardness when the Vickers indenter was pushed with a force of 100 mN was measured with a microindenter (product name: Fisherscope HM2000, manufactured by Fisher Instruments) in an environment of room temperature 23 ° C. with respect to the laminate. .
  • Pencil hardness test The laminate was subjected to a pencil hardness test under a load of 750 g in accordance with JIS K5600-5-4. At 5 minutes after the test, the appearance was visually observed, and the hardness of the pencil without scratches was defined as the pencil hardness. For example, when 2H is not scratched and 3H is scratched, the pencil hardness is expressed as “2H”.
  • Antifouling property The antifouling property was evaluated based on whether or not the fingerprint adhesion trace could be visually observed by carrying out dry wiping or water wiping after attaching the fingerprint. The antifouling property was evaluated according to the following criteria. In Table 2, the case where the fingerprint adhesion trace can be removed by dry wiping is indicated as “dry wiping”, and the case where the fingerprint adhesion trace can be removed by water wiping is indicated as “water wiping”.
  • the fingerprint adhesion site was rubbed 10 times under a load of 1 kg with Keidry (trade name, manufactured by Nippon Paper Crecia Co., Ltd.). Thereafter, the sample was observed by tilting it in multiple directions under a fluorescent lamp (1000 lux), and it was judged whether or not the difference between the part to which the fingerprint was attached and the part to which the fingerprint was not attached could be visually confirmed.
  • Keidry trade name, manufactured by Nippon Paper Crecia Co., Ltd.
  • Wipe Clean cloth (trade name: Toraysee, manufactured by Toray Industries, Inc.) with sufficient ion-exchanged water, squeeze until water drops do not drop, apply a 1 kg load, and rub the fingerprint attachment area 3 times It was. Thereafter, the sample was observed by tilting it in multiple directions under a fluorescent lamp (1000 lux), and it was judged whether or not the difference between the part to which the fingerprint was attached and the part to which the fingerprint was not attached could be visually confirmed.
  • a fluorescent lamp 1000 lux
  • TDP-8 trade name, manufactured by Nikko Chemicals Co., Ltd.
  • Ethoxylated dipentaerythritol hexaacrylate (trade name: “KAYARAD DPEA-12”, Nippon Kayaku Co., Ltd.) 27 parts, polyethylene glycol diacrylate (trade name: “Aronix M260”, manufactured by Toagosei Co., Ltd.) 32 Parts, polypropylene glycol diacrylate (trade name: “NK Ester APG700”, Shin-Nakamura Chemical Co., Ltd.) 32 parts, silicone acrylate (trade name: “BYK3570”, manufactured by BYK Chemie) 9 parts, active energy ray polymerization started 1-hydroxycyclohexylphenylmethanone (trade name: “Irgacure 184”, manufactured by BASF) as an agent, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: “Lucirin TPO”, BASF) 0.5) By mixing the active energy
  • Example 1 (Formation of intermediate layer) A polycarbonate sheet (trade name: “PC1151”, manufactured by Teijin Chemicals Ltd., thickness 400 ⁇ m, elastic modulus 2.00 GPa) was prepared as a base material. On the base material, the count No. Using the bar of 24, the intermediate layer raw material 1 was uniformly applied with a bar coater and allowed to stand in a dryer at 80 ° C. for 5 minutes. Next, ultraviolet rays are irradiated with energy of 1000 mJ / cm 2 using a fusion lamp (D bulb) in the presence of oxygen from the side where the intermediate layer raw material 1 is applied, and the coating film is cured to a state that does not lead to complete curing. An intermediate layer was formed. The thickness of the intermediate layer was 40 ⁇ m.
  • the surface layer raw material 1 was poured onto the pore surface of the stamper, and the base material was spread and coated so that the intermediate layer was in contact therewith.
  • the surface layer raw material 1 was cured by irradiating ultraviolet rays with energy of 1000 mJ / cm 2 from the substrate side using a fusion lamp. Thereafter, the stamper was peeled off to form a surface layer having a fine concavo-convex structure, thereby obtaining a laminate.
  • the fine uneven structure of the stamper is transferred on the surface of the laminate, and as shown in FIG. 1A, the interval w1 between adjacent protrusions 13 is 180 nm, and the height d1 of the protrusions 13 is 180 nm.
  • a certain conical fine concavo-convex structure was formed.
  • the thickness of the surface layer was about 3 ⁇ m.
  • Each evaluation result of the laminate is shown in Table 2.
  • Examples 2 to 11, Comparative Examples 1 to 5 The surface layer raw material, intermediate layer raw material, and bar No. A laminate was produced in the same manner as in Example 1 except that was adopted. The evaluation results of the laminate are shown in Table 2. In addition, when the elasticity modulus was measured also about the laminated body which provided the surface layer and hardened the surface of the intermediate
  • the laminates of Examples 1 to 8 were not scratched by the pencil hardness test, and the fingerprint stains could be removed by wiping, and both antifouling properties and scratch resistance were achieved. It was.
  • the laminates of Examples 9 to 11 can remove fingerprint stains with water, and an appropriate intermediate layer is provided similarly to the laminate that can be wiped dry, thereby preventing damage to the substrate. did it.
  • the laminate according to the present invention exhibits excellent scratch resistance and antifouling properties even if it has a fine concavo-convex structure on its surface, and is used for building materials such as walls and roofs, window materials for houses, automobiles, trains, ships, etc. It can be used for mirrors, displays that can be touched by human hands, etc., and is industrially useful.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un stratifié présentant un bon équilibre entre résistance aux éraflures et propriétés antisalissures. Un stratifié selon la présente invention comprend une base, une couche intermédiaire agencée sur la base, et une couche de surface agencée sur la couche intermédiaire. Lorsqu'un poinçon de Vickers est enfoncé dans le stratifié à 100 mN, son module d'élasticité n'est pas inférieur à 1,30 fois le module d'élasticité lorsqu'un poinçon de Vickers est enfoncé dans la base seule à 100 mN.
PCT/JP2014/063899 2013-05-27 2014-05-27 Stratifié, et procédé de production associé WO2014192709A1 (fr)

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CN115151410A (zh) * 2020-02-17 2022-10-04 三菱化学株式会社 层叠体和层叠体的制造方法

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JP2009230045A (ja) * 2008-03-25 2009-10-08 Dainippon Printing Co Ltd 反射防止積層体
JP2011000856A (ja) * 2009-06-22 2011-01-06 Dnp Fine Chemicals Co Ltd 基材、中間膜及び微細凹凸構造膜を積層してなる積層体
JP2012196965A (ja) * 2011-03-10 2012-10-18 Mitsubishi Rayon Co Ltd 積層体及びその製造方法
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JP2016165812A (ja) * 2015-03-09 2016-09-15 デクセリアルズ株式会社 防曇防汚積層体、及びその製造方法、物品、及びその製造方法、並びに防汚方法
CN107405861A (zh) * 2015-03-09 2017-11-28 迪睿合株式会社 防雾防污层压体及其制造方法、物品及其制造方法、以及防污方法
CN115151410A (zh) * 2020-02-17 2022-10-04 三菱化学株式会社 层叠体和层叠体的制造方法
EP4108445A4 (fr) * 2020-02-17 2024-03-20 Mitsubishi Chem Corp Stratifié et procédé de fabrication de stratifié

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