WO2006054472A1 - Procede de production d’un corps multicouche - Google Patents

Procede de production d’un corps multicouche Download PDF

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Publication number
WO2006054472A1
WO2006054472A1 PCT/JP2005/020574 JP2005020574W WO2006054472A1 WO 2006054472 A1 WO2006054472 A1 WO 2006054472A1 JP 2005020574 W JP2005020574 W JP 2005020574W WO 2006054472 A1 WO2006054472 A1 WO 2006054472A1
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WIPO (PCT)
Prior art keywords
group
refractive index
layer
metal oxide
oxide particles
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PCT/JP2005/020574
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English (en)
Japanese (ja)
Inventor
Hiroomi Shimomura
Mitsunobu Doimoto
Ryosuke Iinuma
Hideaki Takase
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Jsr Corporation
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Priority claimed from JP2005197624A external-priority patent/JP2006231317A/ja
Application filed by Jsr Corporation filed Critical Jsr Corporation
Publication of WO2006054472A1 publication Critical patent/WO2006054472A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials

Definitions

  • the present invention relates to a method for producing a laminate and a laminate obtained thereby, and more particularly to a method for producing a laminate capable of forming two or more layers from one coating film.
  • an antireflection film composed of a low refractive index material has been coated on the substrate of the display device.
  • a method of forming a thin film of a fluorine compound by vapor deposition is known.
  • a technique capable of forming an antireflection film for a large-sized display device at a low cost, especially in a liquid crystal display device is difficult.
  • an antireflection film is formed by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of the substrate.
  • the law is being considered.
  • it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate see, for example, Patent Document 1 and Patent Document 2.
  • a method of applying a fluoropolymer having a specific structure has been proposed (see, for example, Patent Document 3).
  • a laminate using a conductive polymer as an antistatic layer is also known as an antireflection film. (For example, see Patent Document 4).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-40845
  • Patent Document 2 Japanese Patent Publication No. 6-98703
  • Patent Document 3 Japanese Patent Laid-Open No. 6-115023
  • Patent Document 4 Japanese Patent Laid-Open No. 2003-300267
  • These conventional antireflection films are often laminates in which a conductive layer (antistatic layer), a layer having a different refractive index, a hard coat layer, and the like are formed on a substrate. In the conventional manufacturing method, the process of coating each layer on the substrate was repeated.
  • the present invention has been made against the background described above, and its purpose is to provide a method for producing a laminate capable of forming two or more layers by a single coating process, and a laminate obtained thereby. It is to provide. Another object of the present invention is to provide a laminate manufacturing method for efficiently forming a conductive layer and a laminate obtained thereby. Furthermore, another object of the present invention is to provide a method for producing a laminate having excellent anti-reflection effect with excellent adhesion to a substrate and high scratch resistance, and a laminate obtained thereby.
  • the following laminate production method and laminate obtained thereby can be provided.
  • a method for producing a laminate having a base material and a conductive layer and a multilayer structure thereon comprising pyropyrrole, thiophene, furan, selenophene, 3, 4_ethylenedioxythiophene and derivatives thereof Forming a conductive layer by gas phase polymerization of at least one monomer selected from the group;
  • A1 Metal oxide particles having a number average particle diameter of 1 nm or more and less than 40 nm formed by bonding an organic compound (Ab) having a polymerizable unsaturated group (hereinafter referred to as “metal oxide particles of (A1)”)
  • A2) Metal oxide particles having a number average particle diameter of 40 nm to 200 nm hereinafter referred to as “(A2) metal oxide particles”.
  • (C) (B) High solubility of fluorine-containing polymer containing ethylenically unsaturated groups, one or more solvents (hereinafter referred to as “(C) fast volatile solvent”)
  • (D) One or two or more solvents (hereinafter referred to as “(”) that have high dispersion stability of the metal oxide particles of (A1) and (A2) and are compatible with (C) the fast volatile solvent.
  • (D) Slow volatile solvent ”) and (C) Relative evaporation rate of fast volatile solvent is higher than (D) Relative evaporation rate of slow volatile solvent.
  • Each of the two or more layers is a layer in which the metal oxide particles (A1) and / or (A2) are present in high density or the metal oxide particles (A1) and (A2) are substantially present. 2.
  • the layer according to 1 above, wherein at least one of the two or more layers is a layer in which the metal oxide particles (A1) and / or (A2) are present at a high density.
  • the laminated body is an antireflection film that is laminated on a substrate in this order from at least the antistatic layer, the high refractive index layer, and the low refractive index layer.
  • the conductive layer is an antistatic layer
  • the two layers described in 3 above are composed of a high refractive index layer and a low refractive index layer. 4.
  • the refractive index of the low refractive index layer at 589nm is 1.20 ⁇ : 1.55,
  • the two layers described in 3 above are composed of a high refractive index layer and a low refractive index layer.
  • the refractive index of the low refractive index layer at 589 nm is 1.20 to: 1.55,
  • the refractive index of the middle refractive index layer at 589 nm is 1.50 to: 1.90, which is higher than the refractive index of the low refractive index layer.
  • the (C) fast volatile solvent of the curable resin composition is one or more solvents having low dispersion stability of the metal oxide particles (A1) and (A2).
  • the volatile solvent is one or more kinds of solvents having low solubility of the (B) ethylenically unsaturated group-containing fluorine-containing polymer.
  • the metal oxide particle force of (A1) described above is oxidized of at least one element selected from the group consisting of aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. 14. The method for producing a laminate according to any one of 1 to 13 above, wherein the laminate is a product particle.
  • the metal oxide particles (A2) are particles containing silica as a main component. Manufacturing method. 16. In the curable resin composition, the metal oxide particles (A2) are bonded to the organic compound (Ab) having a polymerizable unsaturated group, wherein the above 1 to 15: The manufacturing method of the laminated body as described in any one.
  • the organic compound (Ab) has a group represented by the following formula (A-1) in addition to the polymerizable unsaturated group, A manufacturing method of the laminate described in the crab.
  • U represents NH, O (oxygen atom) or S (ion atom), and V represents ⁇ or S.
  • the organic compound (Ab) is a compound having a silanol group in a molecule or a compound capable of generating a silanol group by hydrolysis. Body manufacturing method.
  • the (B) ethylenically unsaturated group-containing fluoropolymer of the curable resin composition comprises a compound (B_l) containing one isocynate group and at least one ethylenically unsaturated group;
  • the hydroxyl group-containing fluorine-containing polymer (B-2) contains the following structural units (a) 20 to 70 mol%, (b) 10 to 70 mol%, and (c) 5 to 70. 20.
  • R 1 represents a fluorine atom, a fluoroalkyl group, or a group represented by OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is an alkyl group
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • the following structural unit (d) derived from the hydroxyl group-containing fluorine-containing polymer (B-2) strong azo group-containing polysiloxane compound 0.1 to 10 mol
  • R 8 and R 9 may be the same or different and each represents a hydrogen atom, an alkyl group, or a halogen atom.
  • An alkyl group or an aryl group may be the same or different and each represents a hydrogen atom, an alkyl group, or a halogen atom.
  • R 1Q to R 13 represent a hydrogen atom, an alkyl group, or a cyano group
  • R 14 to R 17 represent a hydrogen atom or an alkyl group
  • p and q are numbers of:! To 6, s, t is a number from 0 to 6, y is a number from:! to 200.
  • R 18 represents an emulsifying group
  • the curable resin composition further comprises component (E) a polyfunctional (meth) acrylate compound containing at least two or more (meth) attaroyl groups and / or at least one or more (meth) attaroyl groups. Containing fluorine-containing (meth) atarylate compound The manufacturing method of the laminated body in any one of said 1-24.
  • the method for producing a laminate of the present invention two or more layers can be formed from one coating film obtained by applying the composition, so that the production process of the laminate having a multilayer structure is simplified. Can be used. Moreover, the manufacturing method of the laminated body of this invention can form a conductive layer efficiently. Therefore, the method for producing a laminate of the present invention can be advantageously used particularly for the formation of optical materials such as antireflection films, lenses, and selective transmission film filters. Furthermore, the laminate of the present invention can be suitably used as a paint, weather resistant film, coating, etc. for a substrate requiring weather resistance by utilizing the high fluorine content.
  • the laminate provides a good antireflection effect by providing a low refractive index layer on the outermost layer (the layer farthest from the substrate).
  • a laminate having excellent adhesion to the substrate and high scratch resistance can be obtained. From these facts, the laminate of the present invention is extremely useful as an antireflection film, and its visibility can be improved by applying it to various display devices.
  • FIG. 1A is a diagram for explaining “two or more layers formed from one coating film”.
  • FIG. 1B is a diagram for explaining “two or more layers formed from one coating film”.
  • FIG. 1C is a diagram for explaining “two or more layers formed from one coating film”.
  • FIG. 1D is a diagram for explaining “two or more layers formed from one coating film”.
  • FIG. 2 is a cross-sectional view of an antireflection film according to an embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.
  • FIG. 4 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.
  • FIG. 5 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.
  • FIG. 8 Electron microscope showing the concept of each state of two-layer separation, no separation (partially agglomerated) and uniform structure It is a microscopic photograph.
  • the present invention relates to a substrate, a method for producing a laminate having a conductive layer and a multilayer structure of two or more layers thereon, and a laminate obtained thereby.
  • a monomer is vapor-phase polymerized on a base material or a layer formed on the base material (hereinafter referred to as a base layer) to form a conductive layer.
  • two or more layers are formed by applying a predetermined curable resin composition to be described later and evaporating the solvent from the applied composition (hereinafter also referred to as “drying”). It should be noted that after drying, the solvent may not be completely removed. The solvent may remain as long as the properties as a cured film are obtained.
  • two or more layers are formed thereon. In the present invention, the formation of two or more layers from one coating film can be carried out twice or more.
  • the conductive layer formed by gas phase polymerization can be produced, for example, by the method described in JP-A-2003-82105, and can be specifically formed from a conductive polymer. That is, an oxidizing agent is applied to the base layer in units of several tens of meters / m, and the monomer (monomer) is brought into contact with the oxidizing agent coating film in a gaseous state, so that the polymerization proceeds and the conductive polymer film is formed as a base material. Form on top. At this time, in order to improve the adhesive strength, it is also possible to use a polymer such as polyuretan, polyvinyl chloride, polybutyl alcohol, methylcellulose, chitosan and the like together with an organic solvent.
  • a polymer such as polyuretan, polyvinyl chloride, polybutyl alcohol, methylcellulose, chitosan and the like together with an organic solvent.
  • a monomer is vapor-phase polymerized to form a conductive layer made of a conductive polymer.
  • the reaction temperature is 0 to 140 ° C. That is preferred.
  • oxidizing agent 0.5 to 10% by mass of an oxidizing agent is applied to the surface of the base layer in units of several zm.
  • oxidizing agents include CuCl, iron toluenesulfonate ( ⁇ ),
  • the compounds can be used alone or in combination.
  • the solvent conditions in this case vary depending on the type of base layer used. For example, methyl alcohol, 2-butyl alcohol, ethyl acetate solvent, ethyl alcohol, cyclohexane, acetone, ethyl acetate, toluene and An organic solvent selected from tilethyl ketone can be used. These can be single or
  • Two or more types can be mixed and used, for example, an organic solvent composed of methyl alcohol, 2-butyl alcohol and ethyl acetate sorb 7: 2: 1, 6: 2: 2, 6: 3: 1, Mix in the ratio of 5: 3: 2.
  • the base layer to which the oxidizing agent is applied is dried with a hot air dryer at 80 ° C or lower in consideration of the decomposition of the oxidizing agent.
  • the base layer coated with the oxidizing agent is selected from the group consisting of pyrrole, thiophene, furan, selenophene, 3,4_ethylenedioxythiophene, and derivatives thereof.
  • the monomer is vaporized and brought into contact, and a polymerization reaction is performed on the surface of the base layer.
  • a method for vaporizing the monomer there are a method in which the monomer is distilled at 0 to: 140 ° C. in a sealed chamber, a method by CVD (Chemical Vapor D-marked osition), and the like. Can be mentioned.
  • the polymerization reaction preferably adjusting the temperature conditions and reaction time, is carried out for about 10 seconds to 40 minutes, and generally varies depending on the type of monomer, but the film thickness and surface Repeat until the resistance value reaches the target value.
  • a washing step is performed to remove unreacted monomers and oxidizing agents.
  • the solvent used in this case alcohols such as methanol are usually used, and in some cases, it can be washed with water.
  • the series of steps as described above can be performed stepwise or continuously, and from the polymerization of the monomer to the formation of the conductive film, the process can be performed in a series of working steps.
  • the obtained conductive polymer film has good adhesion to the base layer and has sufficient resistance to alcohol solvents.
  • the thickness of the conductive layer is preferably:! -2000 nm. If the film thickness is less than 1 nm, pinholes or the like are generated, and it is difficult to form a film immediately. Further, the surface resistance is increased and the antistatic property may be deteriorated. On the other hand, when the film thickness exceeds 2000 nm, the surface resistance is good, but the transparency and color tone are extremely inferior, making it difficult to use as an antireflection film. A particularly preferred film thickness is 5 to 300 nm from the viewpoint of the balance of transparency, color tone, and surface resistance.
  • the surface resistance of the conductive layer is usually 10 2 ⁇ to 10 8 ⁇ / port.
  • the two or more layers are “a layer in which the metal oxide particles (A1) and / or (A2) are present at a high density” and “a metal oxide particle (A1) and (A2). It may be two or more layers including both “a layer and a layer that do not substantially exist”, and only from “a layer in which the metal oxide particles of (A1) and / or (A2) are present at high density”. There can be more than two layers.
  • each of two or more layers is a layer in which (A1) and Z or (A2) metal oxide particles exist in high density or (A1) and (A2) metal oxide particles.
  • a layer that does not substantially exist and at least one of the two or more layers is a layer in which the metal oxide particles (A1) and / or (A2) are present in high density is described.
  • FIG. 1A shows a case where there are two or more layer forces “layer 1, la in which metal oxide particles of (A1) or (A2) are present at high density”.
  • FIG. 1B shows that two or more layers are “layer 1, la in which metal oxide particles (A1) or (A2) are present in high density” and “metal oxide particles (A1) and (A2) are This shows the case of three layers, “layer 3” which does not substantially exist.
  • Fig. 1C shows that two or more layers are “layer 1, la in which (A1) or (A2) metal oxide particles are present at high density” and “(A1) and (A2) metal oxide particles are The case where there are three layers of “layer 3” which does not substantially exist is shown.
  • 1D shows that two or more layers are “a layer lb in which metal oxide particles of (A 1) and (A2) are present at high density” and “metal oxide particles of (A1) and (A2) are substantially This shows the case where there are two layers of layer 3 ”that do not exist.
  • the curable resin composition contains two or more types of metal oxide particles, as shown in FIGS. 1A, 1B and 1C, two or more types of “layers in which metal oxide particles exist at high density” are formed. It can be done.
  • the “metal oxide particles” in the “layer in which metal oxide particles are present in high density” means at least one, ie, one or more “metal oxide particles”. Therefore, the “layer in which metal oxide particles are present in high density” may be composed of two or more kinds of metal oxide particles (for example, FIG. 1D).
  • “Layer lb with high density of metal oxide particles” consists of particles X and Y. Since the particle Y is thicker than the “layer lb where the metal oxide particles are present at high density”, the force that protrudes into the “layer 3 where the metal oxide particles are substantially absent” It is included in the layer “lb” in which the particles are present in high density.
  • the “layer 3 substantially free of metal oxide particles” usually contains no metal oxide particles, but is included in a range that does not impair the effects of the present invention. Please May be.
  • “layer 1, la, lb in which metal oxide particles are present at high density” may also contain other substances other than metal oxide particles.
  • a coating method of the curable resin composition a known coating method can be used, and in particular, various methods such as a dipping method, a coater method, and a printing method can be applied.
  • Drying is usually performed for about 1 to 60 minutes by heating from room temperature to about 150 ° C. Specific curing conditions will be described later.
  • the monomer is vapor-phase polymerized, the curable resin composition is applied to various substrates in the form of a solution, and the obtained coating film is dried / cured to obtain a laminate.
  • the substrate is a transparent substrate, an excellent antireflection film is formed by providing a low refractive index layer as the outermost layer.
  • the specific structure of the antireflection film is usually a base material and a low refractive index film, or a base material, a high refractive index film and a low refractive index film laminated in this order.
  • An antistatic layer made of a conductive layer is provided between the refractive index layer and the low refractive index layer.
  • other layers may be interposed between the base material, the high refractive index film, and the low refractive index film, for example, an antistatic layer, a hard coat layer, a middle refractive index layer, a high refractive index layer, Layers such as a combination of low refractive index layers can be provided.
  • FIG. 2 shows an antireflection film in which an antistatic layer 20, a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on a substrate 10.
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in high density
  • the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
  • the antistatic layer 20 can be formed by gas phase polymerization, and the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.
  • FIG. 3 shows an antireflection film in which a hard coat layer 30, an antistatic layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density
  • the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
  • the antistatic layer 20 can be formed by gas phase polymerization, and the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.
  • FIG. 4 shows an antireflection film in which an antistatic layer 20, a hard coat layer 30, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density
  • the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
  • the antistatic layer 20 can be formed by gas phase polymerization, and the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.
  • FIG. 5 shows an antireflection structure in which a hard coat layer 30, an antistatic layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
  • the membrane is shown.
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density
  • the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
  • the medium refractive index layer 60 and the high refractive index layer 40 both have a force equivalent to a layer in which metal oxide particles are present at high density, or the medium refractive index layer 60 has high density in metal oxide particles.
  • the high refractive index layer 40 corresponds to a layer having substantially no metal oxide particles.
  • the antistatic layer 20 is formed by gas phase polymerization, and the medium refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film. Can be formed. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.
  • FIG. 6 shows an antireflection structure in which an antistatic layer 20, a hard coat layer 30, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
  • the membrane is shown.
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density
  • the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
  • the medium refractive index layer 60 and the high refractive index layer 40 both have a force equivalent to a layer in which metal oxide particles are present at high density, or the medium refractive index layer 60 has high density in metal oxide particles.
  • the high refractive index layer 40 corresponds to the layer in which the metal oxide particles are not substantially present in the existing layer.
  • the antistatic layer 20 is formed by gas phase polymerization, and the medium refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film. Can be formed.
  • the high refractive index layer 40 and the low refractive index layer 50 are also formed with a coating strength of 1.
  • FIG. 7 shows an antireflection film in which an antistatic layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the base material 10 in this order.
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density
  • the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
  • the middle refractive index layer 60 corresponds to a layer in which metal oxide particles are present at high density
  • the high refractive index layer 40 corresponds to a layer in which metal oxide particles are not substantially present.
  • the antistatic layer 20 is formed by gas phase polymerization, and the medium refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film. Can be formed.
  • the high refractive index layer 40 and the low refractive index layer 50 are also formed with a coating strength of 1.
  • the transparent substrate include, for example, triacetyl cellulose, polyethylene terephthalate resin (Lumilar manufactured by Toray Industries, Inc.), glass, polycarbonate resin, acrylic resin, styryl resin, arylate resin, norbornene resin CFSR ( Arton Co., Ltd., Nippon Zeon Co., Ltd. ZEONEX, etc.), methylmetatalylate / styrene copolymer resin, polyolefin resin, and other transparent plastic plates, films, and the like.
  • the low refractive index layer refers to a layer having a refractive index of 1.20-1.55 for light having a wavelength of 589 nm.
  • the material used for the low refractive index layer is not particularly limited as long as the desired properties are obtained.
  • a curable composition containing a fluoropolymer, an acrylic monomer, and a fluorine-containing acrylic monomer. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds.
  • silica fine particles and the like can be blended.
  • the high refractive index layer refers to a layer having a refractive index of 1.50 to 2.20 for light having a wavelength of 589 nm.
  • inorganic particles having a high refractive index such as metal oxide particles.
  • metal oxide particles include antimony-doped tin oxide (ATO) particles, tin dough Indium oxide (ITO) particles, phosphorus-doped tin oxide ( ⁇ ) particles, zinc oxide ( ⁇ ) particles, antimony-doped ZnO, A1-doped ⁇ particles ZrO particles, TiO particles, silica-coated TiO
  • Antimony-doped oxide (AT) particles soot-doped indium oxide (ITO) particles, A1 doped Zn particles, AlO / ZrO coated Ti particles. These metal oxide particles
  • the function of a hard coat layer or an antistatic layer can be given to the high refractive index layer.
  • the refractive index of light with a wavelength of 589 nm is usually 1.50 to 1.90, which is higher than the low refractive index layer and lower than the high refractive index layer.
  • a layer having a refractive index is represented as a middle refractive index layer.
  • the refractive index of the middle refractive index layer is preferably 1.50 to: 1.8
  • inorganic particles having a high refractive index for example, metal oxide particles.
  • metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, ZnO particles, antimony-doped ZnO, Al-doped Zn ⁇ particles, ZrO particles, TiO particles, silica-coated TiO particles, A1
  • ATO N-doped tin oxide
  • ITO tin-doped indium oxide
  • PTO phosphorus-doped tin oxide
  • ZnO particles A1-doped ZnO particles
  • ZrO particles These metal oxide particles
  • the medium refractive index layer can have a function of a hard coat layer or an antistatic layer.
  • the reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be lowered by combining the low refractive index layer, the high refractive index layer, and the middle refractive index layer. And can reduce color.
  • the hard coat layer examples include Si0 , epoxy resin, acrylic resin, and melamine.
  • the material strength of the system resin or the like be configured. Also, silica particles are blended with these resins May be.
  • the hard coat layer has the effect of increasing the mechanical strength of the laminate.
  • the antistatic layer is as described above for the gas phase polymerization of the conductive layer.
  • the antistatic layer imparts electrical conductivity to the laminate and prevents dust from adhering due to static electricity.
  • the film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm
  • the film thickness of the hard coat layer is usually 1 to 20 ⁇ m
  • the film thickness of the antistatic layer is usually 5 to 30 nm.
  • the conductive layer of the laminate and any other two or more continuous layers can be formed by the production method of the present invention. It can be carried out by a method such as cloth and curing, vapor deposition or sputtering.
  • the layer made of the curable resin composition in the present invention may give a heat history especially by heating in order to be cured to form a cured film having excellent optical properties and durability. preferable.
  • the curing reaction proceeds with the passage of time, and the desired cured film is formed.In practice, however, heating and curing can shorten the required time. It is effective.
  • the curing reaction can be further promoted by adding a thermal acid generator as a curing catalyst.
  • a thermal acid generator as a curing catalyst.
  • various acids and salts thereof used as curing agents for general urea resins, melamine resins and the like without particular limitation can be used, and in particular, ammonium salts can be preferably used.
  • the heating conditions for the curing reaction can be selected as appropriate. The heating temperature must be equal to or lower than the heat resistant limit temperature of the substrate to be coated.
  • the conductive layer can be formed by gas phase polymerization, a uniform conductive layer can be produced. Moreover, since two or more layers can be formed from one coating film, the production process of the laminate can be simplified.
  • the laminate of the present invention may be, for example, a lens, a selective transmission film filter, etc. Can be used for optical parts.
  • the curable resin composition is a mixture of:
  • Metal oxide particles having a number average particle diameter of 1 nm or more and less than 40 nm formed by bonding an organic compound (Ab) having a polymerizable unsaturated group hereinafter referred to as “metal oxide particles of (A1)”.
  • (A2) Metal oxide particles having a number average particle diameter of 40 nm to 200 nm (hereinafter referred to as “(A2) metal oxide particles”)
  • (C) (B) High solubility of fluorine-containing polymer containing ethylenically unsaturated groups, one or more solvents (hereinafter referred to as “(C) fast volatile solvent”)
  • (D) One or two or more solvents (hereinafter referred to as “(”) that have high dispersion stability of the metal oxide particles of (A1) and (A2) and are compatible with (C) the fast volatile solvent. D) slow volatile solvent ”).
  • Metal oxide particles (A1) and (A2) are Metal oxide particles (A1) and (A2)
  • metal oxide particles (A1) and (A2) having different particle diameters are used.
  • the metal oxide particles (A1) need to be bonded to an organic compound (Ab) having a polymerizable unsaturated group described later.
  • the metal oxide particles (A2) are preferably bonded to the organic compound (Ab) having a polymerizable unsaturated group, but are not essential.
  • the metal oxide particles (A1) and (A2) may be collectively referred to as “metal oxide particle component (A)”.
  • the metal oxide particles not bonded to the organic compound b) are referred to as “metal oxide particles (Aal)” and “metal oxide particles (Aa2)”, respectively.
  • metal oxide particles (Aa) are sometimes referred to as “reactive particles (Aabl)” and “reactive particles (Aab2)”, respectively.
  • both are collectively referred to as “reactive particles (Aab)”.
  • the number average particle diameter of the metal oxide particles (A1) and (A2) is measured by electron microscopy. are within the range of 1 nm to less than 40 nm and 40 nm to 200 nm, respectively.
  • the metal oxide particles may be a combination of three or more metal oxide particles as long as they use a plurality of types each having a particle size within the above range. Further, the substances constituting the plurality of types of metal oxide particles may be the same or different.
  • the metal oxide particles (A1) and (A2) used in the present invention are obtained from the viewpoints of hardness and colorlessness of the cured film, which is the curable resin composition to be obtained, from the viewpoints of silicon, aluminum, dinoleconium, titanium, Metal oxide particles of at least one element selected from the group consisting of zinc, germanium, indium, tin, antimony and cerium are preferred.
  • the metal oxide particles (A1) are preferably oxide particles of at least one element selected from the group consisting of ananolium, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium.
  • zirconium oxide particles are particularly preferable.
  • the refractive index of the metal oxide particle (A1) at a wavelength of 589 nm is 1. It is preferably 5 or more.
  • siri force (refractive index of about 1.45) particles are not preferred.
  • the metal oxide particles (A1) have a number average particle size in the range of 1 nm to less than 40 nm, preferably in the range of 1 nm to 30 nm.
  • the metal oxide particles (A2) are preferably particles mainly composed of silica.
  • the metal oxide particles (A2) have a number average particle size ranging from 40 nm to 200 nm, preferably from 40 nm to lOOnm.
  • the particle diameters of the metal oxide particles (A1) and (A2) are number average particle diameters measured by electron microscopy.
  • the particle diameter in the case of a rod-shaped particle means a short axis.
  • Various surfactants and amines may be added to improve the dispersibility of the metal oxide particles (A1) and (A2).
  • particles of silica, anolemina, zircoure and antimony oxide are preferred because the child is preferred.
  • zirconia particles are preferred because the child is preferred.
  • oxide particles such as dinoleconium titanium
  • PTO particles phosphorus-doped tin oxide
  • the metal oxide particles (Aa) are preferably in the form of powder or dispersion.
  • an organic solvent is preferred as the dispersion medium from the viewpoint of compatibility with other components and dispersibility.
  • an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, and lactate.
  • Estenoles such as chinole, ⁇ -butyla ratatone, propylene glycolenomonomethinoreethenoreacetate, propyleneglycolenomonoethylenoatenoreacetate; ethers such as ethyleneglycolenomonomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
  • methanol isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
  • Examples of commercially available silica particles include colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-0, ST-50, ST-0.
  • colloidal silica manufactured by Nissan Chemical Industries, Ltd.
  • methanol silica sol IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-0, ST-50, ST-0.
  • As powdered silica Nippon Aerosil Co., Ltd. trade names: Aerosil 130, Aerosil 300, Aerogenore 380, Aerosil Nore TT600, Aerosilore 0X50, Asahi Glass Co., Ltd.
  • aqueous dispersion of alumina a product name manufactured by Nissan Chemical Industries, Ltd .: Alumina Sol
  • the metal oxide particles (A1) and (A2) have a spherical shape, a hollow shape, a porous shape, a rod shape (a shape having an aspect ratio of more than 1 and 10 or less), a plate shape. , Fibrous or indefinite shape, preferably (A1) is rod-shaped and (A2) is spherical.
  • metal oxide particles (A1) and (A2) can be used in a state of being dispersed in a dry powder, water or an organic solvent.
  • a dispersion of fine metal oxide particles known in the art as the dispersion can be used directly.
  • the metal oxide particles (A2) used in the present invention may be the metal oxide particles (Aa2) having a predetermined number average particle diameter as they are, but they are polymerized with the metal oxide particles (Aa2). It is preferably a particle formed by binding an organic compound (Ab) containing a reactive unsaturated group (hereinafter sometimes referred to as “reactive particle (Aab2)”).
  • Reactive particle (Aab2) a reactive unsaturated group
  • As the metal oxide particle component (A) a cured product obtained by using reactive particles (Aab2) in which metal oxide particles (Aa2) are combined with an organic compound (Ab) having a polymerizable unsaturated group.
  • the scratch resistance of the cured film made of the conductive resin composition is further improved.
  • the bond may be a covalent bond or a non-covalent bond such as physical adsorption.
  • the organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
  • U represents NH, O (oxygen atom) or S (ion atom), and V represents ⁇ or S.
  • the polymerizable unsaturated group contained in the organic compound (Ab) there are no particular restrictions on the polymerizable unsaturated group contained in the organic compound (Ab) .
  • the polymerizable unsaturated group contained in the organic compound (Ab) there are, but are not limited to, for example, ataryloyl group, methacryloyl group, vinyl group, propenyl group, butagenyl group, styryl group, ethuryl group, cinnamoyl group.
  • Maleate groups and acrylamide groups can be cited as preferred examples.
  • This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
  • These groups can be used alone or in combination of two or more.
  • the organic compound (Ab) is a compound having a silanol group in the molecule or by hydrolysis. It is preferable that the compound generates a silanol group.
  • Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetooxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom.
  • a compound to which an aryloxy group is bonded, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
  • the silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that is bonded to the oxide particles (Aa) by a condensation reaction or a condensation reaction that occurs after hydrolysis.
  • organic compound (Ab) As a preferred example of the organic compound (Ab), a specific example thereof includes a compound represented by the following formula (A_2).
  • R 24 and R 25 are hydrogen atoms which may be the same or different, or an alkyl group or aryl group having from 8 to 8 carbon atoms, such as methinole, ethyl, propyl, butyl, Examples include octanol, phenyl, xylyl groups and the like.
  • j is an integer between:!
  • Examples of the group represented by [(R 24 0) R 25 Si—] include, for example, a trimethoxysilyl group, a triethyloxy 3-j
  • Examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilanol group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
  • R 26 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene.
  • R 27 is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include hexamethylene and otatamethylene. A chain polyalkylene group such as dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene or norbornylene; a divalent group such as phenylene, naphthylene, biphenylene, polyphenylene, etc. And these alkyl group-substituted and aryl-substituted groups. In addition, these divalent organic groups may contain a polyether bond, a polyester bond, a polyamide bond, or a polycarbonate bond, which may contain an atomic group containing an element other than carbon and hydrogen atoms.
  • R 28 is a (k + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
  • Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.
  • K is preferably an integer of:! To 20, more preferably an integer of 1 to 10, and particularly preferably an integer of:! To 5.
  • Specific examples of the compound represented by the formula (A-2) include compounds represented by the following formulas (A-4) and (A-5).
  • mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate, reacted at 60 to 70 ° C. for several hours, and then pentaerythritol tritalylate is added. Furthermore, it is produced by reacting for about several hours at 60 to 70 ° C.
  • An organic compound (Ab) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with metal oxide particles (Aa), hydrolyzed, and the two are combined.
  • the ratio of the organic polymer component, that is, hydrolyzable silane hydrolyzate and condensate in the resulting reactive particles (Aab) is usually reduced by mass when the dry powder is completely burned in air. As a constant value of%, it can be obtained, for example, by thermal mass spectrometry in air from room temperature to usually 800 ° C.
  • the amount of organic compound (Ab) bound to metal oxide particles (Aa) is 100% by mass of reactive particles (Aab) (the sum of metal oxide particles (Aa) and organic compounds (Ab)). Is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. When the amount of the organic compound (Ab) bonded to the metal oxide particle (Aa) is less than 0.01% by mass, the curing can be obtained with sufficient dispersibility of the reactive particle (Aab) in the composition. The transparency and scratch resistance of the object may not be sufficient.
  • the mixing ratio of the reactive particles (Aab) metal oxide particles in the raw material during manufacture (Aa) is preferably a 5 to 99 weight 0/0, more preferably, 10 to 98 weight 0/0 It is.
  • the amount of the metal oxide particles (A1) (that is, the reactive particles (Aabl)) in the curable resin composition is 100% by mass based on the total amount of the composition excluding the organic solvent.
  • a range of 10 to 90% by mass is preferable, and a range of 20 to 80% by mass is more preferable, and a range of 40 to 80% by mass is particularly preferable. If it is less than 10% by mass, a cured film with insufficient hardness or a high refractive index may not be obtained. If it exceeds 90% by mass, film formability may be insufficient.
  • the content of the metal oxide particles (Aal) constituting the reactive particles (Aabl) is preferably 65 to 95% by mass of the reactive particles (Aabl).
  • the compounding (content) amount of the metal oxide particles (A2) (whether the metal oxide particles (Aa2) or the reactive particles (Aab2)) in the curable resin composition is
  • the total amount of the composition excluding the organic solvent is preferably 100% by mass, and preferably in the range of 1 to 30% by mass: more preferably in the range of 20 to 20% by mass.
  • the ethylenically unsaturated group-containing fluorine-containing polymer used in the present invention comprises a compound (B-1) containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. It is preferably obtained by reacting with the compound (B-2) and obtained by reacting the isocyanate group Z hydroxyl group in a ratio of 1.1 to 1.9.
  • (B-1) Compound containing one isocyanate group and at least one ethylenically unsaturated group
  • the compound (B-1) is not particularly limited as long as the compound contains one isocyanate group and at least one ethylenically unsaturated group in the molecule. If two or more isocyanate groups are contained, gelling may occur when reacting with a hydroxyl group-containing fluoropolymer. In addition, as the ethylenically unsaturated group, a (meth) atalyloyl group is more preferable because the curable resin composition can be cured more easily.
  • Examples of such compounds include 2- (meth) ataloyloxychetyl isocyanate, 2 — (meth) ataryloxypropyl isocyanate, 1, 1-bis [(meth) atalylooxymethyl] ethyl
  • isocyanate or a combination of two or more types may be mentioned.
  • diisocyanates include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3-xylylene diisocyanate, 1 isocyanate, p-phenylene diisocyanate, 3,3 'Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-Diphenylmethane diisocyanate, 3,3'-Dimethylphenylene diisocyanate, 4,4'-Bidiylene diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), 2,2,4_trimethylhexamethylenediisocyanate, bis (2isocyanate ethinole) fumarate, 6
  • 2,4-tolylene diisocyanate isophorone diisocyanate, xylylene diisocyanate, methylenbis (4-cyclohexylisocyanate), 1,3_bis (isocyanate) Nate methyl) cyclohexane is particularly preferred.
  • Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, force Prolatataton (meth) acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol nortri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid ⁇ Modification Examples include single (single) or a combination of two or more, such as di (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred.
  • Examples of commercially available hydroxyl group-containing polyfunctional (meth) atalylate are, for example, Osaka Organic Chemical Co., Ltd., trade name ⁇ , Nippon Kayaku Co., Ltd., trade name KAYAR AD DPHA, PET-30, Toagosei Product name Alonics M-215, M-233, M-305, M-400, etc.
  • the amount of the hydroxyl group-containing polyfunctional (meth) acrylate is added to 1 to 1.2 mol with respect to 1 mol of diisocyanate. preferable.
  • the hydroxyl group-containing fluoropolymer (B-2) is preferably composed of the following structural units (a), (b), and (c). Furthermore, the structural units (d), (e), (f ) Is more preferable.
  • the structural unit (a) is represented by the following general formula (1).
  • R 1 represents a fluorine atom, a fluoroalkyl group, or a group represented by —OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • the fluoroalkyl group of R 1 and R 2 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoro mouth.
  • fluorinated alkyl groups having 1 to 6 carbon atoms such as xyl group and perfluorocyclohexyl group.
  • alkyl group for R 2 examples include alkyl groups having 1 to 6 carbon atoms such as a methinole group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.
  • the structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component.
  • a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers.
  • Perfluoro alkyl butyl ether
  • perfluoro methyl vinyl ether
  • perfluoro ethyl vinyl ether
  • propyl vinyl ether propyl vinyl ether
  • perfluoro butyl vinyl ether
  • perfluoro isobutyl vinyl ether
  • perfluoro propoxypropyl
  • One perfluoro (alkoxyalkyl butyl ether) such as buluetenore) may be used alone or in combination of two or more.
  • hexafluoropropylene and perfluoro (alkyl butyl etherate) or perfluoro (alkoxy alkyl butyl ether) are more preferable, and it is more preferable to use these in combination.
  • the content of the structural unit (a) is 25 to 65 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer (B-2). More preferably, it is made into -60 mol%.
  • the structural unit (b) is represented by the following general formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is an alkyl group
  • a group represented by OCOR 5 (R 5 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]
  • the alkyl group represented by R 4 or R 5 is a carbon number such as a methyl group, an ethyl group, a propinole group, a hexyl group, a cyclohexyl group, or a lauryl group.
  • the alkylcarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component.
  • Biel monomers include methyl vinyl ethere, ethino levinino le ethere, n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl butyl ether, tert- Buchirubyuru Etenore, n- pentyl Honoré vinyl Honoré ether Honoré, carboxymethyl Honoré vinyl Honoré ether Honoré to n_, n- Okuchi Honoré vinyl Honoré ether Honoré, n - dodecylcarbamoyl Honoré vinyl Honoré ether Honoré, carboxymethyl Honoré vinyl Honoré ether to 2-Echinore Alkyl butyl etherols such as Nole and cyclohexyl butyl ether or cyclo
  • the content of the structural units (b), with respect to the total weight of the hydroxyl group-containing fluoropolymer (B- 2) preferably from force of 20 to 60 Monore 0/0, More preferably, it is 30-60 monole%.
  • the structural unit (c) is represented by the following general formula (3).
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • the structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl-containing bur monomers include 2-hydroxyethylenovininoleetenore, 3-hydroxypropinorevininoleetenore, 2-hydroxypropinorevininoleetenore, 4-hydroxybutinolebi Ninoreetenore, 3-hydroxybutinorebininore Hydroxyl-containing vinyl ethers such as ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, hydroxyl-containing vinyl ethers such as 2-hydroxyethyl aryl ether, 4-hydroxybutyl aryl ether, glycerol monoallyl ether, And aryl alcohol.
  • the hydroxyl group-containing butyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and force prolatatone.
  • (Meth) acrylate, polypropylene glycol (meth) acrylate, etc. can be used.
  • the content of the structural unit (c) is preferably 5 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. ,.
  • the reason for this is that when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in an organic solvent may decrease, while the content is 70%. This is because if it exceeds mol%, the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer (B-2) may deteriorate.
  • the hydroxyl group-containing fluoropolymer (B-2) preferably further comprises the following structural unit (d).
  • structural unit (d) will be described.
  • the structural unit (d) is represented by the following general formula (4).
  • R 8 and R 9 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]
  • the alkyl group represented by R 8 or R 9 is an alkyl group having 1 to 3 carbon atoms such as a methinore group, an ethyl group, or a propyl group. Is trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group Examples of C1-4 fluoroalkyl group isotopes S and aryl groups include phenyl group, benzyl group, naphthyl group and the like.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the general formula (4).
  • azo group-containing polysiloxane compounds include compounds represented by the following general formula (7).
  • R 1Q to R 13 , R ′′ to R 17 , p, q, s, t, and y are the same as those in the general formula (5), and z is a number of! ]
  • the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the following structural unit (e).
  • the structural unit (e) is represented by the following general formula (5).
  • R 1Q to R 13 represent a hydrogen atom, an alkyl group, or a cyano group
  • R 14 to R 17 represent a hydrogen atom or an alkyl group
  • p and q are numbers of:! To 6, s, t is a number from 0 to 6, y is a number from:! to 200.
  • the alkyl groups represented by R 1Q to R 13 have 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group.
  • the alkyl group of RM to R 17 includes an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
  • the azo group-containing polysiloxane compound represented by the general formula (7) is used.
  • a compound represented by the following general formula (8) is particularly preferred.
  • the content of the structural units (d), the total amount of the hydroxyl group-containing fluoropolymer (B- 2) is 100 mol%, 0.1:! A ⁇ 10 mol 0/0 I prefer it.
  • the reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the cured coating film is lowered, and the scratch resistance of the coating film may be lowered. If it exceeds 10 mol%, the hydroxyl group-containing fluoropolymer (B-2) is inferior in transparency, and when used as a coating material, repelling and the like may easily occur during coating. For this reason, the content of the structural unit (d) is more preferably from 0.:!
  • the content of the structural unit (e) is preferably determined so that the content of the structural unit (d) contained therein falls within the above range.
  • the hydroxyl group-containing fluoropolymer (B-2) preferably further comprises the above structural unit (f).
  • the structural unit (f) will be described.
  • the structural unit (f) is represented by the following general formula (6).
  • R represents a group having an emulsifying action
  • the group having an emulsifying action of R 18 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is polyethylene oxide, polypropylene oxide, etc.
  • a group having a polyether structure is preferred.
  • Examples of the group having an emulsifying action include a group represented by the following general formula (9).
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • a reactive emulsifier examples include compounds represented by the following general formula (10).
  • the content of the structural unit (f) may be 0.:! To 5 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. I like it. The reason for this is that when the content rate is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in the solvent is improved, while if the content rate is within mol%, This is because the adhesiveness of the curable resin composition does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material. For these reasons, the content of the structural unit (f) is more preferably 0.:! To 3 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer (B-2). More preferably, it is 0.2 to 3 mol%.
  • the hydroxyl group-containing fluoropolymer (B-2) has a polystyrene equivalent number average molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. It is preferably 5,000 to 500,000. This reason is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer (B-2) may decrease, while the number average molecular weight exceeds 500,000. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult. For these reasons, the hydroxyl-containing fluoropolymer (B-2) has a polystyrene equivalent number average molecular weight of preferably 10,000 to 300,000, more preferably 10,000 to 100,000. Power S More preferred.
  • the ethylenically unsaturated group-containing fluoropolymer (B) used in the present invention comprises the above-described compound (B_ 1) containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group. It is preferably obtained by reacting the fluorine-containing polymer (B-2) with a molar ratio of isocyanate group Z hydroxyl group of 1.:! To 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be lowered. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be deteriorated.
  • the content of (ii) the ethylenically unsaturated group-containing fluoropolymer in the curable resin composition is usually 3 to 70% by mass with respect to 100% by mass of the total composition excluding the organic solvent. is there .
  • the reason for this is that when the content is less than 3% by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. This is because if the added amount exceeds 70% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
  • the (C) fast volatile solvent contained in the curable resin composition is one or two or more kinds of solvents which have high solubility of the above-mentioned (ii) ethylenically unsaturated group-containing fluoropolymer.
  • the high solubility of the ethylenically unsaturated group-containing fluoropolymer means that (i) the ethylenically unsaturated group-containing fluoropolymer is When a fluoropolymer is added to each solvent so as to be 50% by mass and stirred at room temperature for 8 hours, it means that the solution becomes visually uniform.
  • the relative evaporation rate of the (C) fast volatile solvent needs to be larger than the relative evaporation rate of the later-described (D) slow volatile solvent.
  • the “relative evaporation rate” is the relative value of the evaporation rate based on the time required for 90% by weight of butyl acetate to evaporate. For details, see TECHNIQUES OF CHEMISTRY VOL.2 ORG ANIC. SOLVENTS Physical Properties and methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62).
  • the (C) fast volatile solvent preferably has a low dispersion stability of the metal oxide particles (metal oxide particle component (A)) of (A1) and (A2).
  • the fast volatile solvent has a relative evaporation rate higher than that of (D), and (B) the high solubility of the fluorine-containing polymer containing ethylenically unsaturated groups allows the curable resin composition to be used as a base material.
  • the metal oxide particles 1) and (A2) can be unevenly distributed.
  • (A1) and (A2) can be unevenly distributed.
  • the solvent that can be used as the (C) fast volatile solvent in the present invention is a solvent having a relative evaporation rate of about 1.7 or more, specifically, methyl ethyl ketone (MEK; relative evaporation rate). 3.8), isopropanol (IPA; 1.7), methylisoptyl ketone (MIBK; relative evaporation rate 1.6), methyl amyl ketone ( ⁇ ; 0.3), acetone, methyl propyl ketone, etc. .
  • the (D) slow volatile solvent contained in the curable resin composition is one or two or more kinds of solvents that have high dispersion stability of the metal oxide particles (A1) and ( ⁇ 2).
  • the high dispersion stability of the metal oxide particles (A1) and ( ⁇ 2) means that the glass plate is immersed in an isopropanol dispersion of the metal oxide particles (A1) and ( ⁇ 2) (A1) When (A1) and ( ⁇ 2) are attached to the glass wall, and the glass plate to which the metal oxide particles (A1) and ( ⁇ 2) are attached is immersed in each solvent. ) Is uniformly dispersed visually in the solvent.
  • the slow volatile solvent preferably has the low solubility of the above (ii) ethylenically unsaturated group-containing fluoropolymer.
  • Solvents that can be used as the (D) slow volatile solvent in the present invention include methanol (relative evaporation rate 2 ⁇ 1), isopropanol (1; 1 ⁇ 7), ⁇ -butanol (n-BuOH; 0.5), tert-butanol, propylene glycol monomethyl ether, propylene glycol monoethylenoateolene, propyleneglycolmonopropinoleethenole, ethinorescerosolev, propylcellosolve, butylcetosolve and the like.
  • the solvent used for the production of the (B) ethylenically unsaturated group-containing fluoropolymer is usually used as it is. be able to.
  • the (C) fast volatile solvent and (D) slow volatile solvent used in the present invention must be compatible.
  • the compatibility is sufficient if the specific composition of the composition has such a degree of compatibility that (C) fast volatile solvent and (D) slow volatile solvent do not separate.
  • the total amount of the solvent (C) and the solvent (D) is usually 300 parts by mass with respect to 100 parts by mass of the components other than the solvent (including the components (C) and (D)) in the curable resin composition. To 5000 parts by mass, preferably 300 to 4000 parts by mass, more preferably 300 to 3000 parts by mass.
  • the mixing ratio of the solvent (C) and the solvent (D) can be arbitrarily selected within the range of 1:99 to 99: 1.
  • a polyfunctional (meth) attareito toy compound (E-1) containing at least two (meth) attaroyl groups is a cured product obtained by curing a curable resin composition and a reflection using the same. It can be used to increase the scratch resistance of the protective film.
  • the fluorine-containing (meth) ataretoy compound (E_2) containing at least one (meth) ataryloyl group is used to lower the refractive index of the curable resin composition.
  • At least two (meth) atalyloyl groups are present in the molecule. If it is a compound to contain, it will not restrict
  • neopentyl glycol di (meth) acrylate dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and force prolatathone modification
  • Dipentaerythritol hexa (meth) acrylate a compound represented by the following formula (11) is particularly preferred.
  • the compound (E-2) is not particularly limited as long as it is a fluorine-containing (meth) ataretoy compound containing at least one (meth) ataryloyl group.
  • fluorine-containing (meth) ataretoy compound containing at least one (meth) ataryloyl group.
  • examples thereof include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like alone or in combination. The combination of the above is mentioned.
  • the content of component (E) in the curable resin composition is not particularly limited, but is usually 3 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. is there.
  • the reason for this is that if the addition amount is less than 3% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, while if the addition amount exceeds 80% by mass, This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained.
  • the curable resin composition if necessary, it is possible to add (F) a radical photopolymerization initiator (radiation (photo) polymerization initiator) that generates active radical species by radiation (light) irradiation. .
  • a radical photopolymerization initiator radiation (photo) polymerization initiator
  • the radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization.
  • acetophenone acetophenone benzil ketal, 1-hydroxycyclohexyl.
  • Radial (photo) polymerization initiators include, for example, Ciba 'Specialty' Chemicals Co., Ltd. trade names: Inoregacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, 1173, manufactured by BAS F Product name: Lucirin TPO, manufactured by UCB Product name: Nubekril P36, Fratelli 'manufactured by Lamberti Company Name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, ⁇ 046, ⁇ 75 / ⁇ etc.
  • the amount of the photo radical polymerization initiator (F) used as necessary in the present invention may be 0.01 to 10% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass. Preferred 0.1 to 10% by mass is more preferred. If the content is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 10% by mass, the cured product may not be cured to the inside (lower layer).
  • a photosensitizer for the purposes of the present invention, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, a plasticizer are used as necessary.
  • An agent, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, a solvent other than the solvents (C) and (D), and the like can be appropriately blended.
  • composition can be produced as follows.
  • Dispersion of two types of metal oxide particles (A1) and ( ⁇ 2) and ethylenically unsaturated group-containing fluoropolymer (component (B)), if necessary, polyfunctional (meth) acrylate ((E) Component), radiation (light) polymerization initiator (component (F)), etc. are placed in a reaction vessel equipped with a stirrer and stirred at 35 ° C. to 45 ° C. for 2 hours to obtain a curable resin composition.
  • the curable resin composition is suitable for use as an antireflection film or a coating material.
  • a base material to be antireflection or coated include plastics (polycarbonate, polymetatalylate, polystyrene, polyester, polyolefin, epoxy, Melamine, triacetyl cell mouth Glass, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, etc.
  • the shape of the substrate may be a plate, film or three-dimensional molded body.
  • the coating method may be a normal coating method such as date coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush. For example, paint.
  • the thickness of the coating film by these coatings is usually 0.:! To 40 O zm after drying and curing, and preferably :! to 200 zm.
  • the curable resin composition can be cured by radiation (light).
  • the radiation source is not particularly limited as long as the composition can be cured in a short time after coating.
  • a lamp, a resistance heating plate, a laser, or the like is used as an infrared radiation source.
  • tungsten as a source of visible light, such as sunlight, lamps, fluorescent lamps, and lasers, as a source of ultraviolet rays, such as mercury lamps, halide lamps, and lasers, and as a source of electron beams
  • alpha, beta, and gamma ray sources include fission materials such as 6 ° Co.
  • gamma rays it is possible to use a vacuum tube that collides accelerated electrons with the anode. These radiations can be used alone or in combination of two or more simultaneously or over a period of time.
  • the curing reaction of the curable resin composition must be performed under anaerobic conditions such as nitrogen. The reason is that in the presence of oxygen, radical polymerization is inhibited and the curing reaction becomes insufficient.
  • the cured film can be obtained by coating and curing the curable resin composition on various substrates, for example, a plastic substrate. Specifically, it is possible to obtain a coated molded body by coating the composition, preferably drying the volatile component at 0 to 200 ° C., and then performing the above-mentioned curing treatment with radiation.
  • the curing treatment with radiation is preferably performed using ultraviolet rays or electron beams.
  • the preferable irradiation amount of ultraviolet rays is 0.01 to 10 jZcm 2 , and more preferably is 0.:! To 2 j / cm 2 .
  • preferable electron beam irradiation conditions are a pressurization voltage of 10 to 300 KV, an electron density of 0.02 to 0.30 mA / cm 2 , and an electron beam irradiation amount of 1 to: OMrad.
  • the curable resin composition used in the present invention is preferably ultraviolet curable.
  • the metal oxide particles (A1) and (A2) metal oxide The substance particle component (A)) is unevenly distributed on the coated base side (near the boundary with the adjacent layer) or on the opposite side. Therefore, the metal oxide particle component (A) is present in high density near one interface of the cured film, and the metal oxide particle component (A) is substantially absent near the other interface of the cured film. A resin layer having a low refractive index is formed. Therefore, a cured film having a layer structure of two or more layers can be obtained by curing one coating film made of the curable resin composition.
  • the layer in which the metal oxide particle component (A) is present at a high density is a concept indicating a portion where the metal oxide particle component (A) is aggregated. Although the layer is configured as the main component, component (B) may coexist in the layer.
  • the layer in which the metal oxide particle component (A) does not substantially exist is a concept indicating a portion in which the metal oxide particle component (A) does not exist, but does not impair the effects of the present invention.
  • the layer may contain a slight amount of the metal oxide particle component (A), and this layer is substantially a component other than the metal oxide particle component (A) such as a cured product of the components (B) and (E).
  • the cured film includes a layer in which the metal oxide particle component (A) is present at a high density and a layer in which the metal oxide particle component (A) is substantially absent.
  • Each layer has a two-layer structure in which continuous layers are formed.
  • the layer structure of two or more layers means “a layer in which metal oxide particles of (A1) and (A2) are present in high density” and “metal oxide of (A1) and (A2)” It may consist of two or more layers including both of the particles and layers that are substantially free of particles, and two or more “(A1) or (A2) metal oxide particles exist in high density. In some cases, it consists only of “layers”.
  • two or more “layers in which the metal oxide particles exist at high density” may be formed.
  • the “metal oxide particles” in the “layer in which metal oxide particles are present at high density” means at least one, that is, one or more “metal oxide particles”.
  • one “layer in which metal oxide particles exist at high density” may be composed of two or more kinds of metal oxide particles.
  • the (B) fluorine-containing polymer containing an ethylenically unsaturated group in the curable resin composition has a lower refractive index than that of a thermosetting resin (for example, a melamine compound) and has a low refractive index.
  • the layer has preferable optical characteristics. Further, by using metal oxide particles (Aa) having a high refractive index as a constituent material of the metal oxide particle component (A), a further excellent antireflection film can be formed.
  • the cured film is characterized by being capable of forming a coating film (film) having high hardness and excellent scratch resistance and adhesion to the adjacent layer such as the substrate and the low refractive index layer. is doing.
  • a coating film film
  • the cured film is particularly suitably used for an antireflection film for film type liquid crystal elements, touch panels, plastic optical parts and the like.
  • NK Ester A _TMM_ 3LM_N pentaerythritol tri Atari rate 60 mass 0/0 and pentaerythritol Atari rate 40% by weight in the reaction solution.
  • NK Ester A _TMM_ 3LM_N pentaerythritol tri Atari rate 60 mass 0/0 and pentaerythritol Atari rate 40% by weight in the reaction solution.
  • participating in the reaction (Only pentaerythritol triatallylate having a hydroxyl group.) 549 parts were added dropwise at 30 ° C over 1 hour, and then stirred at 60 ° C for 10 hours to obtain a reaction solution.
  • the product in this reaction solution that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group was measured by FT-IR, and it was 0.1% by mass or less, and each reaction was performed almost quantitatively. I confirmed that.
  • the absorption peak of 2550 Kaiser characteristic of mercapto groups in the raw material
  • the absorption peak of 2260 Kaiser characteristic of the raw isocyanate compound
  • the product in this reaction solution that is, the amount of residual isocyanate was determined in the same manner as in Production Example 1.
  • R When measured by R, it was 0.1% by mass or less, and it was confirmed that the reaction was carried out almost quantitatively.
  • the molecule contained a urethane bond and an attalyloyl group (polymerizable unsaturated group).
  • composition containing an organic compound (Ab) having a polymerizable unsaturated group produced in Production Example 1 (A # 1) 2. 32 parts, silica particle sol (methylethylketone silica sol, MEK_ manufactured by Nissan Chemical Industries, Ltd.) ST, number average particle size 0.022 zm, silica concentration 30%) 91.3 parts (27 parts as silica particles), 0.112 parts ion-exchanged water, and 0.01 parts p-hydroxyphenyl monomethyl ether After stirring the mixture at 60 ° C for 4 hours, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion liquid (A # 3)). It was.
  • silica particle sol methylethylketone silica sol, MEK_ manufactured by Nissan Chemical Industries, Ltd.
  • This dispersion (A # 3) 98 ⁇ 6g
  • Composition (A # 2) 3 ⁇ 4g
  • IRGACURE907 (2-methyl-1 [4 (methylthio) phenyl] —2— Morpholinopropane 1-one, manufactured by Chinoku 'Specialty' Chemicals) 1.2 g
  • cyclohexanone 7 g are mixed and stirred to form a silica particle-containing hard coat layer 145 g of the product (solid content concentration 50%) was obtained.
  • Zircoyu particles made by Daiichi Rare Element Chemical Industry Co., Ltd. 300 parts of UEP-100 (primary particle size 10-30 nm) were added to 700 parts of methyl ethyl ketone (MEK) and 168 hours by glass beads. The glass beads were removed to obtain 950 parts of zirconia-dispersed sol. After weighing 2g of the zirconia dispersion sol in an aluminum dish, it was dried on a hot plate at 120 ° C for 1 hour and weighed to obtain a solid content of 30%.
  • MK methyl ethyl ketone
  • ITO sol (10wt% IPA sol) made by Fuji Chemical Co., Ltd. 700g, DPHA 29.5g, 2 methyl 1 [4 (methylthio) phenyl] 2-morpholinopropane 1on lg, isopropyl alcohol (IP A) 1769. 5g An ITO particle-containing composition having a solid content concentration of 4% was obtained.
  • ATO particles Ishihara Techno Co., Ltd., SN-100P, primary particle size 10-30 nm
  • dispersant Adekapulu Knick TR-701
  • methanol methanol
  • 78/21 1 weight ratio was mixed (total solid content 31%, total inorganic content 29.6%).
  • a 50ml plastic bottle of Pain Tossier put 40g of glass beads (manufactured by T ⁇ SHINRIK ⁇ , BZ-01) (bead diameter: 0.1mm) (volume: about 16ml) and the above mixture (30g) for 3 hours. Dispersion and a dispersion sol having a median diameter of 80 nm were obtained.
  • a mixture of 5.6 g of this sol, 5.6 g of p-methoxyphenol, 0.01 g of p-methoxyphenol, and 0.12 g of ion-exchanged water was stirred at 60 ° C for 3 hours, and 1.3 g of orthoformate methyl ester was added. The surface changes by adding and stirring for 1 hour at the same temperature. 311 g of ATO particle dispersion was obtained.
  • Zinc oxide particles (A1-doped ZnO particles manufactured by Sakai Chemical, primary particle size 10-20 nm), dispersant (manufactured by Takamoto Kasei Co., Ltd., High Blood ED151) and propylene glycol monomethyl ether, 27.6 / 4.8 / 67.6 (weight ratio) was mixed (total solid content 30%, total inorganic content 27.6%).
  • a 50 ml plastic bottle with the best paint cheers 40 g of Zircoia beads (bead diameter 0.1 mm) and the above mixed solution (30 g) were placed and dispersed for 8 hours to obtain a dispersion zone with a median diameter of 40 nm.
  • the number average particle diameter of the TiO particles was 20 nm.
  • the average particle size is transmission type
  • the average particle diameter of the silica-based particles was 50 nm.
  • the average particle diameter was measured with a transmission electron microscope.
  • DPPA Dipentaerythritol pentaatarylate
  • UV curable crosslinker (pentafunctional) Inoregacure 369 2-Benzyl-2-dimethylamino-1- 1- (4-morpholinofenol) 1-butanone
  • the silica particle-containing hard coat layer composition prepared in Production Example 3 (solid content concentration 45%) Using a wire bar coater (# 12), it was applied to a triacetyl cellulose film (LOFO, film thickness 80 / m) and then dried in an oven at 80 ° C for 1 minute. Subsequently, a cured film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 j / cm 2 using a high-pressure mercury lamp in the air. When the film thickness of the cured film layer was measured with a stylus type film thickness meter, it was 5 zm.
  • LOFO triacetyl cellulose film
  • FeCl as oxidizing agent, methyl alcohol, 2-butyl alcohol and ethyl acetate
  • a catalyst solution was prepared by dissolving 3% by mass in a solvent in which the sorb was mixed at a ratio of 6: 3: 1.
  • the catalyst solution prepared above was spin-coated on the surface of the triacetyl cellulose film provided with a hard coat layer, and then the resulting catalyst coating film was dried at 60 ° C. for 3 minutes.
  • the polyester film on which the hard coat layer and the catalyst coating film were formed was then placed in a CV D chamber designed to produce saturated 3,4-ethylenedioxythiophene monomer, 3, 4-Ethylenedioxythiophene was polymerized for 30 seconds, and then washed with a methanol solvent to remove unreacted substances to form a conductive layer.
  • the composition After coating the zirconia particle-containing composition prepared in Production Example 4 (solid content concentration 4%) on the polythiophene layer prepared in (2) using a wire bar coater (# 3), the composition is 80 ° C in the oven. Dry at C for 1 minute. Subsequently, a cured film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 j / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere. The thickness of the cured film layer was calculated with a reflection spectrometer to be 65 nm.
  • the resulting catalyst coating film was dried at 60 ° C. for 3 minutes.
  • the polyester film on which the hard coat layer and the catalyst coating film were formed was placed in a CV D chamber designed to produce a saturated 3,4_ethylenedioxythiophene monomer. After 3,4_ethylenedioxythiophene was polymerized for 30 seconds, a conductive layer was formed by washing with methanol solvent to remove unreacted substances.
  • Example 2 It was produced in the same manner as (1).
  • Example 2 It was produced in the same manner as (2).
  • the ATO particle-containing composition (solid content concentration 5%) or the A1-doped ZnO particle-containing composition (solid content concentration 4%) prepared in Production Example 6 or 7 was used.
  • a wire bar coater (# 3) coating was performed on the hard coat layer prepared in (2), and then dried in an oven at 80 ° C for 1 minute.
  • a cured film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 j / cm 2 using a high pressure mercury lamp in a nitrogen atmosphere. It was 65 nm when the film thickness of the cured film layer was computed with the reflection spectrometer.
  • Example 2 It was produced in the same manner as (1).
  • Example 2 It was produced in the same manner as (2).
  • Example 5 When the cross section of the laminate obtained in! To 5 was observed with a transmission electron microscope, the low refractive index layer and the high refractive index layer were separated into two layers in any laminate. It was confirmed that At this time, the low refractive index layer was a layer in which metal oxide particles were not substantially present, and the high refractive index layer was a layer in which metal oxide particles were present at high density.
  • Figure 8 shows the concept of two-layer separation, no separation (partially agglomerated) and uniform structure.
  • the anti-reflection properties of the resulting anti-reflection laminate were measured using a spectral reflectance measurement device (self-recording spectrophotometer U— 3410 incorporating Hitachi Integrating Sphere 150-09090, manufactured by Hitachi, Ltd.).
  • the reflectance at a wavelength of 550 nm was measured and evaluated.
  • the reflectance of the antireflection laminate (antireflection film) was measured using the reflectance of the deposited aluminum film as a reference (100%). As a result, all the laminates had a reflectance of 1% or less at a wavelength of 550 nm.
  • the method for producing a laminate of the present invention since the conductive layer can be formed by gas phase polymerization, a uniform conductive layer can be produced. Moreover, since two or more layers can be formed from one coating film, the production process of a laminate having a multilayer structure of two or more layers can be simplified. Therefore, the method for producing a laminate of the present invention can be advantageously used particularly for the formation of optical materials such as antireflection films, lenses, and selective transmission film filters. Further, the obtained laminate can be suitably used as a paint, weather resistant film, coating, etc. for a substrate requiring weather resistance by utilizing the fact that a layer having a high fluorine content can be included. In addition, the laminate is excellent in adhesion to the substrate and imparts a good antireflection effect with high scratch resistance, so it is extremely useful as an antireflection film, and can be applied to various display devices. The visibility can be improved.

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  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
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  • Laminated Bodies (AREA)

Abstract

L’invention décrit un procédé de production d’un corps multicouche, ce dernier comprenant une base (30) et, disposées sur ladite base (30), une couche conductrice (20) et une structure multicouche (40, 50). Ledit procédé est caractérisé en ce que la couche conductrice (20) est formée par polymérisation en phase vapeur d’au moins un monomère choisi dans le groupe formé du pyrrole, du thiophène, du furanne, du sélénophène, du 3,4-éthylènedioxythiophène et de leurs dérivés. Une pellicule de revêtement est formée en appliquant une composition de résine durcissable, ladite composition contenant des particules d’oxyde métallique de diamètre particulaire moyen supérieur à 1 nm mais inférieur à 40 nm, des particules d’oxyde métallique de diamètre particulaire moyen allant supérieur à 40 nm mais inférieur à 200 nm, un fluoropolymère contenant un groupe à insaturation éthylénique, un solvant très volatil et un solvant faiblement volatil. Deux couches (40, 50) ou plus sont ensuite formées par évaporation des solvants de la pellicule de revêtement unique.
PCT/JP2005/020574 2004-11-16 2005-11-10 Procede de production d’un corps multicouche WO2006054472A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN106280730A (zh) * 2016-08-14 2017-01-04 安庆市沁之源电器有限公司 一种燃气灶抗菌涂料及其制备方法

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JPH11228631A (ja) * 1998-02-12 1999-08-24 Jsr Corp 硬化性樹脂組成物および反射防止膜
JP2002082207A (ja) * 2000-09-07 2002-03-22 Fuji Photo Film Co Ltd 防眩性反射防止フィルムおよび液晶表示装置
JP2003082105A (ja) * 2001-09-14 2003-03-19 Hanyang Hak Won Co Ltd 気相重合法による伝導性高分子の合成方法及びその製造物
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2004093947A (ja) * 2002-08-30 2004-03-25 Fuji Photo Film Co Ltd 反射防止膜、反射防止フィルムおよび画像表示装置
JP2004317734A (ja) * 2003-04-15 2004-11-11 Fuji Photo Film Co Ltd 反射防止膜、その製造方法、反射防止フィルムおよび画像表示装置
JP2005297539A (ja) * 2004-03-18 2005-10-27 Jsr Corp 積層体の製造方法

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JPH09100111A (ja) * 1995-10-03 1997-04-15 Japan Synthetic Rubber Co Ltd 反応性シリカ粒子、その製法および用途
JPH11228631A (ja) * 1998-02-12 1999-08-24 Jsr Corp 硬化性樹脂組成物および反射防止膜
JP2002082207A (ja) * 2000-09-07 2002-03-22 Fuji Photo Film Co Ltd 防眩性反射防止フィルムおよび液晶表示装置
JP2003082105A (ja) * 2001-09-14 2003-03-19 Hanyang Hak Won Co Ltd 気相重合法による伝導性高分子の合成方法及びその製造物
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2004093947A (ja) * 2002-08-30 2004-03-25 Fuji Photo Film Co Ltd 反射防止膜、反射防止フィルムおよび画像表示装置
JP2004317734A (ja) * 2003-04-15 2004-11-11 Fuji Photo Film Co Ltd 反射防止膜、その製造方法、反射防止フィルムおよび画像表示装置
JP2005297539A (ja) * 2004-03-18 2005-10-27 Jsr Corp 積層体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106280730A (zh) * 2016-08-14 2017-01-04 安庆市沁之源电器有限公司 一种燃气灶抗菌涂料及其制备方法

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