JP6765912B2 - A laminate capable of projecting an image, and an image projection system equipped with the laminate - Google Patents

Description

The present invention relates to a laminate capable of projecting an image while having excellent specular reflectivity like a mirror, an image projection system provided with the laminate, and a spatial effect method using them.

Conventionally, when projecting an image, it is common that the image light is projected onto an image projecting object such as a screen by a projection device, and the observer observes the image (see Patent Document 1). In recent years, there has been an increasing demand for projecting product information, advertisements, etc. on show windows of department stores, transparent partitions of event spaces, etc. using an image projection system including such a projection device and an image projecting object. ..

Furthermore, at present, in order to produce a more attractive space, there is an increasing demand for projecting image light onto an object that has not been conventionally used as an image projected object.

Japanese Unexamined Patent Publication No. 2006-146019

The present inventors have attempted to project an image onto an existing mirror, but the existing mirror has a high specular reflectance, and the projected light is also specularly reflected as it is with natural light or artificial light. The image could not be imaged.

Conventionally, the reflective liquid crystal device has a polarizing plate + a diffusing glue layer (scattering layer) + an LCD + a specular reflecting plate, or a polarizing plate + an LCD + a reflecting plate having a surface uneven structure, that is, a specular reflecting plate + a diffusing glue. Layers or uneven reflectors are used. The reflective layer in these configurations can also project an image, but the reflective layer in this configuration can project an image because the mirror surface state is eliminated by the diffuse glue and the surface uneven structure and diffuse reflection occurs, and natural light or natural light or It is not possible to reflect artificial light as it is.

The present invention has been made in view of the above technical problems, and an object of the present invention is to provide a laminated body capable of projecting an image while having excellent specular reflectivity like a mirror.

As a result of diligent studies in order to solve the above technical problems, the present inventors have obtained a mirror by using a laminated body including a transparent image projection layer and a light reflection layer having a specular reflectance of 60% or more. It was found that a laminate that fulfills the image display function can be obtained by forming an image of the image light produced by the projection device on the transparent image projection layer while having excellent specular reflectance. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention.
Provided is a laminate capable of projecting an image, comprising a transparent image projection layer and a light reflection layer having a specular reflectance of 60% or more.

In the aspect of the present invention, it is preferable that the transparent image projection layer includes a binder and at least one of light-reflecting fine particles and light-diffusing fine particles.

In the aspect of the present invention, the average diameter of the primary particles of the light-reflecting fine particles is preferably 0.01 to 100 μm.

In the aspect of the present invention, it is preferable that the shape of the light-reflecting fine particles is flaky, the average aspect ratio is 3 to 800, and the specular reflectance is 12 to 100.

In the aspect of the present invention, the content of the light-reflecting fine particles is preferably 0.0001 to 5.0% by mass with respect to the binder.

In aspects of the invention, the light-reflecting microparticles are selected from the group consisting of aluminum, silver, copper, platinum, gold, titanium, nickel, tin, tin-cobalt alloys, indium, chromium, aluminum oxide, and zinc sulfide. It is preferable that the metal-based particles to be used, a glittering material in which glass is coated with a metal or a metal oxide, or a glittering material in which a natural mica or a synthetic mica is coated with a metal or a metal oxide.

In the embodiment of the present invention, the difference between the refractive index n ₂ of the light diffusing fine particles and the refractive index n ₁ of the binder is the following mathematical formula (1):
| N _1- n ₂ | ≧ 0.1 ・ ・ ・ (1)
It is preferable to satisfy.

In the embodiment of the present invention, the light diffusing fine particles are zirconium oxide, zinc oxide, titanium oxide, cerium oxide, barium titanate, strontium titanate, magnesium oxide, calcium carbonate, barium sulfate, diamond, crosslinked acrylic resin, and crosslinked. It is preferably at least one selected from the group consisting of styrene resin and silica.

In the aspect of the present invention, the median diameter of the primary particles of the light diffusing fine particles is preferably 0.1 to 500 nm.

In the aspect of the present invention, the content of the light diffusing fine particles is preferably 0.0001 to 2.0% by mass with respect to the binder.

In the embodiment of the present invention, it is preferable that the average secondary particle diameter of the light-reflecting fine particles and / or the light-diffusing fine particles is 100 nm to 200 μm.

In the aspect of the present invention, the haze of the transparent image projection layer is preferably 35% or less.

In the aspect of the present invention, it is preferable that the light reflecting layer includes a metal vapor deposition film.

According to another aspect of the present invention, an image projection system including the above-mentioned laminate and a projection device is provided.

According to another aspect of the present invention, there is provided a spatial effect method using the above-mentioned laminate or the above-mentioned image projection system.

The laminated body of the present invention includes a transparent image projection layer and a light reflection layer having a specular reflectance of 60% or more, so that the image light produced by the projection device can be transmitted as a transparent image while having excellent specular reflectivity like a mirror. An image is formed on the projection layer to perform an image display function. According to such a laminated body, it is possible to produce a more attractive space.

It is sectional drawing in the thickness direction of one Embodiment of the laminated body by this invention. It is a schematic diagram which showed one Embodiment of the image projection system by this invention.

<Laminated body>
The laminated body according to the present invention includes a transparent image projection layer and a light reflection layer, and can project an image. That is, the laminated body according to the present invention can fulfill both a function as a mirror and a function as an image display device. In the present invention, "transparent" means that it is sufficient if it is transparent enough to realize transparent visibility according to the application, and it also includes translucency.

FIG. 1 shows a schematic cross-sectional view in the thickness direction of one embodiment of the laminate according to the present invention. The laminate 15 includes a transparent image projection layer 13 in which at least one of the light-reflecting fine particles 11 and the light-diffusing fine particles 12 is dispersed in the binder 10, and a light-reflecting layer 14. The laminated body 15 anisotropically scatters the projected light 16 projected by the projection device, so that the viewer 18 can visually recognize the scattered light 17. Further, the laminated body 15 can also function as a normal mirror when the projected light 16 is not projected. The laminated body 15 may have a two-layer structure composed of a transparent image projection layer 13 and a light reflection layer 14, and may further include other layers such as a protective layer, a base material layer, an adhesive layer, and an antireflection layer. You may prepare.

The laminate has a haze of preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and a total light transmittance of preferably 70% or less, more preferably. Is 50% or less, more preferably 30% or less. In the present invention, the haze value and the total light transmittance of the laminated body are determined by JIS-K-7361 and JIS-K- using a turbidity meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product number: NDH-5000). It can be measured according to 7136.

The laminate has a specular reflectance of preferably 55% or more, more preferably 60% or more, still more preferably 80% or more. If the specular reflectance of the laminated body is within the above range, the function as a mirror can be sufficiently fulfilled. In the present invention, the specular reflectance of the laminated body is a value measured as follows.
(Specular reflectance of laminated body)
The measurement was performed using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product number: CM-3500d).

The thickness of the laminate is not particularly limited, but is preferably 10 μm to 20 mm, more preferably 20 μm to 15 mm, and further, from the viewpoint of application, productivity, handleability, and transportability. It is preferably 30 μm to 10 mm. In the present invention, the "laminated body" includes a so-called film, a sheet, a coating film formed by coating on a substrate, a plate (plate-shaped molded product), and other molded products having various thicknesses.

(Transparent image projection layer)
The transparent image projection layer includes a binder and at least one of light-reflecting fine particles and light-diffusing fine particles. By containing at least one of the light-reflecting fine particles and the light-diffusing fine particles, the laminated body can sufficiently form an image on the transparent image projection layer.

The transparent image projection layer has a haze of preferably 35% or less, more preferably 30% or less, further preferably 20% or less, and a total light transmittance of preferably 60% or more. It is more preferably 65% or more, still more preferably 70% or more. In the present invention, the haze value and the total light transmittance of the transparent image projection layer are determined by JIS-K-7361 and JIS-using a turbidity meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product number: NDH-5000). It can be measured according to K-7136.

The thickness of the transparent image projection layer is not particularly limited, but is preferably 0.1 μm to 20 mm, more preferably 0.2 μm to 200 mm from the viewpoint of application, productivity, handleability, and transportability. It is 15 mm, more preferably 1 μm to 10 mm, even more preferably 10 μm to 2 mm, and most preferably 50 μm to 1 mm. The transparent image projection layer may be a film, or may be a coating film formed on a substrate made of glass, resin, or the like. The transparent image projection layer may have a single-layer structure, or may have a multi-layer structure in which two or more types of layers are laminated by coating or the like, or two or more types of layers are bonded together with an adhesive or the like.

(Binder)
As the binder for forming the transparent image projection layer, any material may be used as long as it has high transparency, and it is preferable to use an inorganic binder or an organic binder.

Examples of the highly transparent inorganic binder include water glass, a glass material having a low softening point, and a sol-gel material. Water glass refers to a concentrated aqueous solution of an alkali silicate, and usually contains sodium as an alkali metal. A typical water glass can be represented by Na ₂ O · nSiO ₂ (n: any positive number). Commercially available water glasses have n in the range of 2-4. Commercially available water glasses include Nos. 1 to 3 as sodium silicate aqueous solutions, and the ratio of SiO ₂ to Na ₂ O increases in this order. When water is evaporated from water glass, a solid that is hard to break and has elasticity and contains about 10 to 30% by mass of water, which is called Japanese water glass, is formed, and the function as a binder having adhesiveness is exhibited. Further, depending on the case, some K ₂ O may be contained instead of Na ₂ O, but even in this case, the molar ratio with SiO ₂ is preferably in the above range. The function as a binder is that the higher the molecular weight of polysilicate ions contained in water glass, the more likely it is to form a cured film with higher mechanical strength. However, cracks may easily form in the cured film, so it can be used as a coating liquid. It is preferable to use water glass contained at an optimum molar ratio of SiO _{2 to} Na ₂ O depending on the concentration and pH of the water glass contained at the time of use, the ratio to hydroxyapatite, and the like. As the water glass, sodium silicate manufactured by Fuji Chemical Co., Ltd. can be used.

The glass material having a low softening point is a glass having a softening temperature preferably in the range of 150 to 620 ° C, more preferably a softening temperature in the range of 200 to 600 ° C, and most preferably a softening temperature of 250 to 550. It is in the range of ° C. As such a glass material, a mixture containing PbO-B ₂ O ₃ system, PbO-B ₂ O _3- SiO ₂ system, PbO-ZnO-B ₂ O ₃ system, an acid component and a metal chloride is heat-treated. The lead-free low-softening point glass obtained by the above can be mentioned. The low softening point glass material is preferably a so-called glass frit, which is melted in a curing step described later. Further, as the low softening point glass material, it is preferable to use a powder having a median diameter in the range of 1 to 50 μm. A solvent, a high boiling point organic solvent, or the like can be mixed with the low softening point glass material in order to improve the dispersibility and moldability of the fine particles.

A sol-gel material is a group of compounds in which hydrolysis polycondensation proceeds and cures due to the action of heat, light, a catalyst, or the like. For example, a metal alkoxide (metal alcoholate), a metal chelate compound, a metal halide, a liquid glass, a spin-on glass, or a reaction product thereof, which may contain a catalyst that promotes curing. Further, a part of the metal alkoxide functional group may have a photoreactive functional group such as an acrylic group. These may be used alone or in combination of a plurality of types depending on the required physical properties. The cured product of the sol-gel material refers to a state in which the polymerization reaction of the sol-gel material has sufficiently proceeded. The sol-gel material chemically bonds with the surface of the inorganic substrate in the process of the polymerization reaction and adheres strongly. Therefore, a stable cured product layer can be formed by using a cured product of a sol-gel material as the cured product layer.

A metal alkoxide is a group of compounds obtained by reacting an arbitrary metal species with water or an organic solvent using a hydrolysis catalyst or the like. The metal alkoxide is a group of compounds obtained by reacting any metal species with water or an organic solvent. It is a group of compounds in which a functional group such as a group is bonded. Examples of the metal species of the metal alkoxide include silicon, titanium, aluminum, germanium, boron, zirconium, tungsten, sodium, potassium, lithium, magnesium and tin.

For example, metal alkoxides whose metal type is silicon include dimethyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane (MTES), vinyltriethoxysilane, p-styryltriethoxysilane, and methylphenyldi. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 − Methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxy Silane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, triethoxysilane (TEOS), diphenylsilanediol, dimethylsilanediol, etc. Examples thereof include a group of compounds in which the ethoxy group of these compound groups is replaced with a methoxy group, a propyl group, an isopropyl group, a hydroxy group and the like. Among these, TEOS and tetramethoxysilane (TMS) in which the ethoxy group of TEOS is replaced with a methoxy group are particularly preferable. These may be used alone or in combination of a plurality of types.

When using TEOS, MTES or mixtures thereof, their mixing ratio can be, for example, 1: 1 in molar ratio. This sol solution produces amorphous silica by subjecting it to hydrolysis and polycondensation reaction. As a synthetic condition, an acid such as hydrochloric acid or an alkali such as ammonia is added to adjust the pH of the solution. The pH is preferably 4 or less or 10 or more. Water may also be added to carry out hydrolysis. The amount of water added can be 1.5 times or more in molar ratio with respect to the metal alkoxide species.

Further, as the metal alkoxide, a silsesquioxane compound can also be used. Sylsesquioxane is a general term for a group of compounds represented by SiO _1.5 , and is a compound in which one organic group and three oxygen atoms are bonded to one silicon atom. The metal halide is a group of compounds in which the functional group to be hydrolyzed and polycondensed is replaced with a halogen atom in the above metal alkoxide.

Examples of the metal chelate compound include titanium diisopropoxybis acetylacetone, titanium tetrakis acetyl acetone, titanium dibutoxybis octylene glycolate, zirconium tetrakis acetyl acetone, zirconium dibutoxybis acetyl acetone, and aluminum tris acetyl acetone. Examples thereof include aluminum dibutoxymonoacetylacetoneate, zinc bisacetylacetoneate, indium trisacetylacetoneate, and polytitanium acetylacetoneate.

Examples of the highly transparent organic binder include resins such as thermoplastic resins, ionizing radiation curable resins, thermosetting resins, and adhesives. The thermoplastic resin may be any resin that is easily dissolved in a solvent. As such a thermoplastic resin, for example, acrylic resin, polyester resin, polyolefin resin, vinyl resin, polycarbonate resin, and polystyrene resin can be used, and polymethyl methacrylate resin and polyethylene terephthalate resin can be used. , Polyethylene naphthalate resin, polypropylene resin, cycloolefin resin, cellulose acetate propionate resin, polyvinyl butyral resin, polycarbonate resin, ethylene / vinyl acetate copolymer resin, nitrocellulose resin and polystyrene resin can be used. These resins can be used alone or in combination of two or more. Examples of the ionizing radiation curable resin include acrylic-based and urethane-based resins, acrylic urethane-based and epoxy-based resins, and silicone-based resins. Among these, those having an acrylate-based functional group, for example, polyester resin having a relatively low molecular weight, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutagen resin, polythiol polyene resin, many Monofunctional monomers such as (meth) alrilate of polyfunctional compounds such as valent alcohols, or monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylpyrrolidone as reactive diluents. Also, polyfunctional monomers such as polymethylol propantri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol. Those containing a relatively large amount of hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like are preferable. Further, the ionizing radiation curable resin may be a mixture of a thermoplastic resin and a solvent, or may be used as a hard coat layer for imparting scratch resistance and antiglare property. Examples of the ionizing thermosetting resin include silicone-based resins, epoxy resins, urethane resins, and acrylic resins. Examples of the thermosetting resin include phenolic resin, epoxy resin, silicone resin, melamine resin, urethane resin, urea resin and the like. Among these, epoxy resins and silicone resins are preferable. Further, polyvinyl butyral resin and ethylene / vinyl acetate copolymer resin, which are thermoplastic resins, have excellent adhesiveness to substrates such as glass, metal, and ceramics, and can also be used as an adhesive. Commercially available products can be used as the organic binder, for example, acrylic lacquer (Recrack 73 Clear manufactured by Fujikura Kasei Co., Ltd.), urethane acrylate type UV curable resin (Unidic V-4018 manufactured by DIC Corporation), and the like. Product name: EA-415 manufactured by Sanyulek Co., Ltd. can be mentioned.

By using an adhesive as an organic binder, it is possible to impart adhesiveness to the transparent image projection layer. Examples of the pressure-sensitive adhesive include natural rubber-based, synthetic rubber-based, acrylic resin-based, polyvinyl ether resin-based, urethane resin-based, and silicone resin-based adhesives. Specific examples of the synthetic rubber system include styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisobutylene rubber, isobutylene-isoprene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, and styrene-ethylene-butylene block. Examples include copolymers. Specific examples of the silicone resin system include dimethylpolysiloxane. These pressure-sensitive adhesives can be used alone or in combination of two or more. Among these, acrylic adhesives are preferable.

The acrylic resin pressure-sensitive adhesive is polymerized by containing at least a (meth) acrylic acid alkyl ester monomer. It is generally a copolymer of a (meth) acrylic acid alkyl ester monomer having an alkyl group having about 1 to 18 carbon atoms and a monomer having a carboxyl group. The (meth) acrylic acid refers to acrylic acid and / or methacrylic acid. Examples of (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, sec-propyl (meth) acrylic acid, and (meth) acrylic acid. n-butyl, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Examples thereof include n-octyl, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, undecyl (meth) acrylate, and lauryl (meth) acrylate. Further, the (meth) acrylic acid alkyl ester is usually copolymerized in an acrylic pressure-sensitive adhesive at a ratio of 30 to 99.5 parts by mass.

Further, as the monomer having a carboxyl group forming the acrylic resin pressure-sensitive adhesive, a monomer containing a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, monobutyl maleate and β-carboxyethyl acrylate. Can be mentioned.

In addition to the above, the acrylic resin pressure-sensitive adhesive may be copolymerized with a monomer having another functional group within a range that does not impair the characteristics of the acrylic resin pressure-sensitive adhesive. Examples of monomers having other functional groups are monomers containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and allyl alcohol; (meth) acrylamide, N-methyl. Monomers containing amide groups such as (meth) acrylamide and N-ethyl (meth) acrylamide; monomers containing amide groups and methylol groups such as N-methylol (meth) acrylamide and dimethylol (meth) acrylamide; aminomethyl ( Monomers having functional groups such as amino group-containing monomers such as meta) acrylate, dimethylaminoethyl (meth) acrylate and vinylpyridine; epoxy group-containing monomers such as allyl glycidyl ether and glycidyl ether (meth) acrylate. Can be mentioned. In addition to fluorine-substituted (meth) acrylic acid alkyl esters, (meth) acrylonitrile, vinyl group-containing aromatic compounds such as styrene and methyl styrene, vinyl acetate, vinyl halide compounds and the like can be mentioned.

As the acrylic resin pressure-sensitive adhesive, in addition to the above-mentioned monomers having other functional groups, other monomers having an ethylenic double bond can be used. Examples of monomers having an ethylenic double bond include diesters of α, β-unsaturated dibasic acids such as dibutyl maleate, dioctyl maleate and dibutyl fumarate; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers. Vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; (meth) acrylonitrile and the like can be mentioned. Further, in addition to the monomer having an ethylenic double bond as described above, a compound having two or more ethylenic double bonds can also be used in combination. Examples of such compounds include divinylbenzene, diallyl malate, diallyl phthalate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, methylenebis (meth) acrylamide and the like.

Commercially available adhesives may be used, for example, SK Dyne 2094, SK Dyne 2147, SK Dyne 1811L, SK Dyne 1442, SK Dyne 1435, and SK Dyne 1415 (all manufactured by Soken Kagaku Co., Ltd.). Oliverine EG-655, Oliverine BPS5896 (above, manufactured by Toyo Ink Co., Ltd.) and the like (above, trade name) can be preferably used.

The binder for forming the transparent image projection layer according to the present invention may contain a solvent depending on the method for producing the transparent image projection layer. The solvent is not limited to the organic solvent, and any solvent used in general coating compositions can be used. For example, a hydrophilic solvent such as water can also be used. Further, when the binder of the present invention is a liquid, it does not have to contain a solvent.

Specific examples of the solvent according to the present invention include alcohols such as methanol, ethanol, isopropyl alcohol (IPA), n-propanol, butanol, 2-butanol, ethylene glycol and propylene glycol, hexane, heptane, octane and decane. Aliper hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetramethylbenzene, ethers such as diethyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, isophorone, cyclohexanone, cyclopentanone. , N-Methyl-2-pyrrolidone and other ketones, butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol, benzyloxyethanol and other ether alcohols, ethylene glycol, propylene glycol and other glycols, ethylene glycol dimethyl ether , Diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone, and phenols such as phenol and chlorophenol. , N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other amides, chloroform, methylene chloride, tetrachloroethane, monochlorobenzene, dichlorobenzene and other halogen solvents, and heterocarbon disulfide and the like. Included are elemental compounds, water, and mixed solvents thereof. The amount of the solvent added can be appropriately adjusted according to the type of binder and fine particles, the viscosity range suitable for the coating or spraying step described later, and the like.

Conventionally known additives may be added to the transparent image projection layer in addition to the fine particles, depending on the application, as long as the desired optical performance is not impaired. Additives include, for example, antioxidants, surfactants, thickeners, compatibilizers, nucleating agents, UV absorbers, light stabilizers, antistatic agents, mold release agents, flame retardants, plasticizers, lubricants, etc. And coloring materials and the like. As the coloring material, dyes or dyes such as carbon black, azo dyes, anthraquinone dyes, and perinone dyes can be used. Further, a liquid crystal compound or the like may be mixed.

(Light reflective fine particles)
As the light-reflecting fine particles, a brilliant material that can be processed into flakes can be preferably used. The specular reflectance of the light-reflecting fine particles is preferably 12.0% or more, more preferably 15.0% or more and 100% or less, and further preferably 20.0% or more and 95% or less. In the present invention, the specular reflectance of the light-reflecting fine particles is a value measured as follows.
(Specular reflectance of light-reflecting fine particles)
Measured using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product number: CM-3500d. Light-reflecting fine particles dispersed in an appropriate solvent (water or methyl ethyl ketone) are placed on a slide glass with a thickness of 0.5 mm. The glass plate with a coating film was coated and dried as described above. The positive reflectance when light was incident from the glass surface to the coating film at an angle of 45 degrees with respect to the normal line of the glass surface was measured. By measuring the positive reflectance when the light-reflecting fine particles are used as a coating film, it is possible to grasp the reflection performance of the light-reflecting fine particles in consideration of the oxidation state of the surface of the fine particles.

The light-reflecting fine particles may be, for example, aluminum, silver, copper, platinum, gold, titanium, nickel, tin, tin-cobalt alloy, indium, chromium, aluminum oxide, zinc sulfide, etc., depending on the type of binder to be dispersed. Metal-based fine particles, a glittering material in which glass is coated with a metal or a metal oxide, or a glittering material in which a natural mica or a synthetic mica is coated with a metal or a metal oxide can be used.

As the metal material used for the metal-based fine particles, a metal having excellent reflectivity of projected light is used. Specifically, the metal material has a reflectance R at a measurement wavelength of 550 nm, preferably 50% or more, more preferably 55% or more, still more preferably 60% or more, still more preferably 70% or more. Is. Hereinafter, in the present invention, the "reflectance R" refers to the reflectance when light is incident on a metal material from a vertical direction. The reflectance R can be calculated by the following equation (1) using the values of the refractive index n and the extinction coefficient k, which are eigenvalues of the metal material. n and k are described in, for example, Handbook of Optical Constants of Solids: Volume 1 (by Edward D. Palik), PB Johnson and RW Christy, PHYSICAL REVIEW B, Vol.6, No.12, 4370-4379 (1972), etc. Are listed.
R = {(1-n) ² + k ² } / {(1 + n) ² + k ² } Equation (1)
That is, the reflectance R (550) at the measurement wavelength of 550 nm can be calculated from n and k when measured at the wavelength of 550 nm. For metal materials, the absolute value of the difference between the reflectance R (450) at the measurement wavelength 450 nm and the reflectance R (650) at the measurement wavelength 650 nm is within 25% of the reflectance R (650) at the measurement wavelength 550 nm. Yes, preferably within 20%, more preferably within 15%, and even more preferably within 10%. By using such a metal material, the reflectivity and color reproducibility of incident light are excellent.

The metal material used for the metal-based fine particles has a dielectric constant in the real number term ε', preferably -60 to 0, and more preferably -50 to -10. The real number term ε'of the permittivity can be calculated by the following equation (2) using the values of the refractive index n and the extinction coefficient k.
ε'= n ^2- k ² equation (2)
Although the present invention is not bound by any theory, when the real number term ε'of the permittivity of the metal material satisfies the above numerical range, the following actions occur, and a transparent light scatterer is suitable for an image display device. It is thought that it can be used for. That is, when light enters the metal-based fine particles, a oscillating electric field due to the light is generated in the metal-based fine particles, but at the same time, reverse electric polarization is generated by the free electrons of the metal-based fine particles, and the electric field is shielded. When the real number light ε'of the dielectric constant is 0 or less, the light is completely blocked and light cannot enter into the metal-based fine particles, that is, there is no diffusion due to surface irregularities or light absorption by the metal-based fine particles. Assuming that, all the light is reflected on the surface of the metal-based fine particles, so that the light reflectivity is strong. When ε'is greater than 0, the vibration of the free electrons of the metallic fine particles cannot follow the vibration of the light, so the oscillating electric field due to the light cannot be completely canceled, and the light enters the metallic fine particles. , Transparent. As a result, only a part of the light is reflected on the surface of the metal-based fine particles, and the light reflectivity is lowered.

As the metal material, it is particularly preferable that a metal material satisfying the above-mentioned reflectance R, preferably further a dielectric constant is used, and a pure metal or an alloy can also be used. The pure metal is preferably selected from the group consisting of aluminum, silver, platinum, titanium, nickel, and chromium. As the metal-based fine particles, fine particles made of these metal materials and fine particles obtained by coating these metal materials with resin, glass, natural mica, synthetic mica, or the like can be used. For various metal materials, the refractive index n and the extinction coefficient k at each measurement wavelength are summarized in Table 1, and the reflectance R and ε'calculated using the values are summarized in Table 2.

The light-reflecting fine particles have an average primary particle diameter of preferably 0.01 to 100 μm, more preferably 0.05 to 80 μm, still more preferably 0.1 to 50 μm, and even more preferably 0.5 to 30 μm. .. Further, the light-reflecting fine particles have an average aspect ratio (= average diameter / average thickness of the light-reflecting fine particles) preferably 3 to 800, more preferably 4 to 700, still more preferably 5 to 600, and even more preferably 10. ~ 500. When the average diameter and the average aspect ratio of the light-reflecting fine particles are within the above ranges, an image can be sufficiently imaged without impairing the specular reflectivity of the laminated body. In the present invention, the average diameter of the light-reflecting fine particles was measured using a laser diffraction type particle size distribution measuring device (manufactured by Shimadzu Corporation, product number: SALD-2300). The average aspect ratio was calculated from SEM (manufactured by Hitachi High-Technologies Corporation, trade name: SU-1500) image.

As the light-reflecting fine particles, commercially available ones may be used, and for example, aluminum powder manufactured by Daiwa Metal Powder Industry Co., Ltd. and the trade name Metashine manufactured by Matsuo Industry Co., Ltd. can be preferably used.

The content of the light-reflecting fine particles in the binder can be appropriately adjusted according to the specular reflectance of the light-reflecting fine particles. The content of the light-reflecting fine particles in the binder is preferably 0.0001 to 5.0% by mass, preferably 0.0005 to 3.0% by mass, and more preferably 0. It is 001 to 1.0% by mass, more preferably 0.005 to 0.5% by mass. By forming the transparent image projection layer by dispersing the light-reflecting fine particles in the binder at a low concentration as in the above range, the image can be sufficiently imaged without impairing the specular reflectivity of the laminated body.

(Light diffusing fine particles)
The light diffusing fine particles may contain spherical particles, or may include spherical particles having irregularities or protrusions. Refractive index _{n 1} and the refractive index _{n 2} of the substantially spherical fine particles of the binder, the following equation (1):
| N _2- n ₁ | ≧ 0.1 ・ ・ ・ (1)
It is preferable that the following formula (2):
| N _2- n ₁ | ≧ 0.15 ・ ・ ・ (2)
It is more preferable to satisfy the following formula (3):
3.0 ≧ | n ₂ −n ₁ ｜ ≧ 0.2 ・ ・ ・ (3)
It is more preferable to satisfy.
When the refractive index of the binder forming the transparent image projection layer and the light diffusing fine particles satisfies the above formula, the transparent image projection layer can disperse light anisotropically and improve the viewing angle. Further, by using the light diffusing fine particles, light can be scattered in all directions and the brightness can be improved.

As the light diffusing fine particles having a high refractive index, for example, the refractive index is preferably 1.80 to 3.55, more preferably 1.9 to 3.3, and further preferably 2.0 to 3. Metallic particles obtained by atomizing an inorganic substance, a metal oxide or a metal salt, which is 0.0, can be used. Examples of the inorganic substance include diamond (n = 2.42). Examples of the metal oxide include zirconium oxide (n = 2.40), zinc oxide (n = 2.40), titanium oxide (n = 2.72), and cerium oxide (n = 2.20). Can be mentioned. Examples of the metal salt include barium titanate (n = 2.40) and strontium titanate (n = 2.37). Further, as the light diffusing fine particles having a low refractive index, for example, the refractive index is preferably 1.35 to 1.80, more preferably 1.4 to 1.75, and further preferably 1.45. It is about 1.7, and examples thereof include inorganic fine particles obtained by atomizing inorganic substances such as magnesium oxide (n = 1.74), barium sulfate (n = 1.64), and calcium carbonate (n = 1.65). Further, examples of the organic substantially spherical fine particles having a low refractive index include acrylic particles and polystyrene particles. These light-diffusing fine particles can be used alone or in combination of two or more.

The median diameter of the primary particles of the light diffusing fine particles is preferably 0.1 to 500 nm, more preferably 0.2 to 300 nm, and further preferably 0.5 to 200 nm. When the median diameter of the primary particles of the light diffusing fine particles is within the above range, an image can be sufficiently imaged without impairing the specular reflectivity of the laminated body. In the present invention, the median diameter (D ₅₀ ) of the primary particles of the light diffusing fine particles is determined by using a particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., trade name: DLS-8000) by a dynamic light scattering method. It can be obtained from the measured particle size distribution.

The content of the light diffusing fine particles can be appropriately adjusted according to the thickness of the transparent image projection layer and the refractive index of the fine particles. The content of the light diffusing fine particles in the binder is preferably 0.0001 to 2.0% by mass, more preferably 0.001 to 1.0% by mass, and further preferably 0 with respect to the binder. It is .005 to 0.8% by mass, and even more preferably 0.01 to 0.5% by mass. By forming the transparent image projection layer by dispersing the light diffusing fine particles in the binder within the above range, the image can be sufficiently imaged without impairing the specular reflectivity of the laminated body.

The light-reflecting fine particles and the light-scattering fine particles are aggregated in a transparent light scatterer to an appropriate size capable of achieving both transparency, reflectivity, and light scattering property. Specifically, the average secondary particle diameter of the light-reflecting fine particles and the light-scattering fine particles in the transparent light scattering body is preferably 100 nm to 200 μm, more preferably 200 nm to 100 μm, and further preferably 300 nm to 300 nm. It is 10 μm. When the average secondary particle size is about the above range, it is possible to prevent the visually recognized image light from becoming bluish, and it is possible to realize excellent transparency. The average secondary particle size is based on an image measured with a scanning electron microscope (SEM, manufactured by Hitachi High-Technologies Co., Ltd., trade name: SU-1500), and the particle size = (particle size in the major axis direction + short). It is a value obtained by calculating the average value of the particle diameter when the particle diameter in the axial direction) / 2.

When the thickness of the transparent image projection layer is t (μm) and the concentration of the light-reflecting fine particles and / or the light-diffusing fine particles with respect to the binder is c (mass%), t and c are the following formulas. (I):
0.05 ≦ (t × c) ≦ 50 ・ ・ ・ (I)
It is preferable to meet
0.1 ≦ (t × c) ≦ 40 ・ ・ ・ (I-2)
It is more preferable to meet
0.15 ≦ (t × c) ≦ 35 ・ ・ ・ (I-3)
It is more preferable to meet
0.3 ≦ (t × c) ≦ 30 ・ ・ ・ (I-4)
It is even more preferable to satisfy. When the thickness t and the density c of the transparent image projection layer satisfy the above formula (I), the dispersed state of the fine particles in the binder of the transparent image projection layer is sparse (the concentration of the fine particles in the binder is low). The proportion of light that passes straight through is increased (the proportion of light that does not collide with fine particles is increased), and as a result, an image can be sufficiently imaged without impairing the normal reflectivity of the laminated body. When two or more kinds of light-reflecting fine particles and / or light-diffusing fine particles are contained, the concentration c is the total concentration of all the fine particles, and when the transparent image projection layer is manufactured by the coating method described later, the transparent image is obtained. The thickness t of the projection layer is the thickness of the cured film obtained by curing the binder to which the solvent is added. The cured film in the present invention is a transparent film obtained by curing a dispersion in which at least one of light-reflecting fine particles or light-diffusing fine particles is dispersed in a binder, and when the dispersion contains a solvent, the dispersion It is obtained by removing the solvent from the particles and curing the particles. Here, the curing in the present invention is not only a reaction in which hardness is generated by a polymerization reaction of monomers and a cross-linking reaction between polymers by a curing agent, heating, electron beam irradiation, etc., but also a solvent from a dispersion liquid by heating, firing, etc. It also includes reactions that remove and give the binder hardness.

(Light reflective layer)
The light reflecting layer may be a layer capable of specularly reflecting natural light, artificial light, or the like like a mirror, and has a specular reflectance of 60% or more, preferably 70% or more, and more preferably 80% or more. The light-reflecting layer may be any one that reflects light specularly, and preferably has a metal-deposited film, and may have a metal-deposited film on a substrate such as glass or resin. If the specular reflectance of the light reflecting layer is within the above range, the function as a mirror can be sufficiently fulfilled. In the present invention, the specular reflectance of the light reflecting layer is a value measured as follows.
(Specular reflectance of the light reflecting layer)
Measurement was performed using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product number: CM-3500d).

The light-reflecting layer consists of silver, gold, platinum, chromium, nickel, tin, aluminum, titanium oxide, niobium oxide, cerium oxide, zirconium oxide, indium tin oxide, zinc oxide, tantalum oxide, zinc sulfide, and tin oxide. It is preferably formed using at least one more selected material. By using such a material, the specular reflectance can be increased.

The thickness of the light reflecting layer can be appropriately changed according to the specular reflectance that can be realized, preferably 0.2 μm to 1 mm, more preferably 0.5 to 500 μm, and more preferably 1 to 200 μm. Is. If the light reflecting layer has such a thickness, the specular reflectance can be increased.

The method for forming the light reflecting layer is not particularly limited, and a conventionally known method can be used. For example, the light reflective layer can be formed by vapor deposition, sputtering, or coating. The light reflecting layer may be formed directly on the transparent image projection layer, or may be formed on a base material layer made of resin or glass and then bonded to the transparent image projection layer with an adhesive or the like.

(Base layer)
The base material layer is a layer for supporting the laminated body, and the strength of the laminated body can be improved. As such a resin, for example, a highly transparent resin similar to the above-mentioned transparent image projection layer can be used. That is, acrylic resin, acrylic urethane resin, polyester acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, polyester resin, polyolefin resin, urethane resin, epoxy resin, polycarbonate resin, cellulose resin, Acetal resin, vinyl resin, polystyrene resin, polyamide resin, polyimide resin, melamine resin, phenol resin, silicone resin, polyarylate resin, polyvinyl alcohol resin, polyvinyl chloride resin, polysulfone resin A resin, a thermoplastic resin such as a fluororesin, a thermocurable resin, an ionizing radiation curable resin and the like can be preferably used. Further, a laminated body or a sheet in which two or more kinds of the above resins are laminated may be used. The thickness of the base material layer can be appropriately changed depending on the material so that its strength becomes appropriate, and may be in the range of, for example, 10 to 1000 μm.

(Protective layer)
The protective layer may be laminated on both the front surface side (visual side) and the back surface side of the laminate, or on either side, and has functions such as light resistance, scratch resistance, substrate adhesion, and antifouling property. It is a layer for giving. The protective layer is preferably formed using a resin that does not impair the desired optical properties of the laminate.
Examples of the material of the protective layer include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as diacetyl cellulose and triacetyl cellulose, acrylic resins such as polymethyl methacrylate, and polystyrene and acrylonitrile / styrene copolymers. Examples thereof include styrene-based resins such as (AS resin) and polycarbonate-based resins. Further, polyolefin resins such as polyethylene, polypropylene and ethylene / propylene copolymers, olefin resins having a cycloolefin or norbornene structure, vinyl chloride resins, amide resins such as nylon and aromatic polyamides, and imide resins, Sulphonic resin, polyether sulfone resin, polyether ether ketone resin, polyphenylene sulfide resin, vinyl alcohol resin, vinylidene chloride resin, vinyl butyral resin, allylate resin, polyoxymethylene resin, epoxy resin , Or a blend of the above resins is an example of a resin that forms a protective film. In addition, acrylic-based and urethane-based, acrylic urethane-based, epoxy-based, silicone-based and other ionizing radiation-curable resins, ionizing radiation-curable resins mixed with thermoplastic resins and solvents, and thermosetting resins can be mentioned. ..

The film-forming component of the ionizing radiation curable resin composition preferably has an acrylate-based functional group, for example, a polyester resin having a relatively low molecular weight, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, or an alkyd resin. Oligos or prepolymers such as (meth) alrelate of polyfunctional compounds such as spiroacetal resin, polybutagen resin, polythiolpolyene resin, polyhydric alcohol, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene as reactive diluents, Monofunctional and polyfunctional monomers such as methylstyrene and N-vinylpyrrolidone, such as polymethylol propanetri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate. , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like can be used in a relatively large amount. ..

In order to obtain the ionizing radiation curable resin composition into an ultraviolet curable resin composition, acetophenones, benzophenones, Michler benzoylbenzoates, α-amyloxime esters, and tetramethylchurammono are used as photopolymerization initiators in the composition. Sulfide, thioxanthones, n-butylamine, triethylamine, poly-n-butylhosophine and the like can be mixed and used as a photosensitizer. In particular, in the present invention, it is preferable to mix urethane acrylate as the oligomer, dipentaerythritol hexa (meth) acrylate or the like as the monomer.

As a method for curing the ionizing radiation curable resin composition, the method for curing the ionizing radiation curable resin composition can be a normal curing method, that is, curing by irradiation with an electron beam or ultraviolet rays. For example, in the case of electron beam curing, 50 to 50 emitted from various electron beam accelerators such as cockloft Walton type, bandegraph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having an energy of 1000 KeV, preferably 100 to 300 KeV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light rays such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are emitted. Available.

The protective layer is formed by applying the coating liquid of the ionizing radiation (ultraviolet) ray-curable resin composition to the above-mentioned laminate by a method such as spin coating, die coating, dip coating, bar coating, flow coating, roll coating, and gravure coating. It can be formed by applying it to both the front surface side (visual side) and the back surface side or one of the surfaces and curing the coating liquid by the above means. Further, the surface of the protective layer may be provided with a fine structure such as an uneven structure, a prism structure, or a microlens structure, depending on the purpose.

(Adhesive layer)
The adhesive layer is a layer for attaching the laminate to the support. The pressure-sensitive adhesive layer is preferably formed using a pressure-sensitive adhesive composition that does not impair the desired optical properties of the laminate. Examples of the pressure-sensitive adhesive composition include natural rubber-based, synthetic rubber-based, acrylic resin-based, polyvinyl ether resin-based, urethane resin-based, and silicone resin-based. Specific examples of the synthetic rubber system include styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisobutylene rubber, isobutylene-isoprene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, and styrene-ethylene-butylene block. Examples include copolymers. Specific examples of the silicone resin system include dimethylpolysiloxane. These pressure-sensitive adhesives can be used alone or in combination of two or more. Among these, acrylic adhesives are preferable.

The acrylic resin pressure-sensitive adhesive is polymerized by containing at least a (meth) acrylic acid alkyl ester monomer. It is generally a copolymer of a (meth) acrylic acid alkyl ester monomer having an alkyl group having about 1 to 18 carbon atoms and a monomer having a carboxyl group. The (meth) acrylic acid refers to acrylic acid and / or methacrylic acid. Examples of (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, sec-propyl (meth) acrylic acid, and (meth) acrylic acid. n-butyl, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Examples thereof include n-octyl, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, undecyl (meth) acrylate, and lauryl (meth) acrylate. Further, the (meth) acrylic acid alkyl ester is usually copolymerized in an acrylic pressure-sensitive adhesive at a ratio of 30 to 99.5 parts by mass.

Further, as the monomer having a carboxyl group forming the acrylic resin pressure-sensitive adhesive, a monomer containing a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, monobutyl maleate and β-carboxyethyl acrylate. Can be mentioned.

In addition to the above, the acrylic resin pressure-sensitive adhesive may be copolymerized with a monomer having another functional group within a range that does not impair the characteristics of the acrylic resin pressure-sensitive adhesive. Examples of monomers having other functional groups are monomers containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and allyl alcohol; (meth) acrylamide, N-methyl. Monomers containing amide groups such as (meth) acrylamide and N-ethyl (meth) acrylamide; monomers containing amide groups and methylol groups such as N-methylol (meth) acrylamide and dimethylol (meth) acrylamide; aminomethyl ( Monomers having functional groups such as amino group-containing monomers such as meta) acrylate, dimethylaminoethyl (meth) acrylate and vinylpyridine; epoxy group-containing monomers such as allyl glycidyl ether and glycidyl ether (meth) acrylate. Can be mentioned. In addition to fluorine-substituted (meth) acrylic acid alkyl esters and (meth) acrylonitrile, vinyl group-containing aromatic compounds such as styrene and methylstyrene, vinyl acetate, vinyl halide compounds and the like can be mentioned.

As the acrylic resin pressure-sensitive adhesive, in addition to the above-mentioned monomers having other functional groups, other monomers having an ethylenic double bond can be used. Examples of monomers having an ethylenic double bond include diesters of α, β-unsaturated dibasic acids such as dibutyl maleate, dioctyl maleate and dibutyl fumarate; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers. Vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; (meth) acrylonitrile and the like can be mentioned. Further, in addition to the monomer having an ethylenic double bond as described above, a compound having two or more ethylenic double bonds can also be used in combination. Examples of such compounds include divinylbenzene, diallyl malate, diallyl phthalate, ethylene glycol di (meth) acrylicate, trimethylolpropane tri (meth) acrylate, methylenebis (meth) acrylamide and the like.

Further, in addition to the above-mentioned monomers, a monomer having an alkoxyalkyl chain or the like can be used. Examples of (meth) acrylic acid alkoxyalkyl esters include (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid 2-methoxypropyl, and (meth) acrylic acid 3-methoxypropyl. , (Meta) 2-methoxybutyl acrylate, (meth) 4-methoxybutyl acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate And so on.

The pressure-sensitive adhesive composition may be a homopolymer of a (meth) acrylic acid alkyl ester monomer in addition to the above-mentioned acrylic resin pressure-sensitive adhesive. For example, examples of the (meth) acrylic acid ester homopolymer include methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and poly (meth). Examples include octyl acrylate. Examples of the copolymer containing two or more acrylate units include methyl (meth) acrylate- (meth) ethyl acrylate copolymer, methyl (meth) acrylate- (meth) butyl acrylate copolymer, and (1). Examples thereof include methyl acrylate- (meth) acrylate 2-hydroxyethyl copolymer, methyl (meth) acrylate- (meth) acrylate 2-hydroxy 3-phenyloxypropyl copolymer and the like. Examples of the copolymer of (meth) acrylate ester and other functional monomers include (meth) methyl acrylate-styrene copolymer, (meth) methyl acrylate-ethylene copolymer, and (meth) acrylic. Examples thereof include 2-hydroxyethyl-styrene copolymers of methyl- (meth) acrylate.

Commercially available adhesives may be used, for example, SK Dyne 2094, SK Dyne 2147, SK Dyne 1811L, SK Dyne 1442, SK Dyne 1435, and SK Dyne 1415 (all manufactured by Soken Kagaku Co., Ltd.). Oliverine EG-655, Oliverine BPS5896 (above, manufactured by Toyo Ink Co., Ltd.) and the like (above, trade name) can be preferably used.

(Anti-reflective layer)
The antireflection layer is a layer for preventing reflection on the surface of the laminated body and reflection from external light. The antireflection layer may be laminated on the surface side (visual side) of the laminated body, or may be laminated on both sides. In particular, it is preferable to stack them on the viewer side. The antireflection layer is preferably formed using a resin that does not impair the desired optical properties of the laminate. As such a resin, for example, a resin that is cured by ultraviolet rays or electron beams, that is, an ionized radiation curable resin, an ionized radiation curable resin mixed with a thermoplastic resin and a solvent, and a thermosetting resin are used. However, among these, the ionizing radiation curable resin is particularly preferable.

The method for forming the antireflection layer is not particularly limited, but is a method of laminating a coating film, a method of dry coating directly on a film substrate by vapor deposition or sputtering, gravure coating, microgravure coating, bar coating, slide die coating, etc. Methods such as work, slot die coating, and wet coating treatment such as dip coating can be used.

<Manufacturing method of laminated body>
The method for producing a laminated body according to the present invention includes a step of forming a transparent image projection layer and a step of forming a light reflecting layer such as a laminating step. The process of forming the transparent image projection layer is known such as offset printing, gravure printing, screen printing, inkjet printing, spray printing, spin coating, die coating, dip coating, bar coating, flow coating, roll coating, gravure coating and other coating methods. A thin film of an appropriate thickness produced by the above method, an injection molding method, an extrusion molding method consisting of a kneading process and a film forming process, a calendar molding method, a blow molding method, a compression molding method, a cell casting method, a continuous casting method, etc. are known. The extrusion molding method can be preferably used because of the wide range of film thicknesses that can be formed by the above method. Hereinafter, each step of the manufacturing method will be described in detail.

(Kneading process)
The kneading step can be performed using an extruder such as a single-screw kneader or a twin-screw kneading extruder. When a twin-screw kneading extruder is used, the above binder and fine particles (light-reflecting fine particles and light diffusion) are applied while applying a shear stress of preferably 3 to 1800 KPa, more preferably 6 to 1400 KPa as an average value over the entire length of the screw. A resin composition can be obtained by kneading with at least one of the sex fine particles). When the shear stress is within the above range, the fine particles can be sufficiently dispersed in the resin. In particular, when the shear stress is 3 KPa or more, the dispersion uniformity of the fine particles can be further improved, and when it is 1800 KPa or less, decomposition of the resin is prevented and air bubbles are prevented from being mixed in the transparent image projection layer. be able to. The shear stress can be set in a desired range by adjusting the twin-screw kneading extruder. In the present invention, a mixture of a resin to which fine particles have been added in advance (masterbatch) and a resin to which fine particles have not been added is kneaded using a uniaxial kneading extruder or a biaxial kneading extruder. A resin composition may be obtained.

In addition to the above resin and fine particles, conventionally known additives may be added to the resin composition as long as the desired optical performance of the laminate is not impaired. Examples of the additive include antioxidants, lubricants, ultraviolet absorbers, compatibilizers, nucleating agents and stabilizers. The resin and fine particles are as described above.

The twin-screw kneading extruder used in the kneading process has two screws inserted in a cylinder, and is configured by combining screw elements. As the screw, at least a flight screw including a transport element and a kneading element can be preferably used. The kneading element preferably contains at least one selected from the group consisting of kneading elements, mixing elements, and rotary elements. By using a flight screw containing such a kneading element, fine particles can be sufficiently dispersed in the resin while applying a desired shear stress.

(Film formation process)
The film forming step is a step of forming a film of the resin composition obtained in the kneading step. The film-forming method is not particularly limited, and a film made of a resin composition can be formed by a conventionally known method. For example, the resin composition obtained in the kneading step is supplied to a melt extruder heated to a temperature equal to or higher than the melting point (Tm to Tm + 70 ° C.) to melt the resin composition. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose.

Subsequently, the molten resin composition can be extruded into a sheet by a die such as a T die, and the extruded sheet can be rapidly cooled and solidified by a rotating cooling drum or the like to form a film. When the film forming step is continuously performed in the kneading step, the resin composition obtained in the kneading step is directly extruded into a sheet by a die in a molten state to form a film-shaped transparent image projection layer. Can also be molded.

The film-shaped transparent image projection layer obtained by the film forming step may be further uniaxially stretched or biaxially stretched by a conventionally known method. By stretching the transparent image projection layer, the strength of the transparent image projection layer can be improved.

(Laminating process)
The laminating step is a step of further laminating a light reflecting layer on the film-shaped transparent image projection layer obtained in the film forming step. The method of laminating the light reflecting layer is not particularly limited, and a conventionally known method can be used. For example, the light reflective layer can be formed by vapor deposition, sputtering, or coating. Further, a light-reflecting layer such as a commercially available mirror may be laminated on a film-shaped transparent image projection layer by laminating it via an adhesive layer or the like.

<Video projection system>
The image projection system according to the present invention includes the above-mentioned laminated body and a projection device. The projection device is not particularly limited as long as it can project an image on the laminated body, and for example, a commercially available front projector can be used.

A schematic diagram of an embodiment of the image projection system according to the present invention is shown in FIG. The image projection system includes a laminated body 15 and a projection device 22 capable of projecting an image from the viewer 21 side onto the transparent image projection layer surface of the laminated body 15. The projected light 23 projected from the projection device 22 is anisotropically scattered and reflected by the laminated body 15, and the viewer 21 can visually recognize the scattered light 24.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

In the examples and comparative examples, the measurement methods for various physical properties and performance evaluations are as follows.
(1) Measurement was performed in accordance with JIS K7136 using a haze turbidity meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product number: NDH-5000) of the transparent image projection layer and the laminated body.
(2) Total light transmittance of transparent image projection layer and laminated body Measured according to JIS K7361-1 using a turbidity meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product number: NDH-5000).
(3) Specular reflectance of the light reflecting layer The measurement was performed using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., product number: CM-3500d).
(4) Average secondary particle diameter of fine particles in the transparent image projection layer Particle diameter = (length) based on the image measured with a scanning electron microscope (SEM, manufactured by Hitachi High-Technologies Co., Ltd., trade name: SU-1500). It was measured by calculating the average value of the particle diameters when the particle diameter in the axial direction + the particle diameter in the minor axis direction) / 2.
(5) Performance as a mirror and screen performance of the laminate The laminate produced below is placed 50 cm away from the normal direction at an angle of 15 degrees, and is a mobile LED mini projector PP manufactured by Onkyo Digital Solutions Co., Ltd. Images were projected using −D1S. Next, after adjusting the focus knob of the projector so that the focus is on the surface of the laminate, the image was projected onto the laminate from 1 m in front of the laminate (the same side as the projector with respect to the laminate, so-called front projection). The image was visually evaluated according to the following evaluation criteria. The performance as an image display device (reflective screen) can be evaluated by observing from the front of the laminated body. In addition, the performance as a mirror was evaluated by observing the laminated body without projecting an image.
[Evaluation criteria]
⊚: The image could be visually recognized extremely clearly.
◯: The image could be clearly seen.
X: No image was formed on the laminate, which was unsuitable for use as a screen. Alternatively, the specular reflectivity of the light reflecting layer is low, and it is not suitable for use as a mirror.

[Example 1]
(1) Preparation of thermoplastic resin pellets to which light-reflecting fine particles are added (hereinafter referred to as "pellet preparation process")
As a thermoplastic resin, polyethylene terephthalate (PET) pellets (manufactured by Bell Polyester Products Co., Ltd., trade name: IP121B) were prepared. To the PET pellets, 0.004% by mass of flaky aluminum fine particles A (average diameter of primary particles 1 μm, aspect ratio 300, normal reflectance 62.8%) were added as light-reflecting fine particles to the PET pellets. , A PET pellet in which flaky aluminum fine particles were uniformly adhered to the surface of the PET pellet was obtained by mixing with a rotary mixer.
(2) Fabrication of transparent image projection layer (hereinafter referred to as "sheet fabrication process")
The obtained fine particle-added PET pellets were put into a hopper of a twin-screw screw type kneading extruder (manufactured by Technobel Co., Ltd., trade name: KZW-30MG) to prepare a transparent image projection layer having a thickness of 80 μm. The screw diameter of the twin-screw screw type kneading extruder was 20 mm, and the effective screw length (L / D) was 30. In addition, a hanger coat type T-die was installed in the twin-screw screw type kneading extruder via an adapter. The extrusion temperature was 270 ° C., the screw rotation speed was 500 rpm, and the shear stress was 300 KPa. The screw used has a total length of 670 mm, includes a mixing element between 160 mm and 185 mm from the hopper side of the screw, and a kneading element between 185 mm and 285 mm, and the other parts are flight. It was a shape. The average secondary particle diameter of the flaky aluminum fine particles in the obtained transparent image projection layer was 2 μm, the haze was 5%, and the total light transmittance was 83%.
(3) Fabrication of a laminate of a transparent image projection layer and a light reflection layer (hereinafter referred to as "lamination process")
On one side of the obtained transparent image projection layer, an aluminum mirror (manufactured by M & G Kitade Co., Ltd., trade name: optical surface mirror (aluminum specular reflection mirror), specular reflectance 94%) was used as a light reflection layer using an adhesive. It was laminated to obtain a laminated body.
(4) Evaluation of the laminated body When the screen performance of the laminated body was evaluated, an extremely clear image could be visually recognized. In addition, the laminated body in which no image was projected was excellent in specular reflectivity and could be used as a mirror without any problem.

[Example 2]
In the pellet preparation step, zirconium oxide particles (primary particles having a median diameter of 10 nm and a refractive index of 2.40) were added as light diffusible fine particles in place of light reflective fine particles so as to be 0.15% by mass with respect to PET. A transparent image projection layer having a thickness of 80 μm was produced in the same manner as in Example 1 except for the above. The average secondary particle diameter of the zirconium oxide fine particles in the obtained transparent image projection layer was 200 nm, the haze was 8%, and the total light transmittance was 79%.
Using the obtained transparent image projection layer, a laminate was produced in the same manner as in Example 1.
When the screen performance of the laminated body was evaluated, a clear image could be visually recognized. In addition, the laminated body in which no image was projected was excellent in specular reflectivity and could be used as a mirror without any problem.

[Example 3]
In the pellet preparation step, in addition to the light-reflecting fine particles, zirconium oxide particles (primary particles having a median diameter of 10 nm and a refractive index of 2.40) were added as light-diffusing fine particles so as to be 0.15% by mass with respect to PET. A transparent image projection layer having a thickness of 80 μm was produced in the same manner as in Example 1 except for the above. The average secondary particle diameter of the fine particles in the obtained transparent image projection layer was 1.5 μm, the haze was 12%, and the total light transmittance was 75%.
The obtained transparent image projection layer and an aluminum mirror (manufactured by Napolex Co., Ltd., trade name: A360R, specular reflectance 82%) were laminated as a light reflecting layer with an adhesive to obtain a laminated body.
When the screen performance of the laminated body was evaluated, an extremely clear image could be visually recognized. In addition, the laminated body in which no image was projected was excellent in specular reflectivity and could be used as a mirror without any problem.

[Comparative Example 1]
In the pellet preparation step, a transparent layer having a thickness of 80 μm was prepared in the same manner as in Example 1 except that light-reflecting fine particles were not added.
The obtained transparent layer and the aluminum mirror used in Example 1 were laminated with an adhesive to obtain a laminated body.
When the screen performance of the laminated body was evaluated, it was excellent in specular reflectivity and could be used as a mirror, but no image was formed on the laminated body and it was not suitable for use as a screen.

[Comparative Example 2]
In the laminating step of Example 1, titanium oxide was laminated on one side of the obtained transparent image projection layer so as to have a thickness of 15 nm by vapor deposition to form a metal reflective layer (specular reflectance 48%), and the laminated body was formed. Obtained.
When the screen performance of the laminated body was evaluated, an extremely clear image could be visually recognized, but the laminated body in a state where the image was not projected had low specular reflection and was not suitable for use as a mirror.

10 Binder 11 Light-reflecting fine particles 12 Light-diffusing fine particles 13 Transparent image projection layer 14 Light-reflecting layer 15 Laminated body 16 Projected light 17 Scattered light 18 Viewer 21 Viewer 22 Projector 23 Projected light 24 Scattered light

Claims (12)

A laminated body capable of projecting an image, comprising a transparent image projection layer and a light reflection layer having a specular reflectance of 60% or more.
The transparent image projection layer contains a binder and light-reflecting fine particles.
The average diameter of the primary particles of the light-reflecting fine particles is 0.01 to 100 μm.
The shape of the light-reflecting fine particles is flaky, and the average aspect ratio is 3 to 800.
The content of the light reflective fine particles, Ri 0.0001% by mass relative to the binder,
Metallic particles and glass in which the light-reflecting fine particles are selected from the group consisting of aluminum, silver, copper, platinum, gold, titanium, nickel, tin, tin-cobalt alloy, indium, chromium, aluminum oxide, and zinc sulfide. A laminate , which is a brilliant material coated with the metal or metal oxide, or a brilliant material obtained by coating a natural mica or synthetic mica with the metal or metal oxide . A laminated body capable of projecting an image, comprising a transparent image projection layer and a light reflection layer having a specular reflectance of 60% or more.
The transparent image projection layer contains a binder and light-reflecting fine particles.
The average diameter of the primary particles of the light-reflecting fine particles is 0.01 to 100 μm.
The shape of the light-reflecting fine particles is flaky, and the average aspect ratio is 3 to 800.
The content of the light-reflecting fine particles is 0.0001 to 5.0% by mass with respect to the binder.
The light-reflecting fine particles are metal-based fine particles, and the metal material used for the metal-based fine particles is a laminate in which the real number term ε'of the dielectric constant is -60 to 0. The laminate according to claim 1 or 2 , wherein the light-reflecting fine particles have an average secondary particle diameter of 100 nm to 200 μm. The difference between the refractive index n ₂ of the light diffusing fine particles and the refractive index n ₁ of the binder is the following mathematical formula (1):
| N _1- n ₂ | ≧ 0.1 ・ ・ ・ (1)
The laminate according to any one of claims 1 to 3 , which satisfies the above conditions. A group in which the photodiffusible fine particles consist of zirconium oxide, zinc oxide, titanium oxide, cerium oxide, barium titanate, strontium titanate, magnesium oxide, calcium carbonate, barium sulfate, diamond, crosslinked acrylic resin, crosslinked styrene resin and silica. The laminate according to claim 4 , which is at least one selected from the above. The laminate according to claim 4 or 5 , wherein the median diameter of the primary particles of the light diffusing fine particles is 0.1 to 500 nm. The laminate according to any one of claims 4 to 6 , wherein the content of the light diffusing fine particles is 0.0001 to 2.0% by mass with respect to the binder. The laminate according to any one of claims 4 to 7 , wherein the average secondary particle diameter of the light diffusing fine particles is 100 nm to 200 μm. The laminate according to any one of claims 1 to 8 , wherein the haze of the transparent image projection layer is 35% or less. The laminate according to any one of claims 1 to 9 , wherein the light reflecting layer includes a metal vapor deposition film. An image projection system comprising the laminate according to any one of claims 1 to 10 and a projection device. A spatial effect method using the laminate according to any one of claims 1 to 10 or the image projection system according to claim 11 .

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