WO2018167823A1 - Composition for forming film for projection, film for projection, and screen for projection - Google Patents

Composition for forming film for projection, film for projection, and screen for projection Download PDF

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Publication number
WO2018167823A1
WO2018167823A1 PCT/JP2017/009978 JP2017009978W WO2018167823A1 WO 2018167823 A1 WO2018167823 A1 WO 2018167823A1 JP 2017009978 W JP2017009978 W JP 2017009978W WO 2018167823 A1 WO2018167823 A1 WO 2018167823A1
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Prior art keywords
projection
parts
resin
film
projection film
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PCT/JP2017/009978
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French (fr)
Japanese (ja)
Inventor
金野公彦
大谷紀昭
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マクセルホールディングス株式会社
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Priority to PCT/JP2017/009978 priority Critical patent/WO2018167823A1/en
Publication of WO2018167823A1 publication Critical patent/WO2018167823A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B21/00—Projectors or projection-type viewers; Accessories therefor
    • G03B21/54—Accessories
    • G03B21/56—Projection screens
    • G03B21/60—Projection screens characterised by the nature of the surface
    • G03B21/62—Translucent screens

Definitions

  • the present invention relates to a projection film preparation composition, a projection film prepared using the projection film preparation composition, and a projection screen using the projection film.
  • Projectors are used for various purposes such as personal use such as home theater, digital signage such as product advertisements, and corporate activities such as projecting data in conference rooms.
  • the projection screen of such a projector includes a transmissive screen that projects an image on the back of the projection screen and visually recognizes the transmitted light, and a reflective screen that projects the image on the front of the projection screen and visually recognizes the reflected light.
  • a transmissive screen that projects an image on the back of the projection screen and visually recognizes the transmitted light
  • a reflective screen projects the image on the front of the projection screen and visually recognizes the reflected light.
  • There are two types. What is important for each type of screen is that the projected image can be clearly confirmed, that is, visibility. In order to improve visibility, it is necessary for transmitted light to be particularly bright in a transmissive screen.
  • ultra-short focus projectors in which the distance between the projector and the projection screen is shortened have been commercialized.
  • the ultra-short focus projector differs from the conventional projector in the image projection angle.
  • Conventional projectors project images from the front direction onto the projection screen, whereas ultra-short focus projectors place the projector close to the projection screen, so project images from an extremely oblique direction.
  • the incident angle of the projection light with respect to the projection screen increases, so the amount of light transmitted through the screen decreases, and the projected image becomes darker than when a conventional projector is used. It will be inferior.
  • a cyclic olefin resin and a hollow organic olefin resin having an affinity for a cyclic olefin resin and an average particle diameter of 2.0 ⁇ m or more are used. It has been proposed to use a resin composition containing. This resin composition is excellent in moldability. By using this resin composition, it is said that it is possible to provide a transmissive screen diffusion plate with improved brightness and image clarity.
  • a cyclic olefin-based resin has a low tear strength and is also susceptible to impact, so that it is difficult to handle when used in a projection film.
  • Patent Document 2 proposes a transmission screen using hollow beads.
  • a range of 0.1 to 40 ⁇ m is used as the average diameter (hole diameter) of the gas part of the hollow beads.
  • a large amount of scattered light is used. Although the visibility of the image is improved, the confirmation and transparency of the object on the back side of the screen are still insufficient.
  • Patent Documents 3 to 7 there are Patent Documents 3 to 7 and Non-Patent Documents 1 and 2.
  • JP 2008-64951 A Japanese Patent No. 4847329 (International Publication WO2006 / 016556) Japanese Patent No. 4046921 (Japanese Patent Laid-Open No. 2001-233611) Japanese Patent No. 4654428 (Japanese Patent Laid-Open No. 2005-263550) Japanese Patent No. 4816634 (Japanese Patent Laid-Open No. 2006-256922) Japanese Patent No. 4853662 (Japanese Patent Laid-Open No. 2008-247664) Japanese Patent No. 5194935 (Japanese Patent Laid-Open No. 2009-234848)
  • the projection film is not easily torn during cutting or processing of the projection film before being applied to a glass substrate or the like, and even if the application is performed using a squeegee or the like, the projection film It is an object of the present invention to provide a projection film that is less likely to be scratched on the surface, has good visibility, and has good transparency.
  • the composition for producing a projection film of the present invention is a composition for producing a projection film containing hollow particles, a polymerizable compound, and a solvent, and the average particle diameter of primary particles of the hollow particles is 30 nm. More than or equal to 500 nm, the porosity of the hollow particles is 20% by volume or more and 95% by volume or less, and the content of the hollow particles is 100 parts by mass of the polymerizable compound other than the hollow particles. It is characterized by being 10 parts by mass or more and 150 parts by mass or less.
  • the projection film of the present invention is a projection film having a resin layer on at least one surface of a substrate, and the substrate is made of a resin film having a glass transition temperature of 95 ° C. or less, and the resin layer Includes hollow particles and a resin, the average particle diameter of primary particles of the hollow particles is 30 nm or more and 500 nm or less, and the porosity of the hollow particles is 20% by volume or more and 95% by volume or less, The content of the hollow particles is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, and the thickness of the resin layer is at least twice the average particle diameter of the hollow particles. It is characterized by.
  • the projection screen of the present invention is a projection screen including a member and a projection film affixed to the member, wherein the projection film is the projection film of the present invention. To do.
  • a projection film having excellent tear resistance, scratch resistance and optical characteristics can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the projection screen of the present invention.
  • FIG. 2 is a schematic diagram showing an example of a state in which an image is projected onto the projection screen of the present invention using an ultrashort focus projector.
  • composition for producing a projection film of the present invention The present inventors have studied various means for improving scratch resistance and optical properties in the projection film, and found that a resin layer containing hollow particles and a resin may be formed on the surface of the projection film. The composition for producing a projection film of the present invention was completed.
  • the composition for producing a projection film of the present invention includes hollow particles, a polymerizable compound, and a solvent, and the average particle diameter of primary particles of the hollow particles is 30 nm to 500 nm, and the hollow
  • the porosity of the particles is 20% by volume or more and 95% by volume or less, and the content of the hollow particles is 10 parts by mass or more with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles. It is 150 parts by mass or less.
  • composition for producing a projection film of the present invention contains hollow particles having an average primary particle diameter of 30 nm to 500 nm and a porosity of 20 vol% to 95 vol%, A projection film having excellent scratch resistance and optical properties can be provided.
  • the content of the hollow particles must be set to 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles, and 20 parts by mass or more. 120 parts by mass or less is more preferable.
  • the content of the hollow particles is less than 10 parts by mass, the effect of improving the light transmittance of the projection film is reduced.
  • the content of the hollow particles exceeds 150 parts by mass, the scratch resistance of the projection film is reduced. descend.
  • the average particle size of the hollow particles used in the present invention needs to be 30 nm or more and 500 nm or less, and more preferably 60 nm or more and 300 nm or less.
  • the average particle diameter is less than 30 nm, the specific surface area of the particles is increased, and more solvent is required to disperse the particles. In some cases, sufficient thickness cannot be secured.
  • the average particle diameter exceeds 500 nm, light scattering increases, or the haze of the projection film increases and the transparency is not improved.
  • the porosity of the hollow particles needs to be 20% by volume or more and 95% by volume or less, and preferably 30% by volume or more and 75% by volume or less.
  • the porosity is less than 20% by volume, the light transmittance of the projection film is not improved, and the visibility of the image is poor.
  • the porosity exceeds 95% by volume, the shell wall of the particle becomes thin and easily broken, or the light transmittance of the projection film is not improved and the image visibility is poor.
  • the light transmittance of the projection film is improved and the haze is as low as less than 15%. Therefore, when used for a screen for an ultra-short focus projector, a projection film having excellent visibility from the front and oblique directions and excellent transparency can be obtained. Both visibility and transparency of the image depend on the haze value, and the present inventors have found that the haze value may be adjusted to less than 15% in order to achieve both of these, and the present invention has been achieved.
  • the average particle diameter and porosity of the hollow particles can be calculated by observing the hollow particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the hollow particles may be observed directly, or the hollow particles may be cross-sectionally processed by ion milling, and the hollow particles may be cross-sectionally processed with a microtome or the like after being embedded in a resin. May be observed.
  • the particle diameter and the shell wall thickness are measured, and the average particle diameter and the average shell wall thickness are obtained. Find the rate.
  • the particle diameter of the hollow particles refers to the so-called primary particle size, and when the hollow particles are spherical or ellipsoidal in which the ratio of the major axis length to the minor axis length is 1 to 3.5.
  • the maximum delivery diameter is defined as the particle diameter, and in the case of other particles, the major axis diameter is defined as the particle diameter of the particle.
  • Porosity (%) [(average particle size ⁇ average thickness of shell wall ⁇ 2) / average particle size] 3 ⁇ 100 (1)
  • the content of the hollow particles contained in the projection film preparation composition of the present invention is 10 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles.
  • the solid component excluding the polymerizable compound includes, for example, optional components such as a photopolymerization initiator, a resin polymer, a dispersant, and a tackifier.
  • the content of the hollow particles can be measured by, for example, a thermal analysis method. That is, after the non-solid component such as a solvent is removed by heating the film-forming composition for projection, the mass of the remaining solid component is measured, and further heated to around 700 ° C. to obtain a solid component other than the hollow particles. The mass of the residue after burning is measured. Since the mass of the residue is considered to be the mass of the hollow particles, the content of the hollow particles contained in the projection film preparation composition can be determined from the mass of the residue and the mass of the solid component.
  • the material of the hollow particles is not limited, and both hollow inorganic particles and hollow organic particles can be used, but hollow silica particles that are hollow inorganic particles are particularly preferable. This is because the hollow silica particles have high physical strength and are excellent in dispersibility in the composition for producing a projection film.
  • the hollow silica particles may contain other metal elements in addition to SiO 2 as a constituent component, or may be a hydrous compound.
  • the method for producing hollow silica particles having an average particle diameter of 30 nm or more and 500 nm or less is not particularly limited.
  • the hollow silica particles can be produced by a template method as described in Non-Patent Document 1 described above. More specifically, a method using the bubbles described in Non-Patent Document 2 as a template, an inorganic template method using the inorganic particles described in Patent Documents 3, 4, and 5 as a template, Patent Document 6 described above, 7 can be produced by an organic template method using the organic particles described in 7 as a template.
  • the hollow silica particles may be subjected to a surface treatment in order to improve familiarity with a resin formed by polymerizing the polymerizable compound.
  • the surface treatment may be performed, for example, by adding a silicon coupling agent to a dispersion or suspension of hollow silica particles.
  • the organic functional group that modifies the surface of the hollow silica particles varies depending on the silicon coupling agent to be used, it is preferable to modify the surface with a methyl group, a phenyl group, or the like for surface treatment.
  • the polymerizable compound preferably contains at least the oligomer.
  • the oligomer urethane acrylate, polyether acrylate, polyester acrylate and the like can be suitably used.
  • the so-called film-forming property is improved and the molecular weight between cross-linking points is increased, and the warpage of the film after production, so-called curling, can be reduced as compared with the case where the monomer is used alone.
  • the monomer it is preferable to use a conventionally known ultraviolet curable resin monomer.
  • polyfunctional monomers such as pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate may be used.
  • the above-mentioned polymerizable compound contains a functional group that reacts when irradiated with radiation such as gamma rays, electron beams, or ultraviolet rays, and an acrylic group or methacryl group is preferable as the functional group that reacts upon irradiation with radiation.
  • the composition for producing a projection film of the present invention preferably contains a photopolymerization initiator together with the polymerizable compound.
  • the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide or the like can be preferably used.
  • the addition amount of the photopolymerization initiator may be 0.1 to 10 parts by mass, and preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.
  • the method for producing the composition for producing a projection film of the present invention is not particularly limited.
  • the above-described components may be mixed with a solvent to sufficiently disperse each solid component.
  • the said mixing method is not specifically limited, For example, it can mix using a disper, a homomixer, a ribbon mixer, a paddle mixer, a planetary mixer, a roll mill, a kneader, a ball mill, a sand mill, a high-pressure homogenizer, an ultrasonic disperser, etc.
  • a conventionally known solvent can be used as the solvent.
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone
  • esters such as methyl acetate, ethyl acetate and butyl acetate, aliphatics such as hexane and octane, and aromatics such as toluene and xylene
  • Alcohols such as ethylene glycol, methanol, ethanol, isopropanol, terpenes such as terpineol, dihydroterpineol, limonene, methyl glycol, isopropyl glycol, methyl propylene glycol, propyl propylene glycol, butyl propylene glycol, methyl propylene glycol acetate, dimethyl glycol
  • a glycol ether solvent such as dimethyldiglycol may be used alone or in combination. What is
  • the projection film of the present invention includes a base material and a resin layer formed on the base material, and the base material is composed of a resin film having a glass transition temperature of 95 ° C. or less.
  • Hollow particles and a resin the primary particles of the hollow particles have an average particle diameter of 30 nm to 500 nm, the void ratio of the hollow particles is 20% to 95% by volume, and the hollow
  • the particle content is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, and the thickness of the resin layer is twice or more the average particle diameter of the hollow particles.
  • the substrate of the projection film of the present invention is made of a resin film having a glass transition temperature of 95 ° C. or lower, the projection film is cut when the projection film is applied to a glass substrate or the like before cutting. It is hard to tear.
  • the resin layer of the projection film of the present invention contains hollow particles having an average primary particle diameter of 30 nm to 500 nm and a porosity of 20 vol% to 95 vol%, A projection film excellent in scratch resistance and optical properties can be provided.
  • the content of the hollow particles in the resin layer needs to be set to 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, and more preferably 20 parts by mass or more and 120 parts by mass or less.
  • the content of the hollow particles is less than 10 parts by mass, the effect of improving the light transmittance of the projection film is reduced.
  • the content of the hollow particles exceeds 150 parts by mass, the scratch resistance of the projection film is reduced. descend.
  • the content of the hollow particles contained in the resin layer of the projection film of the present invention is set to 10 to 150 parts by mass with respect to 100 parts by mass of the resin. It can be measured by analytical methods. That is, the resin layer of the projection film peeled off from the substrate is heated to around 700 ° C., the mass of the residue is measured, and the mass of the hollow particles contained in the resin layer is determined from the mass of the residue. The content of the hollow particles contained in the resin layer can be determined from the mass of the hollow particles.
  • the thickness of the resin layer needs to be at least twice the average particle diameter of the hollow particles.
  • the surface of the resin layer can be smoothed and rubbed with a squeegee or the like when the projection film is attached to a glass substrate or the like. The film surface is not scratched.
  • the projection film can have a haze of less than 15%.
  • the base material used in the present invention may be a resin film having a glass transition temperature of 95 ° C. or lower.
  • a resin film having a glass transition temperature of 95 ° C. or lower for example, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, etc. can be used. From the viewpoint, a PET film is preferable.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the tear resistance can be improved as described above.
  • the thickness of the substrate is not particularly limited, and can be, for example, 10 to 200 ⁇ m.
  • the resin layer used in the present invention contains hollow particles and a resin, and the same hollow particles used in the above-mentioned composition for producing a projection film of the present invention can be used for the hollow particles.
  • resin for example, acrylic resin, polyurethane resin, polystyrene resin, polycarbonate resin, polyester resin, polyether resin, and the like can be used.
  • polymerized the polymeric compound used with the composition for film production for projection of the above-mentioned this invention can also be used as said resin.
  • the upper limit of the thickness of the resin layer is not particularly limited as long as it is twice or more the average particle diameter of the hollow particles, and can be, for example, 5 ⁇ m or less.
  • the production method of the projection film of the present invention is not particularly limited.
  • a coating liquid containing the hollow particles, the resin, and a solvent is prepared, the coating liquid is applied to the substrate, and dried. It can manufacture by forming the said resin layer on a base material.
  • the method for applying the coating solution is not particularly limited as long as it is a coating method that can form a smooth coating film.
  • a gravure roll method a micro gravure roll method, a micro gravure coater method, a slit die coat Method, comma coat method, spin method, knife method, kiss method, squeeze method, reverse roll method, dipping method, bar coat method and the like.
  • the projection film of the present invention is obtained by polymerizing the polymerizable compound contained in the projection film preparation composition after applying the projection film preparation composition of the present invention to the substrate. It can also be produced by forming the resin layer on the substrate.
  • the method for polymerizing the polymerizable compound is not particularly limited, a method of irradiating the coating film with ionizing radiation such as ultraviolet rays can be used.
  • the ionizing radiation for example, ultraviolet rays, electron beams, ⁇ rays, and the like can be used, but ultraviolet rays are frequently used because they can be easily used.
  • the ultraviolet light source a high-pressure mercury lamp, a metal halide lamp, an ultraviolet LED lamp, or the like can be used.
  • ultraviolet rays it is preferable to include a photopolymerization initiator in the composition for producing a projection film as described above.
  • the projection screen of the present invention comprises a member and a projection film affixed to the member, and the projection film is the projection film of the present invention. Since the projection screen of the present invention includes the projection film of the present invention, it has excellent visibility.
  • the projection screen of the present invention can be used as a transmissive screen or a reflective screen, but is particularly excellent in visibility when used as a transmissive screen.
  • the member and the projection film are bonded together with an adhesive. Thereby, peeling of the projection film from the substrate can be prevented.
  • the said adhesive is not specifically limited.
  • the member is not particularly limited, for example, a glass substrate, a glass sheet, a resin substrate, a resin sheet, or the like can be used.
  • the resin layer of the projection film is disposed on the outermost layer. Thereby, the visibility of a screen can be improved more.
  • the production method of the projection screen of the present invention is not particularly limited.
  • the projection film may be bonded to the member with an adhesive or the like.
  • FIG. 1 is a schematic cross-sectional view showing an example of the projection screen of the present invention.
  • a projection screen 10 of the present invention includes a projection film 11 and a transparent substrate 12, and the projection film 11 is bonded onto the transparent substrate 12 via an adhesive (not shown).
  • the projection film includes a resin film 11a having a glass transition temperature of 95 ° C. or less and a resin layer 11b disposed on the resin film 11a.
  • the resin layer 11b is formed of hollow particles and a resin, and is disposed on the outermost layer of the projection screen.
  • FIG. 2 is a schematic diagram showing an example of a state in which an image is projected by an ultra-short focus projector using the projection screen shown in FIG. 1 as a transmission screen.
  • the projection screen 10 is arranged with the projection film 11 side facing the ultrashort focus projector 13 side.
  • the projection light from the ultra-short focus projector 13 is projected to the projection direction 13a side, and the viewer of the image visually recognizes from the viewing direction 14 side.
  • the projection film 11 is composed of a resin film 11 a and a resin layer 11 b disposed on the resin film 11 a, as in FIG. 1, and is attached to the transparent substrate 12.
  • part means “part by mass”.
  • Example 1 Preparation of a composition for producing a projection film (coating solution)> First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
  • Polymerizable compound urethane acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA-40H”
  • Photopolymerization initiator [2-methyl-1- [4- (methylthio) -phenyl ] -2-Morpholinopropan-1-one]: 1.5 parts
  • Solvent methyl ethyl ketone
  • Example 2 ⁇ Preparation of a composition for producing a projection film (coating solution)> First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
  • Polymerizable compound polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”: 50 parts
  • Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts
  • Solvent methyl ethyl ketone
  • a projection film 2 was produced in the same manner as in Example 1 except that the coating liquid 2 was used and the coating thickness was 1.7 ⁇ m.
  • Example 3 ⁇ Preparation of hollow silica particles> 75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.1 ⁇ m, solid content concentration: 2.5 mass%) was heated to 40 ° C., and the suspension was The following components (1) to (4) were blended with stirring, and further stirred for 30 minutes to prepare a mixed solution.
  • Isopropanol 800 parts
  • the mixture was allowed to stand at 40 ° C. for 10 hours and then returned to room temperature. Thereafter, the produced particles were collected by centrifugation and dispersed in water. The above centrifugation, particle recovery, and water dispersion were repeated twice, and after filtration through a filter, the particles were recovered by centrifugation. Thereafter, the collected particles were dried at 100 ° C. for 5 hours, and then the obtained powder was put into a firing furnace, heated to 500 ° C. at a rate of 1 ° C./minute while airflowing, and fired at 500 ° C. for 3 hours. Furthermore, the temperature was raised to 900 ° C. at a rate of 5 ° C./minute, and after firing at 900 ° C. for 3 hours, the mixture was gradually cooled to room temperature to obtain hollow silica particles.
  • the hollow silica particles prepared above: 45 parts and the solvent (methyl ethyl ketone): 255 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water, whereby a coating liquid 3 was obtained.
  • a projection film 3 was produced in the same manner as in Example 1 except that the coating solution 3 was used and the coating thickness was 2.5 ⁇ m.
  • Example 4 ⁇ Preparation of hollow silica particles> Using 75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 ⁇ m, solid content concentration: 2.5 mass%), the amount of tetraethoxysilane is 7 parts. Except for the change, hollow silica particles were produced in the same manner as in Example 3.
  • the hollow silica particles prepared above: 7.5 parts and the solvent (methyl ethyl ketone): 42.5 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water to obtain a coating liquid 4.
  • a projection film 4 was produced in the same manner as in Example 1 except that the coating solution 4 was used and the coating thickness was 2.8 ⁇ m.
  • Example 5 ⁇ Preparation of hollow silica particles> Using 75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 ⁇ m, solid content concentration: 2.5% by mass), the amount of water added to 465 parts, isopropanol The hollow silica particles were prepared in the same manner as in Example 3 except that the amount was 2400 parts, the amount of ammonia water was 90 parts, and the amount of tetraethoxysilane was 40 parts.
  • polystyrene particle suspension manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 ⁇ m, solid content concentration: 2.5% by mass
  • the hollow silica particles were prepared in the same manner as in Example 3 except that the amount was 2400 parts, the amount of ammonia water was 90 parts, and the amount of tetraethoxysilane was 40 parts.
  • the hollow silica particles prepared above: 15 parts and the solvent (methyl ethyl ketone): 85 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • the hollow silica particle suspension was blended into the mixed solution, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water to obtain a coating solution 5.
  • a projection film 5 was produced in the same manner as in Example 1 except that the coating liquid 5 was used and the coating thickness was 2.4 ⁇ m.
  • the coating liquid 6 is coated on a cyclic olefin-based resin film (trade name “ZEONOR FILM ZF14-100”, glass transition temperature: 136 ° C., manufactured by Nippon Zeon Co., Ltd.) using a bar coater.
  • a bar coater was applied to a thickness of 0.27 ⁇ m and dried.
  • the coating film is cured by irradiating ultraviolet rays so that the integrated light quantity becomes 250 mJ / cm 2 using a high-pressure mercury lamp, and a resin layer is formed on the film to produce a projection film 6. did.
  • the hollow silica particles prepared in Example 3 80 parts and the solvent (methyl ethyl ketone): 453 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and then subjected to ultrasonic dispersion treatment while cooling the container with water, whereby a coating liquid 7 was obtained.
  • a projection film 7 was produced in the same manner as in Example 1 except that the coating liquid 7 was used and the coating thickness was 2.6 ⁇ m.
  • Example 3 2.5 parts of hollow silica particles prepared in Example 3 and 15 parts of solvent (methyl ethyl ketone) were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water, whereby a coating liquid 8 was obtained.
  • a projection film 8 was produced in the same manner as in Example 1 except that the coating liquid 8 was used and the coating thickness was 2.8 ⁇ m.
  • Example 4 ⁇ Preparation of hollow silica particles> Using 75 parts of a polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 ⁇ m, solid content concentration: 2.5 mass%), the amount of water is 1550 parts, and isopropanol is used.
  • the hollow silica particles were prepared in the same manner as in Example 3 except that the amount was 8000 parts, the amount of ammonia water was 300 parts, and the amount of tetraethoxysilane was 125 parts.
  • the hollow silica particles prepared above: 50 parts and the solvent (methyl ethyl ketone): 285 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • the hollow silica particle suspension was blended with the mixed liquid, stirred and mixed, and then subjected to ultrasonic dispersion treatment while cooling the container with water to obtain a coating liquid 9.
  • a projection film 9 was produced in the same manner as in Example 1 except that the coating liquid 9 was used and the coating thickness was 2.4 ⁇ m.
  • Example 5 75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.5 ⁇ m, solid content concentration: 2.5 mass%) is used, and the amount of tetraethoxysilane is 6.0. Hollow silica particles were produced in the same manner as in Example 3 except that the part was changed to the part.
  • the hollow silica particles prepared above: 7.5 parts and the solvent (methyl ethyl ketone): 42.5 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension.
  • ultrasonic dispersion treatment was further performed while the container was cooled with water to obtain a coating solution 10.
  • a projection film 10 was produced in the same manner as in Example 1 except that the coating solution 10 was used and the coating thickness was 0.78 ⁇ m.
  • Example 6 A coating solution 1 prepared in Example 1 using a 100 ⁇ m-thick cyclic olefin resin film (manufactured by Zeon Corporation, trade name “Zeonor film ZF14-100”, glass transition temperature: 136 ° C.) instead of the PET film.
  • a projection film 11 was produced in the same manner as in Example 1 except that was used.
  • ⁇ Tear resistance> First, the end surfaces of the projection film were held at positions where the thumbs and the index fingers contact each other so that the thumbs and index fingers of both hands pinch. Next, the projection film was torn by twisting both hands in the opposite direction. As a result, the tear resistance was judged to be good when the film was not cut, and the tear resistance was judged to be poor when the film was cut.
  • the projection films produced in Examples 1 to 5, Comparative Examples 1 to 6 and Reference Example were attached to a float glass plate having a length of 50 mm, a width of 50 mm, and a thickness of 3 mm, with the resin layer facing outside, and evaluated.
  • a sample was used.
  • a 20 ⁇ m-thick substrate-less optical adhesive tape manufactured by Hitachi Maxell, “highly transparent substrate-less double-sided tape No. 5075” was used.
  • the characteristics of the evaluation samples were evaluated as follows.
  • ⁇ Abrasion resistance> The projection film side of the sample for evaluation was rubbed with a squeegee three times to check for scratches. As a result, when the number of scratches was 2 or less, the scratch resistance was judged to be good, and when the number of scratches was 3 or more, the scratch resistance was judged to be poor.
  • Total light transmittance and haze The sample for evaluation was measured for total light transmittance and haze by a method corresponding to Japanese Industrial Standard (JIS) K7361-1, using a turbidimeter “NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.
  • Table 1 also shows the content, type and coating thickness of the hollow silica particles used.
  • Comparative Example 1 uses a cyclic olefin-based resin film as a base material, so that the tear resistance is inferior, and since solid particles are used, the total light transmittance is reduced as compared with Examples 1-5. did. Comparative Example 2 was inferior in scratch resistance because the amount of hollow particles added exceeded 150 parts by mass. In Comparative Example 3, since the amount of hollow particles added was less than 10 parts by mass, the total light transmittance was reduced as compared with Examples 1-5. In Comparative Example 4, since the porosity of the hollow particles was less than 20% by volume, the total light transmittance was lower than in Examples 1-5.
  • Comparative Example 5 since the average particle diameter of the hollow particles exceeded 500 nm, the total light transmittance was lowered, and the coating thickness was less than twice that of the hollow particles, so that the scratch resistance was inferior. Furthermore, since the average particle diameter of the hollow particles used in Comparative Example 5 was 562 nm, which was larger than other particles, the haze value was high and the transparency was poor. In Comparative Example 6, since a cyclic olefin-based resin film having a glass transition temperature exceeding 95 ° C. was used as the base material of the projection film, the tear resistance was inferior.
  • the present invention can provide a projection film excellent in tear resistance, scratch resistance and optical properties, can realize a projection screen excellent in visibility and transparency, and can be used as a screen for various projectors.

Abstract

A film for projection according to the present invention is provided with a resin layer on at least one surface of a substrate; the substrate is formed from a resin film that has a glass transition temperature of 95°C or less; the resin layer contains hollow particles and a resin; the average particle diameter of primary particles of the hollow particles is from 30 nm to 500 nm (inclusive); the porosity of the hollow particles is from 20% by volume to 95% by volume (inclusive); the content of the hollow particles is from 10 parts by mass to 150 parts by mass relative to 100 parts by mass of the resin; and the thickness of the resin layer is twice the average particle diameter of the hollow particles or more.

Description

投影用フィルム作製用組成物、投影用フィルム及び投影用スクリーンProjection film preparation composition, projection film and projection screen
　本発明は、投影用フィルム作製用組成物とその投影用フィルム作製用組成物を用いて作製した投影用フィルム、及びその投影用フィルムを用いた投影用スクリーンに関する。 The present invention relates to a projection film preparation composition, a projection film prepared using the projection film preparation composition, and a projection screen using the projection film.
　ホームシアターといった個人用途、商品広告等のデジタルサイネージ、更に会議室等での資料投影といった企業内活動等の様々な用途で、プロジェクターが用いられている。このようなプロジェクターの投影用スクリーンには、投影用スクリーンの背面に映像を投影し透過光を視認する透過型スクリーンと、投影用スクリーンの前面に映像を投影して反射光を視認する反射型スクリーンの２つのタイプがある。それぞれのタイプのスクリーンで重要なことは、投影画像が明確に確認できること、即ち視認性である。視認性を良好とするには透過型スクリーンでは、特に透過光が明るいことが必要である。 Projectors are used for various purposes such as personal use such as home theater, digital signage such as product advertisements, and corporate activities such as projecting data in conference rooms. The projection screen of such a projector includes a transmissive screen that projects an image on the back of the projection screen and visually recognizes the transmitted light, and a reflective screen that projects the image on the front of the projection screen and visually recognizes the reflected light. There are two types. What is important for each type of screen is that the projected image can be clearly confirmed, that is, visibility. In order to improve visibility, it is necessary for transmitted light to be particularly bright in a transmissive screen.
　近年、省スペース化のため、プロジェクターと投影用スクリーンとの距離を短縮した超短焦点プロジェクターが商品化されてきている。超短焦点プロジェクターは、従来のプロジェクターと画像の投影角が異なる。従来のプロジェクターは投影用スクリーンに対し正面方向から画像を投影するのに対し、超短焦点プロジェクターは、投影用スクリーンにプロジェクターを近接して設置するため、極端に斜め方向から画像を投影することになる。このように超短焦点プロジェクターを用いると、投影用スクリーンに対する投影光の入射角が大きくなるためスクリーンを透過する光量が減少し、投影画像が従来のプロジェクターを用いた場合に比べて暗くなり、視認性が劣ることになる。 In recent years, in order to save space, ultra-short focus projectors in which the distance between the projector and the projection screen is shortened have been commercialized. The ultra-short focus projector differs from the conventional projector in the image projection angle. Conventional projectors project images from the front direction onto the projection screen, whereas ultra-short focus projectors place the projector close to the projection screen, so project images from an extremely oblique direction. Become. When an ultra-short focus projector is used in this way, the incident angle of the projection light with respect to the projection screen increases, so the amount of light transmitted through the screen decreases, and the projected image becomes darker than when a conventional projector is used. It will be inferior.
　超短焦点プロジェクターを用い、透過型スクリーンにおいて視認性の良好な画像を得るには、従来のプロジェクターより光量を増加させる方法、あるいは投影用スクリーンの光透過率を高める方法を採用することが考えられる。本発明者らは、投影用スクリーンの光透過率を高める方法を採用し、そのための検討を始めた。その結果、投影用スクリーンの光透過率を増すには、投影用スクリーンに用いる投影用フィルムの表面に中空粒子を含む層を設ければよいことを見出した。 In order to obtain an image with good visibility on a transmissive screen using an ultra-short focus projector, it is conceivable to employ a method of increasing the amount of light compared to a conventional projector or a method of increasing the light transmittance of a projection screen. . The present inventors have adopted a method for increasing the light transmittance of the projection screen, and have started studies for that purpose. As a result, it has been found that in order to increase the light transmittance of the projection screen, a layer containing hollow particles may be provided on the surface of the projection film used for the projection screen.
　ところで、投影用フィルムに中空粒子を用いる例として、例えば、特許文献１では、環状オレフィン系樹脂と、環状オレフィン系樹脂と親和性に優れる中空で平均粒子径が２．０μｍ以上の有機架橋粒子とを含む樹脂組成物を用いることが提案されている。この樹脂組成物は成型性に優れており、この樹脂組成物を用いることにより、明るさと像の鮮明さとが向上した透過型スクリーン用拡散板を提供できるとしている。しかし、このような環状オレフィン系樹脂は引き裂き強度が低く、また衝撃にも弱いため、投影用フィルムに用いた場合に、その取扱いが難しい。 By the way, as an example of using hollow particles for a projection film, for example, in Patent Document 1, a cyclic olefin resin and a hollow organic olefin resin having an affinity for a cyclic olefin resin and an average particle diameter of 2.0 μm or more are used. It has been proposed to use a resin composition containing. This resin composition is excellent in moldability. By using this resin composition, it is said that it is possible to provide a transmissive screen diffusion plate with improved brightness and image clarity. However, such a cyclic olefin-based resin has a low tear strength and is also susceptible to impact, so that it is difficult to handle when used in a projection film.
　また、特許文献２には、中空ビーズを用いた透過型スクリーンが提案されている。しかしながら、特許文献２では、中空ビーズの気体部分の平均径（空孔径）として、０．１～４０μｍの範囲を用いるとしているが、このような空孔径の中空ビーズを用いると、散乱光が多く、画像の視認性は向上するが、スクリーン奥側の物体の確認、透視性はまだ十分でなかった。 Also, Patent Document 2 proposes a transmission screen using hollow beads. However, in Patent Document 2, a range of 0.1 to 40 μm is used as the average diameter (hole diameter) of the gas part of the hollow beads. However, when hollow beads having such a hole diameter are used, a large amount of scattered light is used. Although the visibility of the image is improved, the confirmation and transparency of the object on the back side of the screen are still insufficient.
　また、本発明に関連する先行技術文献としては、特許文献３～７及び非特許文献１及び２がある。 In addition, as prior art documents related to the present invention, there are Patent Documents 3 to 7 and Non-Patent Documents 1 and 2.
特開２００８－６４９５１号公報JP 2008-64951 A 特許第４８４７３２９号公報（国際公開ＷＯ２００６／０１６５５６）Japanese Patent No. 4847329 (International Publication WO2006 / 016556) 特許第４０４６９２１号公報（特開２００１－２３３６１１号公報）Japanese Patent No. 4046921 (Japanese Patent Laid-Open No. 2001-233611) 特許第４６５４４２８号公報（特開２００５－２６３５５０号公報）Japanese Patent No. 4654428 (Japanese Patent Laid-Open No. 2005-263550) 特許第４８６１６３４号公報（特開２００６－２５６９２１号公報）Japanese Patent No. 4816634 (Japanese Patent Laid-Open No. 2006-256922) 特許第４８５３６６２号公報（特開２００８－２４７６６４号公報）Japanese Patent No. 4853662 (Japanese Patent Laid-Open No. 2008-247664) 特許第５１９４９３５号公報（特開２００９－２３４８４８号公報）Japanese Patent No. 5194935 (Japanese Patent Laid-Open No. 2009-234848)
　本発明は、ガラス基板等への貼付け作業前の投影用フィルムの裁断、加工等の際に、投影用フィルムの引き裂きが生じにくく、また、スキージ等を用いて貼付け作業を行っても投影用フィルムの表面に傷つきが生じにくく、更に視認性が良好で、透視性の良好な投影用フィルムを提供するものである。 In the present invention, the projection film is not easily torn during cutting or processing of the projection film before being applied to a glass substrate or the like, and even if the application is performed using a squeegee or the like, the projection film It is an object of the present invention to provide a projection film that is less likely to be scratched on the surface, has good visibility, and has good transparency.
　本発明の投影用フィルム作製用組成物は、中空粒子と、重合性化合物と、溶剤とを含む投影用フィルム作製用組成物であって、前記中空粒子の１次粒子の平均粒子径が、３０ｎｍ以上５００ｎｍ以下であり、前記中空粒子の空隙率が、２０体積％以上９５体積％以下であり、前記中空粒子の含有量が、前記中空粒子以外の、前記重合性化合物を含む固形成分１００質量部に対して、１０質量部以上１５０質量部以下であることを特徴とする。 The composition for producing a projection film of the present invention is a composition for producing a projection film containing hollow particles, a polymerizable compound, and a solvent, and the average particle diameter of primary particles of the hollow particles is 30 nm. More than or equal to 500 nm, the porosity of the hollow particles is 20% by volume or more and 95% by volume or less, and the content of the hollow particles is 100 parts by mass of the polymerizable compound other than the hollow particles. It is characterized by being 10 parts by mass or more and 150 parts by mass or less.
　また、本発明の投影用フィルムは、基材の少なくとも一方の面に樹脂層を有する投影用フィルムであって、前記基材は、ガラス転移温度が９５℃以下の樹脂フィルムからなり、前記樹脂層は、中空粒子と、樹脂とを含み、前記中空粒子の１次粒子の平均粒子径が、３０ｎｍ以上５００ｎｍ以下であり、前記中空粒子の空隙率が、２０体積％以上９５体積％以下であり、前記中空粒子の含有量が、前記樹脂１００質量部に対して、１０質量部以上１５０質量部以下であり、前記樹脂層の厚さが、前記中空粒子の平均粒子径の２倍以上であることを特徴とする。 Further, the projection film of the present invention is a projection film having a resin layer on at least one surface of a substrate, and the substrate is made of a resin film having a glass transition temperature of 95 ° C. or less, and the resin layer Includes hollow particles and a resin, the average particle diameter of primary particles of the hollow particles is 30 nm or more and 500 nm or less, and the porosity of the hollow particles is 20% by volume or more and 95% by volume or less, The content of the hollow particles is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, and the thickness of the resin layer is at least twice the average particle diameter of the hollow particles. It is characterized by.
　また、本発明の投影用スクリーンは、部材と、前記部材に貼付した投影用フィルムとを含む投影用スクリーンであって、前記投影用フィルムが、上記本発明の投影用フィルムであることを特徴とする。 The projection screen of the present invention is a projection screen including a member and a projection film affixed to the member, wherein the projection film is the projection film of the present invention. To do.
　本発明によれば、耐引き裂き性、耐擦傷性及び光学特性に優れた投影用フィルムを提供できる。 According to the present invention, a projection film having excellent tear resistance, scratch resistance and optical characteristics can be provided.
図１は、本発明の投影用スクリーンの一例を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing an example of the projection screen of the present invention. 図２は、本発明の投影用スクリーンに超短焦点プロジェクターを用いて映像を投影している状態の一例を示す模式図であるFIG. 2 is a schematic diagram showing an example of a state in which an image is projected onto the projection screen of the present invention using an ultrashort focus projector.
　（本発明の投影用フィルム作製用組成物）
　本発明者らは、投影用フィルムにおいて耐擦傷性及び光学特性を向上させる手段を種々検討したところ、投影用フィルムの表面に中空粒子と樹脂とを含む樹脂層を形成すればよいことを見出し、本発明の投影用フィルム作製用組成物を完成させた。 (Composition for producing a projection film of the present invention)
The present inventors have studied various means for improving scratch resistance and optical properties in the projection film, and found that a resin layer containing hollow particles and a resin may be formed on the surface of the projection film. The composition for producing a projection film of the present invention was completed.
　即ち、本発明の投影用フィルム作製用組成物は、中空粒子と、重合性化合物と、溶剤とを含み、上記中空粒子の１次粒子の平均粒子径は、３０ｎｍ以上５００ｎｍ以下であり、上記中空粒子の空隙率は、２０体積％以上９５体積％以下であり、上記中空粒子の含有量は、上記中空粒子以外の、上記重合性化合物を含む固形成分１００質量部に対して、１０質量部以上１５０質量部以下である。 That is, the composition for producing a projection film of the present invention includes hollow particles, a polymerizable compound, and a solvent, and the average particle diameter of primary particles of the hollow particles is 30 nm to 500 nm, and the hollow The porosity of the particles is 20% by volume or more and 95% by volume or less, and the content of the hollow particles is 10 parts by mass or more with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles. It is 150 parts by mass or less.
　本発明の投影用フィルム作製用組成物は、１次粒子の平均粒子径が３０ｎｍ以上５００ｎｍ以下であり、且つ、空隙率が２０体積％以上９５体積％以下の中空粒子を含んでいるため、耐擦傷性及び光学特性に優れた投影用フィルムを提供できる。 Since the composition for producing a projection film of the present invention contains hollow particles having an average primary particle diameter of 30 nm to 500 nm and a porosity of 20 vol% to 95 vol%, A projection film having excellent scratch resistance and optical properties can be provided.
　また、上記中空粒子の含有量は、上記中空粒子以外の、上記重合性化合物を含む固形成分１００質量部に対して、１０質量部以上１５０質量部以下に設定する必要があり、２０質量部以上１２０質量部以下がより好ましい。上記中空粒子の含有量が１０質量部を下回ると、投影用フィルムの光透過率の向上効果が小さくなり、上記中空粒子の含有量が１５０質量部を超えると、投影用フィルムの耐擦傷性が低下する。 Further, the content of the hollow particles must be set to 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles, and 20 parts by mass or more. 120 parts by mass or less is more preferable. When the content of the hollow particles is less than 10 parts by mass, the effect of improving the light transmittance of the projection film is reduced. When the content of the hollow particles exceeds 150 parts by mass, the scratch resistance of the projection film is reduced. descend.
　以下、本発明の投影用フィルム作製用組成物の各成分について詳細に説明する。 Hereinafter, each component of the composition for producing a projection film of the present invention will be described in detail.
　＜中空粒子＞
　本発明で使用する中空粒子の平均粒子径は、３０ｎｍ以上５００ｎｍ以下であることが必要であり、６０ｎｍ以上３００ｎｍ以下であることが更に好ましい。上記平均粒子径が３０ｎｍを下回ると、粒子の比表面積が大きくなり、その粒子を分散させるためにより多くの溶剤が必要となるため、投影用フィルム作製用組成物の粘度が低下して、塗膜の厚さを十分に確保できない場合がある。また、上記平均粒子径が５００ｎｍを超えると光の散乱が増すためか、投影用フィルムのヘイズが増加して透視性が向上しない。 <Hollow particles>
The average particle size of the hollow particles used in the present invention needs to be 30 nm or more and 500 nm or less, and more preferably 60 nm or more and 300 nm or less. When the average particle diameter is less than 30 nm, the specific surface area of the particles is increased, and more solvent is required to disperse the particles. In some cases, sufficient thickness cannot be secured. On the other hand, if the average particle diameter exceeds 500 nm, light scattering increases, or the haze of the projection film increases and the transparency is not improved.
　また、上記中空粒子の空隙率は、２０体積％以上９５体積％以下であることが必要であり、３０体積％以上７５体積％以下であることが好ましい。上記空隙率が２０体積％を下回ると、投影用フィルムの光透過率が向上せず、画像の視認性が劣る。また、上記空隙率が９５体積％を超えると、粒子の殻壁が薄くなり、破砕されやすくなるためか、投影用フィルムの光透過率が向上せず、画像の視認性が劣る。 The porosity of the hollow particles needs to be 20% by volume or more and 95% by volume or less, and preferably 30% by volume or more and 75% by volume or less. When the porosity is less than 20% by volume, the light transmittance of the projection film is not improved, and the visibility of the image is poor. On the other hand, if the porosity exceeds 95% by volume, the shell wall of the particle becomes thin and easily broken, or the light transmittance of the projection film is not improved and the image visibility is poor.
　上記中空粒子の平均粒子径を３０ｎｍ以上５００ｎｍ以下とし、空隙率を２０体積％以上９５体積％以下とすることで、投影用フィルムの光透過率が向上し、また、ヘイズが１５％未満と低くなるため、超短焦点プロジェクター用のスクリーンに用いた場合、正面や斜めからの視認性に優れ、また、透視性が良好な投影用フィルムを得ることができる。画像の視認性と透視性とは、ともにヘイズ値に依存し、本発明者らは、これらを両立するにはヘイズ値を１５％未満に調整すればよいことを見出し、本発明に至った。 By making the average particle diameter of the hollow particles 30 nm or more and 500 nm or less and the porosity 20 volume% or more and 95 volume% or less, the light transmittance of the projection film is improved and the haze is as low as less than 15%. Therefore, when used for a screen for an ultra-short focus projector, a projection film having excellent visibility from the front and oblique directions and excellent transparency can be obtained. Both visibility and transparency of the image depend on the haze value, and the present inventors have found that the haze value may be adjusted to less than 15% in order to achieve both of these, and the present invention has been achieved.
　上記中空粒子の平均粒子径及び空隙率は、中空粒子を走査型電子顕微鏡（ＳＥＭ）又は透過型電子顕微鏡（ＴＥＭ）で観察して算出できる。上記観察では、上記中空粒子を直接観察してもよいし、上記中空粒子をイオンミリングで断面加工して観察してもよく、また、上記中空粒子を樹脂包埋した後にミクロトーム等で断面加工して観察してもよい。いずれにしても、上記中空粒子の１０個以上の粒子について、その粒子径、殻壁の厚さを測定し、その平均粒子径及び殻壁の平均厚さを求め、下記式（１）から空隙率を求めればよい。ここで、上記中空粒子の粒子径は、いわゆる１次粒子の大きさを指し、上記中空粒子が長軸長と短軸長の比が１～３．５である球状ないし楕円体状の場合は最大差し渡し径をその粒子径とし、それ以外の粒子の場合には長軸径をその粒子の粒子径とする。
　空隙率（％）＝［（平均粒子径－殻壁の平均厚さ×２）／平均粒子径］3×１００　　（１） The average particle diameter and porosity of the hollow particles can be calculated by observing the hollow particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM). In the above observation, the hollow particles may be observed directly, or the hollow particles may be cross-sectionally processed by ion milling, and the hollow particles may be cross-sectionally processed with a microtome or the like after being embedded in a resin. May be observed. In any case, with respect to 10 or more particles of the hollow particles, the particle diameter and the shell wall thickness are measured, and the average particle diameter and the average shell wall thickness are obtained. Find the rate. Here, the particle diameter of the hollow particles refers to the so-called primary particle size, and when the hollow particles are spherical or ellipsoidal in which the ratio of the major axis length to the minor axis length is 1 to 3.5. The maximum delivery diameter is defined as the particle diameter, and in the case of other particles, the major axis diameter is defined as the particle diameter of the particle.
Porosity (%) = [(average particle size−average thickness of shell wall × 2) / average particle size] 3 × 100 (1)
　本発明の投影用フィルム作製用組成物に含まれる中空粒子の含有量は、前述のとおり、上記中空粒子以外の上記重合性化合物を含む固形成分１００質量部に対して、１０質量部以上１５０質量部以下に設定されるが、上記重合性化合物を除く固形成分としては、例えば、光重合開始剤、樹脂ポリマー、分散剤、粘着付与剤等の任意成分が該当する。また、上記中空粒子の含有量は、例えば、熱分析法により測定できる。即ち、上記投影用フィルム作製用組成物を加熱して溶剤等の非固形成分を除去した後、残りの固形成分の質量を測定し、更に７００℃付近まで加熱して、中空粒子以外の固形成分を焼失させた後の残渣の質量を測定する。その残渣の質量は中空粒子の質量と考えられるため、その残渣の質量と上記固形成分の質量から、投影用フィルム作製用組成物に含まれる中空粒子の含有率を求めることができる。 As described above, the content of the hollow particles contained in the projection film preparation composition of the present invention is 10 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles. The solid component excluding the polymerizable compound includes, for example, optional components such as a photopolymerization initiator, a resin polymer, a dispersant, and a tackifier. The content of the hollow particles can be measured by, for example, a thermal analysis method. That is, after the non-solid component such as a solvent is removed by heating the film-forming composition for projection, the mass of the remaining solid component is measured, and further heated to around 700 ° C. to obtain a solid component other than the hollow particles. The mass of the residue after burning is measured. Since the mass of the residue is considered to be the mass of the hollow particles, the content of the hollow particles contained in the projection film preparation composition can be determined from the mass of the residue and the mass of the solid component.
　上記中空粒子の材質は限定されず、中空無機粒子及び中空有機粒子のいずれも使用できるが、中空無機粒子である中空シリカ粒子が特に好ましい。上記中空シリカ粒子は、物理的強度が大きく、投影用フィルム作製用組成物中での分散性に優れているからである。上記中空シリカ粒子は、その構成成分としてＳｉＯ2以外に他の金属元素を含んでいてもよく、また、含水化合物であってもよい。 The material of the hollow particles is not limited, and both hollow inorganic particles and hollow organic particles can be used, but hollow silica particles that are hollow inorganic particles are particularly preferable. This is because the hollow silica particles have high physical strength and are excellent in dispersibility in the composition for producing a projection film. The hollow silica particles may contain other metal elements in addition to SiO 2 as a constituent component, or may be a hydrous compound.
　上記平均粒子径が３０ｎｍ以上５００ｎｍ以下の中空シリカ粒子の作製方法は特に限定されないが、例えば、前述の非特許文献１に記載されているようなテンプレート法により作製できる。より具体的には、前述の非特許文献２に記載の気泡をテンプレートとして用いる方法、前述の特許文献３、４、５に記載の無機粒子を鋳型とする無機テンプレート法、前述の特許文献６、７に記載の有機粒子を鋳型とする有機テンプレート法等により作製できる。 The method for producing hollow silica particles having an average particle diameter of 30 nm or more and 500 nm or less is not particularly limited. For example, the hollow silica particles can be produced by a template method as described in Non-Patent Document 1 described above. More specifically, a method using the bubbles described in Non-Patent Document 2 as a template, an inorganic template method using the inorganic particles described in Patent Documents 3, 4, and 5 as a template, Patent Document 6 described above, 7 can be produced by an organic template method using the organic particles described in 7 as a template.
　更に、上記中空シリカ粒子には、上記重合性化合物を重合して形成する樹脂との馴染みをよくするため、表面処理を施してもよい。上記表面処理は、例えば中空シリカ粒子の分散液又は懸濁液にシリコンカップリング剤を添加して行ってもよい。用いるシリコンカップリング剤により、中空シリカ粒子の表面を修飾する有機官能基は異なるが、メチル基、フェニル基等で修飾して表面処理することが好ましい。 Furthermore, the hollow silica particles may be subjected to a surface treatment in order to improve familiarity with a resin formed by polymerizing the polymerizable compound. The surface treatment may be performed, for example, by adding a silicon coupling agent to a dispersion or suspension of hollow silica particles. Although the organic functional group that modifies the surface of the hollow silica particles varies depending on the silicon coupling agent to be used, it is preferable to modify the surface with a methyl group, a phenyl group, or the like for surface treatment.
　＜重合性化合物＞
　本発明で使用する重合性化合物は、各種のモノマー又はオリゴマーを用いることができるが、上記重合性化合物は、少なくとも上記オリゴマーを含むことが好ましい。上記オリゴマーとしては、ウレタンアクリレート、ポリエーテルアクリレート、ポリエステルアクリレート等を好適に用いることができる。上記オリゴマーを用いると、モノマーを単独で用いるより、いわゆる製膜性が向上し、架橋点間分子量が大きくなって作製後のフィルムのそり、いわゆるカールを低減することができる。 <Polymerizable compound>
Although various monomers or oligomers can be used for the polymerizable compound used in the present invention, the polymerizable compound preferably contains at least the oligomer. As the oligomer, urethane acrylate, polyether acrylate, polyester acrylate and the like can be suitably used. When the oligomer is used, the so-called film-forming property is improved and the molecular weight between cross-linking points is increased, and the warpage of the film after production, so-called curling, can be reduced as compared with the case where the monomer is used alone.
　上記モノマーとしては、従来公知の紫外線硬化型樹脂モノマーを用いることが好ましい。例えば、ペンタエリスリトールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート等の多官能モノマーを使用してもよい。 As the monomer, it is preferable to use a conventionally known ultraviolet curable resin monomer. For example, polyfunctional monomers such as pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate may be used.
　上記重合性化合物は、ガンマー線、電子線、紫外線等の放射線を照射すると反応する官能基を含むものであり、放射線照射で反応する官能基としては、アクリル基、メタクリル基が好ましい。上記放射線として紫外線を用いる場合は、本発明の投影用フィルム作製用組成物は上記重合性化合物と共に光重合開始剤を含むことが好ましい。上記光重合開始剤としては、例えば、１－ヒドロキシシクロヘキシルフェニルケトン、２,２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－ヒドロキ－２－メチル－１－フェニルプロパン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、ビス（２,４,６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、２,４,６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド等を好適に用いることができる。上記光重合開始剤の添加量は、上記重合性化合物１００質量部に対して、０．１～１０質量部とすればよく、０．３～５質量部が好ましい。 The above-mentioned polymerizable compound contains a functional group that reacts when irradiated with radiation such as gamma rays, electron beams, or ultraviolet rays, and an acrylic group or methacryl group is preferable as the functional group that reacts upon irradiation with radiation. When ultraviolet rays are used as the radiation, the composition for producing a projection film of the present invention preferably contains a photopolymerization initiator together with the polymerizable compound. Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one. 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide or the like can be preferably used. The addition amount of the photopolymerization initiator may be 0.1 to 10 parts by mass, and preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.
　本発明の投影用フィルム作製用組成物の製造方法は特に限定されず、例えば、上記各成分を溶剤と混合して、各固形成分を十分に分散すればよい。上記混合方法は特に限定されないが、例えば、ディスパー、ホモミキサー、リボンミキサー、パドルミキサー、プラネタリミキサー、ロールミル、ニーダー、ボールミル、サンドミル、高圧ホモジナイザー、超音波分散機等を用いて混合することができる。 The method for producing the composition for producing a projection film of the present invention is not particularly limited. For example, the above-described components may be mixed with a solvent to sufficiently disperse each solid component. Although the said mixing method is not specifically limited, For example, it can mix using a disper, a homomixer, a ribbon mixer, a paddle mixer, a planetary mixer, a roll mill, a kneader, a ball mill, a sand mill, a high-pressure homogenizer, an ultrasonic disperser, etc.
　上記溶剤としては、従来公知のものを用いることができる。例えば、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、イソホロン等のケトン系、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系、ヘキサン、オクタン等の脂肪族系、トルエン、キシレン等の芳香族系、エチレングリコール、メタノール、エタノール、イソプロパノール等のアルコール系、ターピネオール、ジヒドロターピネオール、リモネン等のテルペン系、メチルグリコール、イソプロピルグリコール、メチルプロピレングリコール、プロピルプロピレングリコール、ブチルプロピレングリコール、メチルプロピレングリコールアセテート、ジメチルグリコール、ジメチルジグリコール等のグリコールエーテル系の溶剤を単独もしくは混合して用いてもよい。上記溶剤の使用量は、上記投影用フィルム作製用組成物に対し塗布に適した流動性を与えるのに必要な量を使用すればよい。 A conventionally known solvent can be used as the solvent. For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as methyl acetate, ethyl acetate and butyl acetate, aliphatics such as hexane and octane, and aromatics such as toluene and xylene , Alcohols such as ethylene glycol, methanol, ethanol, isopropanol, terpenes such as terpineol, dihydroterpineol, limonene, methyl glycol, isopropyl glycol, methyl propylene glycol, propyl propylene glycol, butyl propylene glycol, methyl propylene glycol acetate, dimethyl glycol A glycol ether solvent such as dimethyldiglycol may be used alone or in combination. What is necessary is just to use the amount of the said solvent used in order to give the fluidity | liquidity suitable for application | coating with respect to the said composition for film production for projection.
　（本発明の投影用フィルム）
　本発明の投影用フィルムは、基材と、上記基材の上に形成された樹脂層とを含み、上記基材は、ガラス転移温度が９５℃以下の樹脂フィルムからなり、上記樹脂層は、中空粒子と、樹脂とを含み、上記中空粒子の１次粒子の平均粒子径が、３０ｎｍ以上５００ｎｍ以下であり、上記中空粒子の空隙率が、２０体積％以上９５体積％以下であり、上記中空粒子の含有量が、上記樹脂１００質量部に対して、１０質量部以上１５０質量部以下であり、上記樹脂層の厚さが、上記中空粒子の平均粒子径の２倍以上である。 (Projection film of the present invention)
The projection film of the present invention includes a base material and a resin layer formed on the base material, and the base material is composed of a resin film having a glass transition temperature of 95 ° C. or less. Hollow particles and a resin, the primary particles of the hollow particles have an average particle diameter of 30 nm to 500 nm, the void ratio of the hollow particles is 20% to 95% by volume, and the hollow The particle content is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, and the thickness of the resin layer is twice or more the average particle diameter of the hollow particles.
　本発明の投影用フィルムの基材は、ガラス転移温度が９５℃以下の樹脂フィルムからなるため、ガラス基板等への貼付け作業前の投影用フィルムの裁断、加工等の際に、投影用フィルムの引き裂きが生じにくい。 Since the substrate of the projection film of the present invention is made of a resin film having a glass transition temperature of 95 ° C. or lower, the projection film is cut when the projection film is applied to a glass substrate or the like before cutting. It is hard to tear.
　また、本発明の投影用フィルムの樹脂層は、１次粒子の平均粒子径が３０ｎｍ以上５００ｎｍ以下であり、且つ、空隙率が２０体積％以上９５体積％以下の中空粒子を含んでいるため、耐擦傷性及び光学特性に優れた投影用フィルムを提供できる。 Moreover, since the resin layer of the projection film of the present invention contains hollow particles having an average primary particle diameter of 30 nm to 500 nm and a porosity of 20 vol% to 95 vol%, A projection film excellent in scratch resistance and optical properties can be provided.
　また、上記樹脂層における上記中空粒子の含有量は、上記樹脂１００質量部に対して、１０質量部以上１５０質量部以下に設定する必要があり、２０質量部以上１２０質量部以下がより好ましい。上記中空粒子の含有量が１０質量部を下回ると、投影用フィルムの光透過率の向上効果が小さくなり、上記中空粒子の含有量が１５０質量部を超えると、投影用フィルムの耐擦傷性が低下する。 Further, the content of the hollow particles in the resin layer needs to be set to 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, and more preferably 20 parts by mass or more and 120 parts by mass or less. When the content of the hollow particles is less than 10 parts by mass, the effect of improving the light transmittance of the projection film is reduced. When the content of the hollow particles exceeds 150 parts by mass, the scratch resistance of the projection film is reduced. descend.
　本発明の投影用フィルムの樹脂層に含まれる中空粒子の含有量は、上記樹脂１００質量部に対して、１０質量部以上１５０質量部以下に設定されるが、その含有量は、例えば、熱分析法により測定できる。即ち、上記基材から剥がした上記投影用フィルムの樹脂層を７００℃付近まで加熱して、残渣の質量を測定し、その残渣の質量から上記樹脂層に含まれる中空粒子の質量を求めて、その中空粒子の質量から上記樹脂層に含まれる中空粒子の含有率を求めることができる。 The content of the hollow particles contained in the resin layer of the projection film of the present invention is set to 10 to 150 parts by mass with respect to 100 parts by mass of the resin. It can be measured by analytical methods. That is, the resin layer of the projection film peeled off from the substrate is heated to around 700 ° C., the mass of the residue is measured, and the mass of the hollow particles contained in the resin layer is determined from the mass of the residue. The content of the hollow particles contained in the resin layer can be determined from the mass of the hollow particles.
　更に、上記樹脂層の厚さは、上記中空粒子の平均粒子径の２倍以上とする必要がある。上記樹脂層の厚さを上記中空粒子の平均粒子径の２倍以上とすることにより、上記樹脂層の表面を平滑にでき、投影用フィルムをガラス基板等に貼り付ける時に、スキージ等で擦ってもフィルム表面に傷が付かない。 Furthermore, the thickness of the resin layer needs to be at least twice the average particle diameter of the hollow particles. By making the thickness of the resin layer at least twice the average particle diameter of the hollow particles, the surface of the resin layer can be smoothed and rubbed with a squeegee or the like when the projection film is attached to a glass substrate or the like. The film surface is not scratched.
　上記投影用フィルムは、そのヘイズを１５％未満にすることができる。 The projection film can have a haze of less than 15%.
　以下、本発明の投影用フィルムの各構成部材について詳細に説明する。 Hereinafter, each component of the projection film of the present invention will be described in detail.
　＜基材＞
　本発明で使用する基材は、ガラス転移温度が９５℃以下の樹脂フィルムであればよく、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンナフタレート（ＰＥＮ）フィルム等を使用できるが、その汎用性の点から、ＰＥＴフィルムが好ましい。ガラス転移温度が９５℃以下の樹脂フィルムを使用することにより、前述のとおり、耐引き裂き性を向上できる。 <Base material>
The base material used in the present invention may be a resin film having a glass transition temperature of 95 ° C. or lower. For example, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, etc. can be used. From the viewpoint, a PET film is preferable. By using a resin film having a glass transition temperature of 95 ° C. or lower, the tear resistance can be improved as described above.
　上記基材の厚さは特に限定されず、例えば１０～２００μｍとすることができる。 The thickness of the substrate is not particularly limited, and can be, for example, 10 to 200 μm.
　一方、ガラス転移温度が９５℃を超える、例えば環状オレフィン系樹脂フィルムを用いると、高弾性率である反面、耐引き裂き性が低くなる。 On the other hand, when a cyclic olefin-based resin film having a glass transition temperature exceeding 95 ° C. is used, for example, the elastic modulus is high, but the tear resistance is low.
　＜樹脂層＞
　本発明で使用する樹脂層は、中空粒子と樹脂とを含むものであるが、上記中空粒子については、前述の本発明の投影用フィルム作製用組成物で使用する中空粒子と同じものが使用できる。 <Resin layer>
The resin layer used in the present invention contains hollow particles and a resin, and the same hollow particles used in the above-mentioned composition for producing a projection film of the present invention can be used for the hollow particles.
　上記樹脂としては、例えば、アクリル系樹脂、ポリウレタン系樹脂、ポリスチレン系樹脂、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂等を用いることができる。また、上記樹脂として、前述の本発明の投影用フィルム作製用組成物で使用する重合性化合物を重合した樹脂を使用することもできる。 As the resin, for example, acrylic resin, polyurethane resin, polystyrene resin, polycarbonate resin, polyester resin, polyether resin, and the like can be used. Moreover, resin which superposed | polymerized the polymeric compound used with the composition for film production for projection of the above-mentioned this invention can also be used as said resin.
　上記樹脂層の厚さは、上記中空粒子の平均粒子径の２倍以上であれば、その上限値は特に限定されず、例えば５μｍ以下とすることができる。 The upper limit of the thickness of the resin layer is not particularly limited as long as it is twice or more the average particle diameter of the hollow particles, and can be, for example, 5 μm or less.
　本発明の投影用フィルムの製造方法は特に限定されず、例えば、上記中空粒子と上記樹脂と溶剤とを含む塗布液を調製し、その塗布液を上記基材に塗布して乾燥して、上記基材の上に上記樹脂層を形成することにより製造できる。 The production method of the projection film of the present invention is not particularly limited. For example, a coating liquid containing the hollow particles, the resin, and a solvent is prepared, the coating liquid is applied to the substrate, and dried. It can manufacture by forming the said resin layer on a base material.
　また、上記塗布液を塗布する方法は、平滑な塗膜を形成しうる塗布方法であれば特に制限されるものではなく、例えば、グラビアロール法、マイクログラビアロール法、マイクログラビアコータ法、スリットダイコート法、コンマコート法、スピン法、ナイフ法、キス法、スクイズ法、リバースロール法、ディップ法、バーコート法等が挙げられる。 The method for applying the coating solution is not particularly limited as long as it is a coating method that can form a smooth coating film. For example, a gravure roll method, a micro gravure roll method, a micro gravure coater method, a slit die coat Method, comma coat method, spin method, knife method, kiss method, squeeze method, reverse roll method, dipping method, bar coat method and the like.
　また、本発明の投影用フィルムは、前述の本発明の投影用フィルム作製用組成物を上記基材に塗布した後、上記投影用フィルム作製用組成物に含まれる重合性化合物を重合して、上記基材の上に上記樹脂層を形成することによっても製造できる。上記重合性化合物を重合する方法は特に限定されないが、塗膜に紫外線等の電離放射線を照射する方法を用いることができる。 Further, the projection film of the present invention is obtained by polymerizing the polymerizable compound contained in the projection film preparation composition after applying the projection film preparation composition of the present invention to the substrate. It can also be produced by forming the resin layer on the substrate. Although the method for polymerizing the polymerizable compound is not particularly limited, a method of irradiating the coating film with ionizing radiation such as ultraviolet rays can be used.
　上記電離放射線としては、例えば、紫外線、電子線、β線等を用いることができるが、簡便に利用できることから、紫外線が多用される。紫外線の光源としては、高圧水銀灯、メタルハライドランプ、紫外線ＬＥＤランプ等が使用できる。上記電離放射線として紫外線を用いる場合には、前述のとおり上記投影用フィルム作製用組成物には光重合開始剤を含めることが好ましい。 As the ionizing radiation, for example, ultraviolet rays, electron beams, β rays, and the like can be used, but ultraviolet rays are frequently used because they can be easily used. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, an ultraviolet LED lamp, or the like can be used. When ultraviolet rays are used as the ionizing radiation, it is preferable to include a photopolymerization initiator in the composition for producing a projection film as described above.
　（本発明の投影用スクリーン）
　本発明の投影用スクリーンは、部材と、上記部材に貼付した投影用フィルムとを備え、上記投影用フィルムが、上記本発明の投影用フィルムであることを特徴とする。本発明の投影用スクリーンは、本発明の投影用フィルムを備えているため、視認性に優れる。 (Projection screen of the present invention)
The projection screen of the present invention comprises a member and a projection film affixed to the member, and the projection film is the projection film of the present invention. Since the projection screen of the present invention includes the projection film of the present invention, it has excellent visibility.
　本発明の投影用スクリーンは、透過型スクリーンとしても、反射型スクリーンとしても用いることができるが、透過型スクリーンとして使用した場合に、特に視認性に優れる。 The projection screen of the present invention can be used as a transmissive screen or a reflective screen, but is particularly excellent in visibility when used as a transmissive screen.
　上記部材と上記投影用フィルムとは、粘着剤により貼り合わせられていることが好ましい。これにより、上記投影用フィルムの上記基材からの剥離を防止できる。また、上記粘着剤は、特に限定されない。 It is preferable that the member and the projection film are bonded together with an adhesive. Thereby, peeling of the projection film from the substrate can be prevented. Moreover, the said adhesive is not specifically limited.
　上記部材としても特に限定されないが、例えば、ガラス基板、ガラスシート、樹脂基板、樹脂シート等を使用できる。 Although the member is not particularly limited, for example, a glass substrate, a glass sheet, a resin substrate, a resin sheet, or the like can be used.
　また、上記投影用フィルムの上記樹脂層は、最表層に配置されていることが好ましい。これにより、スクリーンの視認性をより向上できる。 Further, it is preferable that the resin layer of the projection film is disposed on the outermost layer. Thereby, the visibility of a screen can be improved more.
　本発明の投影用スクリーンの製造方法は特に限定されず、例えば、上記部材に上記投影用フィルムを粘着剤等により貼り合わせればよい。 The production method of the projection screen of the present invention is not particularly limited. For example, the projection film may be bonded to the member with an adhesive or the like.
　次に、本発明の投影用スクリーンを図面に基づき説明する。図１は、本発明の投影用スクリーンの一例を示す模式断面図である。図１において、本発明の投影用スクリーン１０は、投影用フィルム１１と透明基板１２とを備え、投影用フィルム１１は、透明基板１２の上に粘着剤（図示せず。）を介して貼り合わされている。投影用フィルムは、ガラス転移温度が９５℃以下の樹脂フィルム１１ａと、樹脂フィルム１１ａの上に配置された樹脂層１１ｂとからなる。樹脂層１１ｂは、中空粒子と樹脂とから形成され、投影用スクリーンの最表層に配置されている。 Next, the projection screen of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the projection screen of the present invention. In FIG. 1, a projection screen 10 of the present invention includes a projection film 11 and a transparent substrate 12, and the projection film 11 is bonded onto the transparent substrate 12 via an adhesive (not shown). ing. The projection film includes a resin film 11a having a glass transition temperature of 95 ° C. or less and a resin layer 11b disposed on the resin film 11a. The resin layer 11b is formed of hollow particles and a resin, and is disposed on the outermost layer of the projection screen.
　また、図２は、図１に示した投影用スクリーンを透過型スクリーンとして用いて、超短焦点プロジェクターにより映像を投影している状態の一例を示す模式図である。図２において、投影用スクリーン１０は、その投影用フィルム１１側を超短焦点プロジェクター１３側に向けて配置されている。図２において、超短焦点プロジェクター１３からの投影光は、投影方向１３ａ側に投光され、映像の視認者は視認方向１４側から視認する。また、図２において、投影用フィルム１１は、図１と同様に、樹脂フィルム１１ａと、樹脂フィルム１１ａの上に配置された樹脂層１１ｂとからなり、透明基板１２に貼付されている。 FIG. 2 is a schematic diagram showing an example of a state in which an image is projected by an ultra-short focus projector using the projection screen shown in FIG. 1 as a transmission screen. In FIG. 2, the projection screen 10 is arranged with the projection film 11 side facing the ultrashort focus projector 13 side. In FIG. 2, the projection light from the ultra-short focus projector 13 is projected to the projection direction 13a side, and the viewer of the image visually recognizes from the viewing direction 14 side. In FIG. 2, the projection film 11 is composed of a resin film 11 a and a resin layer 11 b disposed on the resin film 11 a, as in FIG. 1, and is attached to the transparent substrate 12.
　以下、実施例により本発明を詳細に説明する。但し、本発明は以下の実施例に限定されるものではない。また、以下の実施例では「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In the following examples, “part” means “part by mass”.
　（実施例１）
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（ウレタンアクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＨＡ－４０Ｈ”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：１３７９部 Example 1
<Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (urethane acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA-40H”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio) -phenyl ] -2-Morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 1379 parts
　次に、上記混合液に下記成分（４）を配合して攪拌・混合した後、更に容器を水冷しながら混合液に対し超音波分散処理を行い、最後に孔径１μｍのフィルターを通してろ過して塗布液１を得た。
（４）中空シリカ粒子のメチルイソブチルケトン溶液（日揮触媒化成社製、商品名“スルーリア”、固形分濃度：２５質量％）：１００部 Next, the following component (4) is blended into the above mixed solution, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water, and finally filtered through a filter having a pore size of 1 μm. Liquid 1 was obtained.
(4) Methyl isobutyl ketone solution of hollow silica particles (manufactured by JGC Catalysts & Chemicals, trade name “Thruria”, solid content concentration: 25 mass%): 100 parts
　＜投影用フィルムの作製＞
　厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東レ社製、商品名“ルミラー”、ガラス転移温度：７０℃）の上に、バーコーターを用いて上記塗布液１を、塗膜厚さが０．１５μｍとなるよう塗布して乾燥した。次に、高圧水銀灯を用いて積算光量を２５０ｍＪ／ｃｍ2となるように紫外線を照射して上記塗膜の硬化処理を行い、ＰＥＴフィルムの上に樹脂層を形成して投影用フィルム１を作製した。 <Production of projection film>
On a 100 μm-thick polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., trade name “Lumirror”, glass transition temperature: 70 ° C.), the coating solution 1 was coated with a coating thickness of 0. 0 using a bar coater. It apply | coated and dried so that it might become 15 micrometers. Next, ultraviolet rays are irradiated using a high pressure mercury lamp so that the integrated light quantity is 250 mJ / cm 2 , the coating film is cured, and a resin layer is formed on the PET film to produce a projection film 1. did.
　（実施例２）
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：１５５部 (Example 2)
<Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 155 parts
　次に、上記混合液に下記成分（４）を配合して攪拌・混合した後、更に容器を水冷しながら混合液に対し超音波分散処理を行い、最後に孔径１μｍのフィルターを通してろ過して塗布液２を得た。
（４）中空シリカ粒子のメチルイソブチルケトン溶液（日揮触媒化成社製、商品名“スルーリア”、固形分濃度：２５質量％）：３００部 Next, the following component (4) is blended into the above mixed solution, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water, and finally filtered through a filter having a pore size of 1 μm. Liquid 2 was obtained.
(4) Methyl isobutyl ketone solution of hollow silica particles (manufactured by JGC Catalysts & Chemicals, trade name “Thruria”, solid content concentration: 25 mass%): 300 parts
　上記塗布液２を用い、塗膜厚さを１．７μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム２を作製した。 A projection film 2 was produced in the same manner as in Example 1 except that the coating liquid 2 was used and the coating thickness was 1.7 μm.
　（実施例３）
　＜中空シリカ粒子の作製＞
　ポリスチレン粒子懸濁液（ポリサイエンス社製、アミノ基修飾、粒子の平均粒子径：０．１μｍ、固形分濃度：２．５質量％）７５部を４０℃に加温し、その懸濁液を攪拌しながら以下の成分（１）～（４）を配合し、更に３０分攪拌して混合液を調製した。
（１）水：１５５部
（２）イソプロパノール：８００部
（３）アンモニア水（濃度：２８％）：３０部
（４）テトラエトキシシラン：１５部 (Example 3)
<Preparation of hollow silica particles>
75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.1 μm, solid content concentration: 2.5 mass%) was heated to 40 ° C., and the suspension was The following components (1) to (4) were blended with stirring, and further stirred for 30 minutes to prepare a mixed solution.
(1) Water: 155 parts (2) Isopropanol: 800 parts (3) Ammonia water (concentration: 28%): 30 parts (4) Tetraethoxysilane: 15 parts
　続いて、上記混合液を４０℃で１０時間静置した後、室温に戻した。その後、遠心分離により、生成した粒子を回収し、水に分散させた。上記遠心分離、粒子回収、水分散を２回繰り返し、フィルターでろ過した後、遠心分離により粒子を回収した。その後、回収した粒子を１００℃で５時間乾燥した後、得られた粉末を焼成炉に入れてエアフローしながら１℃／分の速度で５００℃まで昇温し、５００℃で３時間焼成した。更に、５℃／分の速度で９００℃まで昇温し、９００℃で３時間焼成した後、徐々に室温まで冷却し、中空シリカ粒子を得た。 Subsequently, the mixture was allowed to stand at 40 ° C. for 10 hours and then returned to room temperature. Thereafter, the produced particles were collected by centrifugation and dispersed in water. The above centrifugation, particle recovery, and water dispersion were repeated twice, and after filtration through a filter, the particles were recovered by centrifugation. Thereafter, the collected particles were dried at 100 ° C. for 5 hours, and then the obtained powder was put into a firing furnace, heated to 500 ° C. at a rate of 1 ° C./minute while airflowing, and fired at 500 ° C. for 3 hours. Furthermore, the temperature was raised to 900 ° C. at a rate of 5 ° C./minute, and after firing at 900 ° C. for 3 hours, the mixture was gradually cooled to room temperature to obtain hollow silica particles.
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：２９０部 <Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 290 parts
　次に、上記で作製した中空シリカ粒子：４５部と、溶剤（メチルエチルケトン）：２５５部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液３を得た。 Next, the hollow silica particles prepared above: 45 parts and the solvent (methyl ethyl ketone): 255 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water, whereby a coating liquid 3 was obtained.
　上記塗布液３を用い、塗膜厚さを２．５μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム３を作製した。 A projection film 3 was produced in the same manner as in Example 1 except that the coating solution 3 was used and the coating thickness was 2.5 μm.
　（実施例４）
　＜中空シリカ粒子の作製＞
　ポリスチレン粒子懸濁液（ポリサイエンス社製、アミノ基修飾、粒子の平均粒子径：０．２μｍ、固形分濃度：２．５質量％）７５部を用い、テトラエトキシシランの配合量を７部に変更した以外は、実施例３と同様にして中空シリカ粒子を作製した。 Example 4
<Preparation of hollow silica particles>
Using 75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 μm, solid content concentration: 2.5 mass%), the amount of tetraethoxysilane is 7 parts. Except for the change, hollow silica particles were produced in the same manner as in Example 3.
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：２９２部 <Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 292 parts
　次に、上記で作製した中空シリカ粒子：７．５部と、溶剤（メチルエチルケトン）：４２．５部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液４を得た。 Next, the hollow silica particles prepared above: 7.5 parts and the solvent (methyl ethyl ketone): 42.5 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water to obtain a coating liquid 4.
　上記塗布液４を用い、塗膜厚さを２．８μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム４を作製した。 A projection film 4 was produced in the same manner as in Example 1 except that the coating solution 4 was used and the coating thickness was 2.8 μm.
　（実施例５）
　＜中空シリカ粒子の作製＞
　ポリスチレン粒子懸濁液（ポリサイエンス社製、アミノ基修飾、粒子の平均粒子径：０．２μｍ、固形分濃度：２．５質量％）７５部を用い、水の配合量を４６５部に、イソプロパノールの配合量を２４００部に、アンモニア水の配合量を９０部に、テトラエトキシシランの配合量を４０部に、それぞれ変更した以外は、実施例３と同様にして中空シリカ粒子を作製した。 (Example 5)
<Preparation of hollow silica particles>
Using 75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 μm, solid content concentration: 2.5% by mass), the amount of water added to 465 parts, isopropanol The hollow silica particles were prepared in the same manner as in Example 3 except that the amount was 2400 parts, the amount of ammonia water was 90 parts, and the amount of tetraethoxysilane was 40 parts.
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：２９２部 <Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 292 parts
　次に、上記で作製した中空シリカ粒子：１５部と、溶剤（メチルエチルケトン）：８５部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液５を得た。 Next, the hollow silica particles prepared above: 15 parts and the solvent (methyl ethyl ketone): 85 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, the hollow silica particle suspension was blended into the mixed solution, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water to obtain a coating solution 5.
　上記塗布液５を用い、塗膜厚さを２．４μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム５を作製した。 A projection film 5 was produced in the same manner as in Example 1 except that the coating liquid 5 was used and the coating thickness was 2.4 μm.
　（比較例１）
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（ウレタンアクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＨＡ－４０Ｈ”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：６２０部 (Comparative Example 1)
<Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (urethane acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA-40H”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio) -phenyl ] -2-Morpholinpropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 620 parts
　次に、上記混合液に下記成分（４）を配合して攪拌・混合した後、更に容器を水冷しながら混合液に対し超音波分散処理を行い、最後に孔径２μｍのフィルターを通してろ過して塗布液６を得た。
（４）中実シリカ粒子のメチルエチルケトン溶液（日産化学工業社製、商品名“ＭＥＫ－ＳＴ－ＺＬ”、固形分濃度：３０質量％）：８３．３部 Next, the following component (4) is blended into the above mixture and stirred and mixed, and then the mixture is subjected to ultrasonic dispersion treatment while cooling the vessel with water, and finally filtered through a filter having a pore size of 2 μm. Liquid 6 was obtained.
(4) Methyl ethyl ketone solution of solid silica particles (manufactured by Nissan Chemical Industries, trade name “MEK-ST-ZL”, solid content concentration: 30% by mass): 83.3 parts
　＜投影用フィルムの作製＞
　厚さ１００μｍの環状オレフィン系樹脂フィルム（日本ゼオン社製、商品名“ゼオノアフィルム　ＺＦ１４－１００”、ガラス転移温度：１３６℃）の上に、バーコーターを用いて上記塗布液６を、塗膜厚さが０．２７μｍとなるよう塗布して乾燥した。次に、高圧水銀灯を用いて積算光量を２５０ｍＪ／ｃｍ2となるように紫外線を照射して上記塗膜の硬化処理を行い、上記フィルムの上に樹脂層を形成して投影用フィルム６を作製した。 <Production of projection film>
The coating liquid 6 is coated on a cyclic olefin-based resin film (trade name “ZEONOR FILM ZF14-100”, glass transition temperature: 136 ° C., manufactured by Nippon Zeon Co., Ltd.) using a bar coater. Was applied to a thickness of 0.27 μm and dried. Next, the coating film is cured by irradiating ultraviolet rays so that the integrated light quantity becomes 250 mJ / cm 2 using a high-pressure mercury lamp, and a resin layer is formed on the film to produce a projection film 6. did.
　（比較例２）
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：２９２部 (Comparative Example 2)
<Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 292 parts
　次に、実施例３で作製した中空シリカ粒子：８０部と、溶剤（メチルエチルケトン）：４５３部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液７を得た。 Next, the hollow silica particles prepared in Example 3: 80 parts and the solvent (methyl ethyl ketone): 453 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and then subjected to ultrasonic dispersion treatment while cooling the container with water, whereby a coating liquid 7 was obtained.
　上記塗布液７を用い、塗膜厚さを２．６μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム７を作製した。 A projection film 7 was produced in the same manner as in Example 1 except that the coating liquid 7 was used and the coating thickness was 2.6 μm.
　（比較例３）
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：２９２部 (Comparative Example 3)
<Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 292 parts
　次に、実施例３で作製した中空シリカ粒子：２．５部と、溶剤（メチルエチルケトン）：１５部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液８を得た。 Next, 2.5 parts of hollow silica particles prepared in Example 3 and 15 parts of solvent (methyl ethyl ketone) were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, the hollow silica particle suspension was blended into the mixed liquid, stirred and mixed, and further subjected to ultrasonic dispersion treatment while cooling the container with water, whereby a coating liquid 8 was obtained.
　上記塗布液８を用い、塗膜厚さを２．８μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム８を作製した。 A projection film 8 was produced in the same manner as in Example 1 except that the coating liquid 8 was used and the coating thickness was 2.8 μm.
　（比較例４）
　＜中空シリカ粒子の作製＞
　ポリスチレン粒子懸濁液（ポリサイエンス社製、アミノ基修飾、粒子の平均粒子径：０．２μｍ、固形分濃度：２．５質量％）７５部を用い、水の配合量を１５５０部に、イソプロパノールの配合量を８０００部に、アンモニア水の配合量を３００部に、テトラエトキシシランの配合量を１２５部に、それぞれ変更した以外は、実施例３と同様にして中空シリカ粒子を作製した。 (Comparative Example 4)
<Preparation of hollow silica particles>
Using 75 parts of a polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.2 μm, solid content concentration: 2.5 mass%), the amount of water is 1550 parts, and isopropanol is used. The hollow silica particles were prepared in the same manner as in Example 3 except that the amount was 8000 parts, the amount of ammonia water was 300 parts, and the amount of tetraethoxysilane was 125 parts.
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：２９０部 <Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 290 parts
　次に、上記で作製した中空シリカ粒子：５０部と、溶剤（メチルエチルケトン）：２８５部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液９を得た。 Next, the hollow silica particles prepared above: 50 parts and the solvent (methyl ethyl ketone): 285 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, the hollow silica particle suspension was blended with the mixed liquid, stirred and mixed, and then subjected to ultrasonic dispersion treatment while cooling the container with water to obtain a coating liquid 9.
　上記塗布液９を用い、塗膜厚さを２．４μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム９を作製した。 A projection film 9 was produced in the same manner as in Example 1 except that the coating liquid 9 was used and the coating thickness was 2.4 μm.
　（比較例５）
　ポリスチレン粒子懸濁液（ポリサイエンス社製、アミノ基修飾、粒子の平均粒子径：０．５μｍ、固形分濃度：２．５質量％）７５部を用い、テトラエトキシシランの配合量を６．０部に変更した以外は、実施例３と同様にして中空シリカ粒子を作製した。 (Comparative Example 5)
75 parts of polystyrene particle suspension (manufactured by Polysciences, amino group modification, average particle diameter of particles: 0.5 μm, solid content concentration: 2.5 mass%) is used, and the amount of tetraethoxysilane is 6.0. Hollow silica particles were produced in the same manner as in Example 3 except that the part was changed to the part.
　＜投影用フィルム作製用組成物（塗布液）の調製＞
　先ず、以下の成分（１）～（３）をステンレス鋼製容器に入れて攪拌・混合して混合液を調製した。
（１）重合性化合物（多官能アクリレート：日本化薬社製、商品名“ＫＡＹＡＲＡＤ　ＤＰＣＡ－６０”）：５０部
（２）光重合開始剤〔２－メチル－１－[４－(メチルチオ)－フェニル]－２－モルフォリノプロパン－１－オン〕：１．５部
（３）溶剤（メチルエチルケトン）：１９４部 <Preparation of a composition for producing a projection film (coating solution)>
First, the following components (1) to (3) were placed in a stainless steel container and stirred and mixed to prepare a mixed solution.
(1) Polymerizable compound (polyfunctional acrylate: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPCA-60”): 50 parts (2) Photopolymerization initiator [2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropan-1-one]: 1.5 parts (3) Solvent (methyl ethyl ketone): 194 parts
　次に、上記で作製した中空シリカ粒子：７．５部と、溶剤（メチルエチルケトン）：４２．５部とを十分に攪拌・混合して、中空シリカ粒子懸濁液を作製した。次に、上記混合液に上記中空シリカ粒子懸濁液を配合して攪拌・混合した後、更に容器を水冷しながら超音波分散処理を行い、塗布液１０を得た。 Next, the hollow silica particles prepared above: 7.5 parts and the solvent (methyl ethyl ketone): 42.5 parts were sufficiently stirred and mixed to prepare a hollow silica particle suspension. Next, after the hollow silica particle suspension was blended with the mixed solution and stirred and mixed, ultrasonic dispersion treatment was further performed while the container was cooled with water to obtain a coating solution 10.
　上記塗布液１０を用い、塗膜厚さを０．７８μｍとなるように塗布した以外は、実施例１と同様にして投影用フィルム１０を作製した。 A projection film 10 was produced in the same manner as in Example 1 except that the coating solution 10 was used and the coating thickness was 0.78 μm.
　（比較例６）
　ＰＥＴフィルムに代えて、厚さ１００μｍの環状オレフィン系樹脂フィルム（日本ゼオン社製、商品名“ゼオノアフィルム　ＺＦ１４－１００”、ガラス転移温度：１３６℃）を用い、実施例１で作製した塗布液１を用いた以外は、実施例１と同様にして投影用フィルム１１を作製した。 (Comparative Example 6)
A coating solution 1 prepared in Example 1 using a 100 μm-thick cyclic olefin resin film (manufactured by Zeon Corporation, trade name “Zeonor film ZF14-100”, glass transition temperature: 136 ° C.) instead of the PET film. A projection film 11 was produced in the same manner as in Example 1 except that was used.
　（参考例）
　実施例１で用いたＰＥＴフィルムのみを投影用フィルムとして用いた。即ち、投影用フィルムには、樹脂層を設けていない。 (Reference example)
Only the PET film used in Example 1 was used as the projection film. That is, the resin film is not provided on the projection film.
　次に、実施例１～５及び比較例１～６で作製した投影用フィルムを用いて下記特性を評価した。 Next, the following characteristics were evaluated using the projection films produced in Examples 1 to 5 and Comparative Examples 1 to 6.
　＜耐引き裂き性＞
　先ず、投影用フィルムの端面を両手の親指と人差し指でつまむように、親指同士、人差し指同士が接触する位置で保持した。次に、両手を逆方向にひねるようにして投影用フィルムを引き裂いた。その結果、フィルムが切れなかった場合を耐引き裂き性が良好と判断し、フィルムが切れた場合を耐引き裂き性が不良と判断した。 <Tear resistance>
First, the end surfaces of the projection film were held at positions where the thumbs and the index fingers contact each other so that the thumbs and index fingers of both hands pinch. Next, the projection film was torn by twisting both hands in the opposite direction. As a result, the tear resistance was judged to be good when the film was not cut, and the tear resistance was judged to be poor when the film was cut.
　＜中空シリカ粒子の平均粒子径及び空隙率＞
　参考例を除き、作製した投影用フィルムを断面加工したサンプルを作製し、そのサンプルをＳＥＭ観察し、中空シリカ粒子２０個の１次粒子の粒子径及び殻壁の厚さを測定して算術平均することにより、中空シリカ粒子の平均粒子径と殻壁の平均厚さを求め、これらの値から、前述の式（１）から中空シリカ粒子の空隙率を求めた。 <Average particle diameter and porosity of hollow silica particles>
Except for reference examples, a sample obtained by processing a cross section of the produced projection film was prepared, the sample was observed with an SEM, and the primary particle diameter of 20 hollow silica particles and the thickness of the shell wall were measured to obtain an arithmetic average. By doing this, the average particle diameter of hollow silica particles and the average thickness of the shell wall were determined, and from these values, the porosity of the hollow silica particles was determined from the above formula (1).
　続いて、実施例１～５、比較例１～６及び参考例で作製した投影用フィルムを、縦５０ｍｍ、横５０ｍｍ、厚さ３ｍｍのフロートガラス板に、樹脂層を外側にして貼り付け、評価用サンプルとした。上記貼り付けには、厚さ２０μｍの基材レスの光学用粘着テープ（日立マクセル社製、“高透明基材レス両面テープＮｏ.５０７５”）を用いた。上記評価用サンプルの特性を下記のように評価した。 Subsequently, the projection films produced in Examples 1 to 5, Comparative Examples 1 to 6 and Reference Example were attached to a float glass plate having a length of 50 mm, a width of 50 mm, and a thickness of 3 mm, with the resin layer facing outside, and evaluated. A sample was used. For the attachment, a 20 μm-thick substrate-less optical adhesive tape (manufactured by Hitachi Maxell, “highly transparent substrate-less double-sided tape No. 5075”) was used. The characteristics of the evaluation samples were evaluated as follows.
　＜耐擦傷性＞
　評価用サンプルの投影用フィルム側をスキージで３回擦り、傷の有無を確認した。その結果、傷が２本以下の場合を耐擦傷性が良好と判断し、傷が３本以上の場合を耐擦傷性が不良と判断した。 <Abrasion resistance>
The projection film side of the sample for evaluation was rubbed with a squeegee three times to check for scratches. As a result, when the number of scratches was 2 or less, the scratch resistance was judged to be good, and when the number of scratches was 3 or more, the scratch resistance was judged to be poor.
　＜全光線透過率及びヘイズ＞
　評価用サンプルを、日本電色工業社製の濁度計“ＮＤＨ２０００”を用い、日本工業規格（ＪＩＳ）Ｋ７３６１－１に対応した方法で全光線透過率及びヘイズを測定した。 <Total light transmittance and haze>
The sample for evaluation was measured for total light transmittance and haze by a method corresponding to Japanese Industrial Standard (JIS) K7361-1, using a turbidimeter “NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.
　＜透視性＞
　また、実施例１～５、比較例１～６及び参考例で作製した投影用フィルムを、縦１５０ｍｍ、横１５０ｍｍ、厚さ２ｍｍのガラス板に、光学用粘着フィルム（厚さ：２５μｍ）を用いて、樹脂層を外側にして貼り付け、評価用サンプルとした。その評価用サンプルを垂直に立て、ガラス板のフィルム貼付面から１５ｃｍ離れた位置に花瓶を置き、ガラス板のガラス面側から花瓶を観察した。その際、花瓶がすっきり確認できた場合を透視性が良好と判断し、花瓶がかすんで確認された場合を透視性が不良と判断した。 <Transparency>
In addition, the projection films produced in Examples 1 to 5, Comparative Examples 1 to 6 and Reference Example were used on an optical adhesive film (thickness: 25 μm) on a glass plate having a length of 150 mm, a width of 150 mm and a thickness of 2 mm. Then, the resin layer was attached to the outside to prepare a sample for evaluation. The sample for evaluation was set up vertically, a vase was placed at a position 15 cm away from the film application surface of the glass plate, and the vase was observed from the glass surface side of the glass plate. At that time, the case where the vase was clearly confirmed was judged as having good transparency, and the case where the vase was confirmed as being hazy was judged as having poor transparency.
　以上の結果を表１及び表２に示す。また、表１には、用いた中空シリカ粒子の含有量、種類及び塗膜厚さも示した。 The results are shown in Tables 1 and 2. Table 1 also shows the content, type and coating thickness of the hollow silica particles used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び表２から、実施例１～５では、投影用フィルムの樹脂層において、平均粒子径が３０～５００ｎｍで、空隙率が２０～９５体積％の中空粒子を用い、上記中空粒子の添加量を上記樹脂１００質量部に対して１０～１５０質量部としたので、作製した評価用サンプルの全光線透過率は９２％以上となり、ヘイズは１５％未満となり、視認性が良好で、透視性が良好な投影用フィルムが得られた。また、実施例１～５では、投影用フィルムの基材にＰＥＴフィルムを用いたので、耐引き裂き性が良好となり、塗膜厚さ（樹脂層厚さ）を中空粒子の平均粒子径の２倍以上としたので、耐擦傷性が良好となった。 From Tables 1 and 2, in Examples 1 to 5, in the resin layer of the projection film, hollow particles having an average particle diameter of 30 to 500 nm and a porosity of 20 to 95% by volume are used. Since the amount was 10 to 150 parts by mass with respect to 100 parts by mass of the resin, the total light transmittance of the prepared evaluation sample was 92% or more, the haze was less than 15%, the visibility was good, and the transparency was good. Was obtained. In Examples 1 to 5, since a PET film was used as the substrate for the projection film, the tear resistance was good, and the coating thickness (resin layer thickness) was twice the average particle diameter of the hollow particles. As described above, the scratch resistance was good.
　一方、比較例１は、基材に環状オレフィン系樹脂フィルムを用いたので、耐引き裂き性が劣り、また、中実粒子を用いたので、実施例１～５に比べて全光線透過率が低下した。比較例２は、中空粒子の添加量が１５０質量部を超えたので、耐擦傷性が劣った。比較例３は、中空粒子の添加量が１０質量部を下回ったため、実施例１～５に比べて全光線透過率が低下した。比較例４は、中空粒子の空隙率が２０体積％を下回ったため、実施例１～５に比べて全光線透過率が低下した。比較例５は、中空粒子の平均粒子径が５００ｎｍを超えたため、全光線透過率が低下し、塗膜厚さが中空粒子の２倍を下回ったため、耐擦傷性が劣った。更に、比較例５で用いた中空粒子の平均粒子径は５６２ｎｍと他の粒子に比較し大きいので、ヘイズ値が高くなり、透視性が劣った。比較例６は、投影用フィルムの基材に、ガラス転移温度が９５℃を超える環状オレフィン系樹脂フィルムを用いたので、耐引き裂き性が劣った。 On the other hand, Comparative Example 1 uses a cyclic olefin-based resin film as a base material, so that the tear resistance is inferior, and since solid particles are used, the total light transmittance is reduced as compared with Examples 1-5. did. Comparative Example 2 was inferior in scratch resistance because the amount of hollow particles added exceeded 150 parts by mass. In Comparative Example 3, since the amount of hollow particles added was less than 10 parts by mass, the total light transmittance was reduced as compared with Examples 1-5. In Comparative Example 4, since the porosity of the hollow particles was less than 20% by volume, the total light transmittance was lower than in Examples 1-5. In Comparative Example 5, since the average particle diameter of the hollow particles exceeded 500 nm, the total light transmittance was lowered, and the coating thickness was less than twice that of the hollow particles, so that the scratch resistance was inferior. Furthermore, since the average particle diameter of the hollow particles used in Comparative Example 5 was 562 nm, which was larger than other particles, the haze value was high and the transparency was poor. In Comparative Example 6, since a cyclic olefin-based resin film having a glass transition temperature exceeding 95 ° C. was used as the base material of the projection film, the tear resistance was inferior.
　本発明は、その趣旨を逸脱しない範囲で、上記以外の形態としても実施が可能である。本出願に開示された実施形態は一例であって、これらに限定はされない。本発明の範囲は、上述の明細書の記載よりも、添付されている請求の範囲の記載を優先して解釈され、請求の範囲と均等の範囲内での全ての変更は、請求の範囲に含まれるものである。 The present invention can be implemented in forms other than those described above without departing from the spirit of the present invention. The embodiments disclosed in the present application are merely examples, and the present invention is not limited thereto. The scope of the present invention is construed in preference to the description of the appended claims rather than the description of the above specification, and all modifications within the scope equivalent to the claims are construed in the scope of the claims. It is included.
　本発明は、耐引き裂き性、耐擦傷性及び光学特性に優れた投影用フィルムを提供でき、視認性及び透視性に優れた投影用スクリーンを実現でき、各種プロジェクターのスクリーンとして対応できる。 The present invention can provide a projection film excellent in tear resistance, scratch resistance and optical properties, can realize a projection screen excellent in visibility and transparency, and can be used as a screen for various projectors.
１０　投影用スクリーン
１１　投影用フィルム
１１ａ　樹脂フィルム
１１ｂ　樹脂層
１２　透明基板
１３　超短焦点プロジェクター
１３ａ　投影方向
１４　視認方向 DESCRIPTION OF SYMBOLS 10 Projection screen 11 Projection film 11a Resin film 11b Resin layer 12 Transparent substrate 13 Ultra-short focus projector 13a Projection direction 14 Viewing direction

Claims (13)

  1. 　中空粒子と、重合性化合物と、溶剤とを含む投影用フィルム作製用組成物であって、
    　前記中空粒子の１次粒子の平均粒子径が、３０ｎｍ以上５００ｎｍ以下であり、
    　前記中空粒子の空隙率が、２０体積％以上９５体積％以下であり、
    　前記中空粒子の含有量が、前記中空粒子以外の、前記重合性化合物を含む固形成分１００質量部に対して、１０質量部以上１５０質量部以下であることを特徴とする投影用フィルム作製用組成物。     A composition for producing a projection film comprising hollow particles, a polymerizable compound, and a solvent,
    The average particle diameter of the primary particles of the hollow particles is 30 nm or more and 500 nm or less,
    The porosity of the hollow particles is 20% by volume or more and 95% by volume or less,
    The composition for producing a projection film, wherein the content of the hollow particles is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the solid component containing the polymerizable compound other than the hollow particles. object.
  2. 　前記中空粒子が、中空シリカ粒子である請求項１に記載の投影用フィルム作製用組成物。 The composition for producing a projection film according to claim 1, wherein the hollow particles are hollow silica particles.
  3. 　前記重合性化合物が、重合性オリゴマーを含む請求項１又は２に記載の投影用フィルム作製用組成物。 The composition for producing a projection film according to claim 1 or 2, wherein the polymerizable compound contains a polymerizable oligomer.
  4. 　前記重合性オリゴマーが、ウレタンアクリレート、ポリエーテルアクリレート及びポリエステルアクリレートからなる群から選ばれる少なくとも一種である請求項３に記載の投影用フィルム作製用組成物。 The composition for producing a projection film according to claim 3, wherein the polymerizable oligomer is at least one selected from the group consisting of urethane acrylate, polyether acrylate and polyester acrylate.
  5. 　光重合開始剤を更に含む請求項１～４のいずれか１項に記載の投影用フィルム作製用組成物。 The composition for producing a projection film according to any one of claims 1 to 4, further comprising a photopolymerization initiator.
  6. 　基材の少なくとも一方の面に樹脂層を有する投影用フィルムであって、
    　前記基材は、ガラス転移温度が９５℃以下の樹脂フィルムからなり、
    　前記樹脂層は、中空粒子と、樹脂とを含み、
    　前記中空粒子の１次粒子の平均粒子径が、３０ｎｍ以上５００ｎｍ以下であり、
    　前記中空粒子の空隙率が、２０体積％以上９５体積％以下であり、
    　前記中空粒子の含有量が、前記樹脂１００質量部に対して、１０質量部以上１５０質量部以下であり、
    　前記樹脂層の厚さが、前記中空粒子の平均粒子径の２倍以上であることを特徴とする投影用フィルム。     A projection film having a resin layer on at least one surface of a substrate,
    The substrate consists of a resin film having a glass transition temperature of 95 ° C. or less,
    The resin layer includes hollow particles and a resin,
    The average particle diameter of the primary particles of the hollow particles is 30 nm or more and 500 nm or less,
    The porosity of the hollow particles is 20% by volume or more and 95% by volume or less,
    The content of the hollow particles is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin.
    A film for projection, wherein the resin layer has a thickness of at least twice the average particle diameter of the hollow particles.
  7. 　前記中空粒子が、中空シリカ粒子である請求項６に記載の投影用フィルム。 The projection film according to claim 6, wherein the hollow particles are hollow silica particles.
  8. 　前記樹脂が、ポリウレタン系樹脂、ポリエーテル系樹脂及びポリエステル系樹脂からなる群から選ばれる少なくとも一種である請求項６又は７に記載の投影用フィルム。 The projection film according to claim 6 or 7, wherein the resin is at least one selected from the group consisting of a polyurethane resin, a polyether resin, and a polyester resin.
  9. 　ヘイズが１５％未満である請求項６～８のいずれか1項に記載の投影用フィルム。 The projection film according to any one of claims 6 to 8, wherein the haze is less than 15%.
  10. 　部材と、前記部材に貼付した投影用フィルムとを含む投影用スクリーンであって、
    　前記投影用フィルムが、請求項６～９のいずれか１項に記載の投影用フィルムであることを特徴とする投影用スクリーン。     A projection screen comprising a member and a projection film affixed to the member,
    The projection screen according to any one of claims 6 to 9, wherein the projection film is the projection film according to any one of claims 6 to 9.
  11. 　前記部材と前記投影用フィルムとは、粘着剤により貼り合わせられている請求項１０に記載の投影用スクリーン。 The projection screen according to claim 10, wherein the member and the projection film are bonded together with an adhesive.
  12. 　前記部材が、ガラス基板、ガラスシート、樹脂基板及び樹脂シートからなる群から選ばれる少なくとも一種である請求項１０又は１１に記載の投影用スクリーン。 The projection screen according to claim 10 or 11, wherein the member is at least one selected from the group consisting of a glass substrate, a glass sheet, a resin substrate, and a resin sheet.
  13. 　前記投影用フィルムの前記樹脂層が、最表層に配置されている請求項１０～１２のいずれか１項に記載の投影用スクリーン。


    　                                                                                             The projection screen according to any one of claims 10 to 12, wherein the resin layer of the projection film is disposed on an outermost layer.


PCT/JP2017/009978 2017-03-13 2017-03-13 Composition for forming film for projection, film for projection, and screen for projection WO2018167823A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008250345A (en) * 2001-04-06 2008-10-16 Three M Innovative Properties Co Information providing method using projection screen
JP4847329B2 (en) * 2004-08-10 2011-12-28 株式会社きもと Transmission screen
JP2012212092A (en) * 2011-03-24 2012-11-01 Mitsubishi Paper Mills Ltd Transmission type transparent screen and manufacturing method thereof
JP2015232630A (en) * 2014-06-10 2015-12-24 平岡織染株式会社 Transmission projection screen
JP2015232629A (en) * 2014-06-10 2015-12-24 平岡織染株式会社 Transmission projection screen
JP2016018195A (en) * 2014-07-11 2016-02-01 旭硝子株式会社 Picture display system and picture display method
JP2016109778A (en) * 2014-12-03 2016-06-20 旭硝子株式会社 Light-transmissive transparent screen, and system and method for displaying image

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008250345A (en) * 2001-04-06 2008-10-16 Three M Innovative Properties Co Information providing method using projection screen
JP4847329B2 (en) * 2004-08-10 2011-12-28 株式会社きもと Transmission screen
JP2012212092A (en) * 2011-03-24 2012-11-01 Mitsubishi Paper Mills Ltd Transmission type transparent screen and manufacturing method thereof
JP2015232630A (en) * 2014-06-10 2015-12-24 平岡織染株式会社 Transmission projection screen
JP2015232629A (en) * 2014-06-10 2015-12-24 平岡織染株式会社 Transmission projection screen
JP2016018195A (en) * 2014-07-11 2016-02-01 旭硝子株式会社 Picture display system and picture display method
JP2016109778A (en) * 2014-12-03 2016-06-20 旭硝子株式会社 Light-transmissive transparent screen, and system and method for displaying image

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