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WO1995031737A1 - Film anti-reflechissant - Google Patents

Film anti-reflechissant Download PDF

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Publication number
WO1995031737A1
WO1995031737A1 PCT/JP1995/000955 JP9500955W WO9531737A1 WO 1995031737 A1 WO1995031737 A1 WO 1995031737A1 JP 9500955 W JP9500955 W JP 9500955W WO 9531737 A1 WO9531737 A1 WO 9531737A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
ionizing radiation
resin
curable resin
glare
Prior art date
Application number
PCT/JP1995/000955
Other languages
English (en)
Japanese (ja)
Inventor
Nobuyuki Tomizawa
Masahumi Shimizu
Yugo Noritake
Toru Sakamoto
Norinaga Nakamura
Original Assignee
Dai Nippon Printing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Nippon Printing Co., Ltd. filed Critical Dai Nippon Printing Co., Ltd.
Publication of WO1995031737A1 publication Critical patent/WO1995031737A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0215—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having a regular structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H01J29/89—Optical or photographic arrangements structurally combined or co-operating with the vessel
    • H01J29/896—Anti-reflection means, e.g. eliminating glare due to ambient light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/003—Reflective

Definitions

  • the present invention relates to a liquid crystal display, such as various displays such as a warp, a computer, a television, an in-vehicle instrument panel, and the like.
  • the finolem used on the surface of the display is located on the outermost surface of the display, so it can be touched directly by hand or sprayed with synthetic detergent. First, they may be wiped with various chemicals or exposed to sunlight, so the base finolem may have scratch resistance, chemical resistance, weather resistance, etc. Certain codes are applied to grant. In addition, in order to make the screen displayed on the display easier to see, it is necessary to satisfy the antiglare properties and other required performances as follows. Various types of processing or processing are being performed.
  • a concave-convex shape is formed on the surface or a matting agent is applied to a hard coat. It is known that an anti-glare effect is imparted by being mixed. With these methods, it is possible to reduce the glossiness by 60 degrees by increasing the haze. However, on the contrary, this method has a strong effect of lowering the total light transmittance and the screen resolution.
  • the present invention provides a method for displaying images on a display surface without observing dazzling, displaying displayed characters and other images at a high resolution.
  • the purpose is to provide an anti-glare film that also makes the trust clear.
  • an anti-glare film according to the present invention comprises a transparent film and an all-optical line provided on the transparent film. It has an optical characteristic of a transmittance of 85% or more, a haze of 3.0 to 35%, a gloss of 60 degrees and a gloss of 90% or less, and a surface center line average roughness of 0.05. 00.6 iz m, characterized in that the surface is formed from an ionizing radiation curable resin layer having a surface roughness of 5 to 200 m.
  • FIG. 1 is a schematic sectional view showing an embodiment of the present invention.
  • FIG. 2 is a conceptual diagram showing the reflection and transmission of light with respect to the antiglare film of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing an example of a case where the anti-glare film of the present invention is manufactured.
  • FIG. 4A is a schematic cross-sectional view showing an example of the film base material that has been matted.
  • FIG. 4B is a cross-sectional view of a shaped film obtained by applying resin to a shaped film base material.
  • FIG. 5 is an explanatory diagram showing a process in the case of manufacturing an anti-glare film.
  • FIG. 5A is a cross-sectional view of a shaped film obtained by applying a resin to a shaped film substrate.
  • FIG. 5B is a cross-sectional view of a laminated film in which an ionizing radiation-curable resin before curing is formed on an antiglare film substrate.
  • FIG. 5C is a cross-sectional view of a laminated sheet obtained by laminating the shaped film of FIG. 5A on the laminated film of FIG. 5B.
  • Fig. 5D shows the laminated film of Fig. 5C irradiated with ionizing radiation to cure the ionizing radiation-curable resin layer and then exfoliated when the molded film was peeled off. Sectional view of the glare film.
  • FIG. 6A is a cross-sectional view of a molding film coated with a resin to which fine silica particles are added.
  • Figure 6B was made using the shaped film of Figure 6A Sectional view of the anti-glare film.
  • FIG. 7 is a diagram showing an example of a coating apparatus used for applying the ionizing radiation-curable resin composition.
  • FIGS. 8 and 9 are cross-sectional views of a polarizing plate to which the anti-glare film of the present invention is applied.
  • FIGS. 10 to 11 are cross-sectional views each showing a specific example of a polarizing plate to which a moisture-proof sheet is applied.
  • FIGS. 12A to 12D are cross-sectional views each showing a specific example of a liquid crystal cell to which the polarizing plate of the present invention is applied.
  • the anti-glare film according to the present invention comprises a transparent film and a total light transmitting film provided on the transparent film. It has optical characteristics of 85% or more, haze of 3.0 to 35%, and 60% of gloss of 90% or less, and has a surface centerline average roughness of 0.05 to 0.5%. pitch between 6 beta m N surface unevenness that features a 5 to 2 0 0 ⁇ Table roughness der Ru this ionizing radiation-curable resin layer or et ing of um.
  • the total light transmittance is 85% or more, practically And found that it can be used without any problems.
  • the haze is required to be in the range of 3.0 to 35% to obtain a good screen. If the haze exceeds the upper limit of the above range, the display screen looks whitish, whereas if the haze is less than the lower limit, the gloss increases and the anti-glare effect does not exist. You Decrease.
  • the 60-degree gloss is a value defined by the reflection of light incident on the screen from the outside.If the value exceeds 90%, the glare will increase.
  • the numerical range of the pitch between the surface irregularities and the surface roughness, which does not conform to the purpose of the present invention, is the above-mentioned total light transmittance, haze degree and 60 degrees. This is a necessary condition in the present invention for obtaining appropriate physical properties of glossiness.
  • the above 60 degree glossiness can be measured based on the method specified in JISZ8741, and as shown in Fig. 2, the angle of incidence on the uneven surface 2 is as shown in Fig. 2.
  • the light P 0 is applied at 60 degrees, and the light receiving rate of the reflected light P 1 is a value expressed in%.
  • the total light transmittance can be measured based on the method specified in JISK 6714, and as shown in Fig. 2, the reflected light Q0 This is a value in which the light reception rate of the light Q 1 transmitted through the light is expressed in%.
  • the surface center average roughness is set to 0. It is preferable to control in the range of .05 to .4 // m, and more preferably in the range of .05 to .25.
  • the term "high-definition”, also the number of pixels per unit area equivalent Ri is increased, you can, for example, diagonal 2 6 cm Roh, and have you to-zero value zone Les, 6 4 0 X A pixel whose 480 pixels have been further increased to 800 000 pixels.
  • a transparent film for example, a polarizing plate is mainly used.
  • TAC triacetyl cellulose film
  • TAC triacetyl cellulose film
  • other known transparent plastic films are also used. It can be used by appropriately selecting from the film.
  • the transparent plastic film include the following. Polyester film, Polyethylene film, Polypropylene film, Polyvinyl chloride film, Assay Polyethylene film, Polystyrene film, Polycarbonate film Polymetal film Innolem, Polyphonic Innolem, etc.
  • an acrylurethane-based ionizing radiation-curable resin or the like is widely used as the resin for forming the hard coat layer. Select a resin that has the property of being cured by UV * EB and adheres to the TAC, and is durable.
  • the light diffuser used is 0.5 to 5 / m silica beads. Norwegian is mainly used.
  • all of the light diffusing agent imparts an optical function to the light diffusing agent. In some cases, glare may occur, and in order to prevent this, it is desirable to mix the light diffusing agent to such an extent that coating aptitude is not lost.
  • the light diffusing agent is ionized radiation-curable resin When kneading to a fat, the light diffusing agent is kneaded in an organic resin to coat the surface of the light diffusing agent, thereby ensuring transparency and ensuring wettability. I do .
  • the light diffusing agent that has been subjected to the organic coating treatment is dispersed in the ionizing radiation-curable resin, and its content is relative to 120 parts of the ionizing radiation-curable resin.
  • the light diffusing agent is 10 parts by weight or less.
  • this light diffusing agent exhibits good properties is effective in limiting its particle size, and it is effective for organic coating silica.
  • the beads having a particle size of 0.5 to 5 m showed an excellent effect.
  • the ionizing radiation-curable resin used is not particularly limited as long as it is a resin that is hardened by ionizing radiation, which is so-called UV * EB or the like. It is not something that will be done.
  • UV-curable resins used with photosensitizers include UV-curable acrylic resin and UV-curable polyester clear. Resin, ultraviolet curable epoxy resin, etc.
  • UV-curable acrylic urethane-based resin can be used in a polystyrene polyol with an isolated mono- or pre-polymer. The resulting product is reacted with an acrylic or metadarylate-based monomer having a hydroxyl group. Is obtained.
  • the photopolymerization initiator include a benzophenone derivative, an acetate pentanone derivative, An anthraquinone derivative or the like can be used alone or in combination.
  • a component that further improves the film formation for example, an acrylic resin may be appropriately selected and combined.
  • a viscosity modifier, a solvent, etc. are blended to make a coating liquid.
  • the coating of the ionizing radiation-curable resin for forming a film of the liquid composition containing the ionizing radiation-curable resin as a main component on a base film as described above.
  • General means such as roll coating, lean coating, gravure coating, and slot-relief coating are used as the means of coating.
  • it can be implemented c
  • Co over DOO amount of the coating amount after removal of the solvent 1 ⁇ 2 0 g / m 2, good or to rather is Ru Ah in 5 ⁇ 1 5 g Z m 2 .
  • the coating After coating the transparent film with the coating liquid containing ionizing radiation-curable resin as a main component and drying the solvent, the coating has flexibility and at least one side thereof.
  • the imprint film with fine irregularities is placed on the dried coat surface, the concave and convex surfaces are superimposed, and the transparent film is passed through the imprint film or the imprint film.
  • the shaping film After irradiating ultraviolet rays through the film to cure the ionizing radiation-curable resin, the shaping film is peeled off, and the concavities and convexities are transferred to the surface of the coating layer. .
  • the above coating liquid is applied to the concave and convex surfaces of the shaping film.
  • the transparent film is overlaid, and the ultraviolet curing and the exfoliation of the molding film are performed in the same manner as described above.
  • the performance of the film thus obtained as a scratch-resistant and anti-glare film is within the range of the following physical property values, and is extremely high in practical use. It is useful.
  • an anti-reflection layer made of a metal compound is further formed on the surface of the ionizing radiation-curable resin layer, whereby the anti-glare film is formed.
  • the optical properties can be further improved. Is the Yo will Do the anti-reflection layer of this, was example, if, A 1 o 0 3, Z n 0 0 All good beauty M g F o, etc. obtained deposited layer Re et al. Have use of metallic compound of .
  • An anti-reflection layer can also be provided by sequentially providing a vapor deposition layer of an Angstrom.
  • the surface of the imprinted film is made to have a desired unevenness by coating the resin more on the imprinted film.
  • the shape makes it possible to obtain an anti-glare finole with low haze loss, high anti-glare effect, and excellent scratch and chemical resistance. Wear .
  • a resin is applied to a matt film having an uneven shape on the film surface, and the film surface is formed into a desired uneven shape.
  • An improved shaped film is formed on the base material film, and the ionizing radiation-curable resin layer formed on the base film is formed into an irregular shape by using the shaped film.
  • An irregular shape is formed on the film surface.
  • a resin is applied to a matted film having an uneven shape on the film surface, and the film surface is formed into a desired uneven shape.
  • the shaping film is laminated on the surface of the substrate film coated with the ionizing radiation-curable resin, which is coated with the ionizing radiation-curable resin, and the shaping of the laminated film is performed.
  • the ionizing radiation curable resin is cured by irradiating ionizing radiation from the sheet side or the base material side, the shaping film is peeled off, and the prescribed anti-glare film is removed. Can be obtained.
  • the shaped film coated with the resin is applied to a matteich film by a transparent resin or a particle size.
  • L 0 // m is a shaped film formed by coating a resin to which fine particles of m are added to form an uneven shape, and the ionizing radiation curable resin is made of ultraviolet light. It is a curable resin, and the ionizing radiation may be ultraviolet light.
  • the surface roughness of the shaped film is preferably center line average roughness (R a) of 0.1 to: L 0 m.
  • the surface of the imprinted film can be formed in a desired manner by coating the resin on the matted imprinted film base material further.
  • the anti-glare film has a low haze and dross, a high anti-glare effect, and excellent abrasion resistance and chemical resistance. It can be manufactured.
  • FIG. 3 is a schematic cross-sectional view showing an example of an anti-glare film manufactured by using a shaped film.
  • FIG. 4A is a cross-sectional view of the matted shaped film base material
  • FIG. 4B is a cross-sectional view of the matted shaped film base material.
  • FIG. 3 is a cross-sectional view of a molding film provided with a resin layer.
  • Figures 5A to 5D are explanatory diagrams when manufacturing an anti-glare film using a shaped film provided with a coating resin layer.
  • FIG. 6A is a cross-sectional view of a molded film formed by coating a resin obtained by adding a fine screw to a matted molded film substrate.
  • FIG. 6B is a cross-sectional view of an anti-glare film produced using the shaped film of FIG. 6A.
  • a film such as a polyethylene terephthalate (hereinafter referred to as PET) film is used.
  • embossing, sand blur An uneven shape is formed by a method such as a stroking method, and a matted shaped film base material is produced.
  • thermosetting resin or an ionizing radiation-curable resin is coated on the uneven surface of the molded film substrate 11. Then, the coating resin layer 12 is formed, and the roughness of the uneven shape is adjusted to obtain a shaped film 20 having a desired surface roughness.
  • a tri-acetyl cellulose film is used as the base material 14 of the anti-glare film.
  • a film that is transparent, heat-resistant, and dimensionally stable such as a film
  • an ionizing radiation-curable resin is coated on this shaped film substrate 14.
  • an ionizing radiation-curable resin layer 13a before curing is formed.
  • the uneven surface of the shaped film 20 is superimposed on the ionizing radiation-curable resin layer 13 a before the film is cured, as shown in FIG. 5C.
  • an uneven shape is formed on the ionizing radiation-curable resin layer.
  • the ionizing radiation is irradiated from the imprint film side of the laminated sheet to cure the ionizing radiation-curable resin layer.
  • the imprint film is peeled off from the laminated sheet to form irregularities on the surface of the base film.
  • An anti-glare film 10 is manufactured.
  • Curing the ionizing radiation-curable resin with ionizing radiation it is also possible to irradiate with ionizing radiation from the opposite side of the shaping film to cause the film to harden.
  • ultraviolet rays when ultraviolet rays are used as ionizing radiation, ultraviolet rays are irradiated from the side of the shaping film to cure the ultraviolet-curable resin, and then the shaping film is peeled off. In some cases, the anti-glare film is irradiated with ultraviolet rays again to increase the crosslink density, thereby improving solvent resistance and abrasion resistance.
  • a resin obtained by adding fine particles having a particle size of 0.5 to: L 0 // m to a matted shaped film base material when forming a shaped film, a resin obtained by adding fine particles having a particle size of 0.5 to: L 0 // m to a matted shaped film base material. Then, a shaped film as shown in FIG. 6A was produced, and an anti-glare film was produced by using the film, as shown in FIG. 6B. An anti-glare film with a high anti-glare effect can be obtained.
  • the substrate film used in the above-mentioned imprinting film only needs to have dimensional stability and heat resistance and transmit ionizing radiation. Since ultraviolet light such as a high-pressure mercury lamp is often used as ionizing radiation, a transparent PET film can be preferably used as a substrate finolem. Thicknesses of 10 to 200 // m can be used, but the thickness may be 2 in consideration of fabrication, reuse, cost, etc. of the shaped film. About 5 m is desirable. However, when an electron beam is used as the ionizing radiation, the film only needs to be a film that transmits the electron beam and does not need to be transparent.
  • thermosetting resin or an ionizing radiation-curable resin is generally used, but the ionizing resin applied to the surface of the anti-glare film is generally used.
  • the radiation-curable resin can be used as long as it can form a predetermined concave and convex shape in the ionizing radiation-curable resin layer without softening or swelling. It is not particularly limited. Even thermoplastic resins can be used depending on the combination with the type of ionizing radiation curable resin.
  • the thermosetting resin to be coated on the shaped film includes phenol resin, urea resin, diaryl phthalate resin, and melamine resin.
  • Resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalgide resin, and melamine-urea There are condensed resin, silicon resin, polysiloxane resin, cellulose acetate propionate, etc., and if necessary, additives such as crosslinking agent, polymerization initiator, etc. , A curing agent, a polymerization accelerator, a solvent, a viscosity modifier, an extender, and the like.
  • isocyanate is generally used for unsaturated polyester resin or polyester resin, and methyl alkyl ketone is used. Peroxides, such as peroxides, and radical initiators, such as azoisobutyronitrile, are commonly used in unsaturated polyesters. . Further, as the isocyanate as a curing agent, a divalent or higher valent aliphatic or aromatic isocyanate can be used. An ionizing radiation curable resin is also used as the coating resin. However, since the ionizing radiation curable resin is also used for manufacturing an anti-glare film, the anti-glare resin is used. This is described in detail in the section on films.
  • the base film used for the anti-glare film may be transparent, has dimensional stability and heat resistance, and is capable of transmitting ionizing radiation.
  • display devices such as LCD, CRT, LED, etc.
  • a large number of triacetinolose cellulose films are used.
  • ultraviolet rays such as a high-pressure mercury lamp are often used as ionizing radiation. Films are used, but when the ionizing radiation-curable resin layer is cured by irradiating it with ultraviolet light only from the side of the forming film, it is not necessary to transmit ultraviolet light. Absent.
  • Thicknesses of 10 to 200 m can be used, but considering workability and cost, about 80 m is desirable.
  • an ultraviolet-curable resin or an electron beam-curable resin is usually used as the ionizing radiation-curable resin that forms a concave-convex shape on the surface of the anti-glare film.
  • a (meta) acryloyl group or a (meta) acryloyloxy group ((meta) acryloyl Is used in the meaning of acryl or metal acryl, and the following (meta) has the same meaning.) If a prepolymer, an oligomer, or a composition containing an appropriate mixture of monomers having a polymerizable unsaturated bond or an epoxy group is used. It is.
  • pre- and oligomers include urethane (meta) clear, polyester (meta) clear Acrylates such as metal and epoxy (meta) acrylates, silicon resins such as siloxane, unsaturated polyesters, epoxys, etc. Are listed.
  • the monomer examples include styrene, a styrene monomer such as a-methylstyrene, a (meth) methyl acrylate,
  • the above-mentioned prepolymer is used. It is preferable that the content of the monomer or the polyol is 5% by weight or more, and the content of the monomer and / or the polyol is 95% by weight or less.
  • the amount of the monomer may be reduced within a range that does not hinder coating suitability.
  • a structure with a relatively low crosslink density using a functional or bifunctional acrylic monomer may be reduced.
  • an acrylate monomer of this type When the heat resistance, hardness, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder coating suitability, or use a trifunctional or higher functional compound. It is preferable to use an acrylate monomer of this type to have a structure with a high crosslinking density.
  • Examples of the monofunctional acrylate-based monomers as described above include 2-hydroxy acrylate, 2-hexaacrylate acrylate, and fluorinated acrylate. ⁇ Nokietinoirerekureto and the like.
  • bifunctional functional monomer examples include ethylene glycol diacrylate, 1,6-hexadiol functional diacrylate.
  • the trifunctional acrylate-based monomers such as methacrylate, trimethylolone propane acrylate, penta-erythrate ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ And the like.
  • the ionizing radiation-curable resin composition may be used as an acetate phenone, a benzophenone, or a mihylene benzoyl benzo.
  • Acetamide, -Amiloxime ester, Tetramethinolamide, Monosanolide, Thioxanthones, and / or Photosensitizer For example, it is possible to use a mixture of ⁇ -butylisoamine, triethylenamine hU- ⁇ -butylphosphine, and the like.
  • ionizing radiation irradiation is used as a method for completely curing a resin composition containing an ionizing radiation curable resin applied to an antiglare film substrate.
  • the resin layer is irradiated with ionizing radiation such as ultraviolet rays or nicknames.
  • ionizing radiation such as ultraviolet rays or nicknames.
  • an ultraviolet irradiator or an electron beam irradiator is usually used as an ionizing radiation irradiator.
  • ultraviolet irradiation devices such as ultra-high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, black lights and metal lamps, etc.
  • a light source is used.
  • the electron beam source can be a cockroach / note-type, band-graft-type, resonant transformer-type, insulated core-transformer-type, or linear type.
  • the electron beam source can be a cockroach / note-type, band-graft-type, resonant transformer-type, insulated core-transformer-type, or linear type.
  • one Irradiation is performed with an electron having an energy of 100 to 100 KeV, preferably 100 to 300 KeV.
  • the irradiation dose is usually about 0.5 to 30 KGy (kilo gray).
  • a transparent protective substrate having antiglare properties is provided with a coating film made of a resin composition containing amorphous silica on the surface.
  • a paint containing amorphous silica is applied to the surface of the transparent substrate in order to impart antiglare properties to the surface of the transparent protective substrate.
  • silica is blended in an amount of about 2 parts by weight with respect to 100 parts by weight of the resin, but such a blending ratio of silica is used.
  • the coating containing silica will not only lose transparency, but the coating containing silica will not be as described above.
  • the haze value of the obtained triacetate film becomes large, The film had reduced resolution, contrast, and transparency.
  • the haze value is a value represented by diffuse transmittance / total light transmittance, and indicates the ratio of diffused light out of transmitted light.
  • the transparency is also excellent at the same time, and further, the resolution and contrast are excellent, and the surface hardness and the solvent resistance are excellent.
  • transparent protective substrate with good performance Provided are a manufacturing method, a transparent protective substrate obtained by the manufacturing method, and a polarizing plate using the transparent protective substrate.
  • acetylcellulose finolem even when acetylcellulose finolem is particularly used as the transparent substrate, it may be subjected to a genification treatment.
  • a method for producing a transparent protective substrate which does not decrease the haze value, contrast and transparency, a transparent protective substrate obtained by the production method, and this transparent protective substrate A polarizing plate.
  • a resin bead having a refractive index of 1.40 to 1.60 on a transparent substrate and an ionizing radiation-curable resin composition are essentially constituted.
  • the coating composition to be coated is applied, and an uncured coating film of the coating composition is irradiated with ionizing radiation to cure the coating film of the coating composition, thereby preventing glare. It is possible to obtain a transparent protective substrate having a transparent film.
  • the transparent substrate includes a triacetyl cellulose film film, an acetate cell cellulose film, an acetate butter cell film.
  • Film Polyethylene resin, Polyurethane resin film, Polyacrylic resin film, Polyurethane resin film, Polyer Stele finolem, Polycarbonate film, Polystyrene film, Polyether film, Trimezololepe Non-innovative films, polyetherketone films, (meta) acrylonitrino films and the like can be used, but especially Tri-acetyl phenolic phenolic for transparency It is suitably used because of its superiority.
  • the film-forming component used in the ionizing radiation-curable resin composition preferably has an acrylic functional group, for example, has a relatively low functional group.
  • Such as (meta) acrylate of polyfunctional compounds such as polyresin, polybutadiene resin, polycarbonate resin and polyvalent alcohol Rigomers or prepolymers and reactive diluents include ethyl (meta) acrylates, ethylhexyl (meta) Monofunctional monomers such as relay, styrene, methyl styrene, N-vinylpyrrolidone, and many others Sensory monomers, for example, trimethylone propane (meta) create, hexandiol (meta) crele Recall, trip recollection recollection (meta) recall, rejection recall recollection (meta) recall, Penta
  • polyester acrylate is very hard and hard. Although it is suitable for obtaining a coating, it can be used alone with Polyester tenacre acrylate because the coating is low in impact strength and brittle. Polypropylene creators are also used in order to provide impact resistance and flexibility to the vehicle. Polyester Clear
  • the mixing ratio of polyurethan acrylate to 100 parts by weight shall be 30 parts by weight or less. If the value exceeds this value, the coating film will be too soft and the hardness will be lost.
  • an acetate phenone, a benzophenone and a benzophenone are used as a photopolymerization initiator.
  • Phenonones, Michler Benzo Norebenzoate, ⁇ — Ami-mouth Kimi Estel, Tetramethylenolium Amides such as amides, thixosanthones, and photosensitizers such as ⁇ -butylamine, triethylamine, and tri- ⁇ -butylbutylamine Can be used as a mixture.
  • the oligomer is a perennial arylate, and the monomer is a diphenyl erythritol. It is preferable to mix the rates.
  • the ionizing radiation-curable resin composition is preferably mixed with a resin bead having a refractive index of 1.40 to 1.60 in order to impart antiglare properties.
  • the reason for limiting the refractive index of the resin bead to such a value is that the ionizing radiation-curable resin usually has a refractive index of 1.40 to 1.50, Choosing a resin bead with a refractive index as close as possible to the refractive index of the radiation-curable resin allows the transparency of the coating to be maintained without impairing the transparency. This is because the anti-glare property can be increased.
  • a resin bead with a refractive index close to that of ionizing radiation-curable resin is shown below.
  • Polycarbonate beads 5 8 Polystyrene beads. 50 Polyacrylic beads. 57 Polychlorinated vinyl beads.
  • the particle size of these resin beads is preferably 3 to 8 m, and is preferably 2 to 100 parts by weight with respect to 100 parts by weight of resin. Usually about 4 parts by weight
  • the coating composition of the present invention may be used as an anti-settling agent for resin beads having a particle diameter of 0.5 jtzm or less, preferably 0.
  • a 0.25m series bead may be included.
  • the coating composition for forming the hard-coated coating film having anti-glare properties used in the present invention has a purpose of preventing electrification of the coating film.
  • An antistatic agent may be added for this purpose.
  • As the antistatic agent metal filler, tin oxide, indium oxide, and the like can be used.
  • the paint composition for forming the anti-glare film used in the present invention is composed of 100 parts by weight of the resin, 100 parts by weight or more of the solvent-dried resin and 100 parts by weight of the resin. Part or less may be included.
  • the solvent-drying resin a thermoplastic resin is mainly used. It is used especially when a mixture of polyester acrylate and poly acrylate is used for the ionizing radiation-curable resin composition.
  • Solvent-dried resins include poly (methyl acrylate) acrylate, poly (methyl acrylate) acrylate or acetate acetate. Cellulose phosphate is preferably used.
  • the reason for including the solvent-drying resin in the ionizing radiation-curable resin composition will be described below.
  • the paint used in the present invention is a roll coater having a metal rolling, for example, a slit reverse coater.
  • a solvent-drying resin is included in the paint composition essentially composed of the ionizing radiation-curable resin composition as described above, when the composition is applied to a transparent substrate with a roll, The reason is that no coating failure occurs at night.
  • Figure 7 shows a specific example of slit reno and scoring.
  • the base material is transferred to a backup apparatus 102, and the composition is applied to the base material by the nozzle coating apparatus 101. Is applied.
  • the coating composition is adjusted in part B by means of a metallizing nozzle 103 and the unneeded composition is removed by means of a doctor 104 .
  • the method of curing a coating composition which is essential from such an ionizing radiation-curable resin composition, is a conventional method of curing an ionizing radiation-curable resin composition, that is, an electron beam or ultraviolet ray. It can be cured by irradiation.
  • an ionizing radiation-curable resin composition that is, an electron beam or ultraviolet ray. It can be cured by irradiation.
  • UV curing light from an ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon lamp, xenon lamp, metal lamp, etc. Ultraviolet rays and the like emitted from the light source can be used.
  • the present invention provides a method for laminating a polarizing element on a transparent protective substrate having a coated antiglare coating film produced as described above.
  • a polarizing plate is obtained.
  • This polarizing element is made of a polyvinyl alcohol, dyed and stretched with iodine or a dye, and is made of polyvinyl alcohol. Film, polyvinyl acetate film, ethylenic acetate vinyl copolymer genated film, etc. be able to .
  • the transparent protective substrate may be made of, for example, a triacetyl phenol resin. If it is a norm, perform a genification process on the triacetyl cellulose film. This genification process may be performed before or after applying a hardcoat to the triacetylcellulose film.
  • High-definition LCD polarizers are made of cellulosic triacetate 'sheet (hereinafter referred to as TAC sheet) that has excellent light transmittance and excellent adhesion to other materials. ) Has been used.
  • Transparent sheets that have been used for polarizing plates in the past provide TAC sheets with excellent optical functions, such as haze, reflectivity, light transmittance, and image clarity, as well as anti-glare properties.
  • the layer is made of a binder made of an ionizing radiation-curable resin to satisfy abrasion resistance, abrasion resistance, etc. in consideration of adhesiveness to a transparent sheet, and the like. It has been used by selecting one of them.
  • the TAC sheet used for conventional polarizers has optical characteristics. Although it has excellent quality, it has the disadvantage of poorer moisture resistance and lower moisture permeability than other plastic sheets such as polyester. It is a great thing. For this reason, a polarizing plate using a TAC sheet is deteriorated due to hydrolytic decomposition of the sheet itself due to environmental moisture, and is likely to deteriorate due to permeated moisture. There has been a problem that the function of a polarizer made of polyvinyl alcohol is deteriorated or the durability is poor.
  • a TAC sheet having excellent optical properties is used for a polarizing plate to provide moisture resistance and prevent its hydrolysis by hydrolysis.
  • the present invention provides a polarizing plate having excellent durability, which does not cause functional deterioration, using a polarizer made of polyvinyl alcohol.
  • a polarizer is provided between the transparent sheets of the two sheets. and have you in a plate, sheet over the city of one also with small greens rather is, that prescribed in JISZ 0 2 0 8, in Tsu by the moisture-proof packaging material moisture permeability test method 5 0 0 g / m 2 ⁇ 2 It has a moisture permeability of 4 hr s. Or less.
  • the transparent sheet is a cellulose acetate sheet, and the hard coat layer and the sheet are separated from each other.
  • the thickness of the hard coat layer which is formed on the surface and is composed of the pentaerythritol triacrylate and the polymerization initiator, is 3 / m or more. It is a polarizing plate of 20 // m.
  • the anti-glare polarizing plate AB of this embodiment has a transmission
  • the moisture permeability of the transparent sheet provided with the anti-glare film layer 203b is 500 g / m '* 24 1 S. (hereinafter, the moisture permeability is , Simply described as g / m 2 ). It is configured as follows.
  • the transparent sheet used in the present embodiment includes a stretched polyester sheet, a polycarbonate sheet, a porous metal sheet, and a transparent sheet.
  • a stretched polyester sheet a polycarbonate sheet, a porous metal sheet, and a transparent sheet.
  • Polyvinyl chloride sheet, ethylene / vinyl acetate copolymer saponified sheet, polymethylpentene sheet, etc. a transparent sheet.
  • the optical functions are excellent in haze, reflectance, light transmittance, and image clarity, and the thickness of the sheet is not uneven, and the accuracy is good. This is a necessary condition, and 80 m TAC sheets manufactured by the casting method are often used.
  • a polarizer composed of a polyvinyl alcohol film is a 20 m thick polarizer that is uniaxially stretched and has polarizability in one molecular orientation. It is a stack of the above finolems.
  • the liquid crystal cell for the LCD is constructed by enclosing a liquid crystal cell with a force filter panel between two glass plates with transparent electrodes.
  • a polarizing plate is laminated on the outer surface of the device via an adhesive layer. Then, as shown in, for example, FIG. 8, the polarizing plate is provided with a transparent sheet 201 and an anti-glare hard coat layer 203b. It is configured with a polarizer 202 interposed between the SB and the SB.
  • the surface of the transparent sheet 201 and the binder of the anti-glare hard coat layer 203b to be provided take into consideration the adhesion to the sheet and the abrasion resistance. From among ionizing radiation-curable resins, select an ultraviolet-curable resin that is easy to handle as a binder.
  • the ionizing radiation-curable resin may contain a polymerizable unsaturated bond or an epoxy group in the molecule, a prepolymer, an oligomer, and / or a monomer. Use the mixed composition.
  • These resin systems include urethane acrylates, pentameters, acrylates, polyesters, and polyesters. Acceleration rate, meta-creation rate, etc., such as no-meter attribute rate, epoxy recreation rate, epoxy recreation rate, etc. ⁇ Silicon resin such as lipstick and polyester epoxy etc. are available.
  • Prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols. Is o
  • Unidentified fields include Penta Eri Retrieval Race Retrie Polyfunctional acrylate monomers such as tonolehexarate, styrene, 0; — methionolestyren, atalinolenic acid Methyl, methacrylic acid methyl acrylate, acrylic amide, ethylene glycol phenolic create, trimethyl phenol , Zero -three-dimensional collection, and the like.
  • the ionizing radiation-curable resin composition is added to photopolymerization initiators such as acetate funon, benzophenone, and michrolar.
  • photopolymerization initiators such as acetate funon, benzophenone, and michrolar.
  • Benzozole Benzoate, thioxanthones, and Z or triethylamine as a photosensitizer, tri-n-petitinole A mixture of phosphine etc. can also be used.
  • the surfactant is appropriately selected from nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • hydrocarbons for the purpose of improving the abrasion resistance of the anti-glare hard coat layer of the polarizing plate used on the surface of the liquid crystal cell, hydrocarbons, fatty acids, fatty acid esters, and lubricants as lubricants It can also be appropriately selected from the group consisting of molds, amides, silicones and the like.
  • Examples of light diffusing agents include silica, calcium carbonate, precipitated calcium sulfate, aluminum hydroxide powder, powdered aluminum powder, and polyethylene.
  • organic fine particles such as len particles, polymetametal atalylate particles, and polycarbonate particles. It is used by selecting it appropriately.
  • silica powder has a high transmittance to ultraviolet light, and is an excellent material that does not hinder the curing of the ultraviolet-curable resin as a binder.
  • the thickness of the antiglare hard coat layer capable of obtaining a desired moisture permeability is 3 / m or more, preferably 5 // m or more and 20 m or less.
  • the thickness of the coating layer is 3 or less, the defects of the protruding material cannot be covered, and if it exceeds 2 O / im, the curling becomes severe.
  • the preferred application amount is 7 to 8 m, which causes the problem of poor machine suitability.
  • the resin varnish has a viscosity of 200 to 150 centimeters suitable for the reverse roll coating method to smooth the coating surface. However, in order to provide leveling properties after coating and to cover fine projections, it is preferable that the solid content is 60% or more. Then, in order to satisfy the above conditions, a curing agent was added to 100 parts of the above-mentioned monomer from the above-mentioned monomers. Those whose viscosity has been adjusted by adding, and a solvent are preferred.
  • the moisture permeability may be large.
  • the same surface of the sheet has the desired moisture permeability due to the two-layer coat of the transparent layer and the anti-glare hard coat layer made of ionizing radiation curable resin. You can also set up things
  • the coating method for forming the anti-glare hard coat layer is determined by the properties and amount of the coating solution, but it is necessary to obtain a smooth surface.
  • directing to curing after application such as direct or linoleic roll coat, bar coat, and gravure coat
  • the coating is carried out with a centrifugal centimeter of 200 to 1500, which has a viscosity suitable for flowability, whereby the coating surface spreads and a smooth uniform surface is obtained.
  • the polarizing plate of the present invention has the one as shown in FIGS. 8 to 12. FIG. That is,
  • the anti-glare polarizing plate AB shown in FIG. 8 is obtained by sequentially laminating a transparent sheet 210 without a hard coat layer and a transparent sheet 201 without a hard coat layer.
  • the moisture-proof hard coat layer 203c is provided on the transparent sheet 201, and the moisture-proof sheet SC and the polarizer 200 are provided. And a transparent sheet 201 without a hard coat layer, which is laminated in this order, on a moisture-proof polarizing plate AC.
  • the transparent sheet 201 without the hard coat layer, the polarizer 202, and the hard coat layer are not provided.
  • the transparent sheet is slightly inferior in optical and surface strength, but is superior in moisture-proof property. You can also use one sheet. That is, a transparent sheet 201, a polarizer 202, and a moisture-proof transparent sheet without a hard coat layer (Polyethylene Teleray) G)
  • the above-mentioned polarizing plate is appropriately selected, and the liquid crystal 4 is used to constitute a “liquid crystal cell” for LCD. That is,
  • a "liquid crystal cell” constructed by using a polarizing plate AA without a hard coat layer on the polarizing plate on both sides as shown at 4AA in Fig. 12A.
  • an anti-glare polarizing plate AB is used on one surface, and a polarizing plate AA without a hard coat layer is used on the other surface. Constituting "Anti-glare liquid crystal cell" for LCD.
  • one anti-glare polarizing plate AB with an anti-glare hard coat layer on one polarizer, and a moisture-proof hard core on the other surface With a moisture-proof polarizing plate AC provided with a coating layer, and a coating layer made of an ionizing radiation curable resin on both transparent sheets 201, the LCD has an anti-glare and moisture-proof property. Liquid crystal cells ”can be constructed.
  • one of the polarizing plates has no hard coat layer, but has a moisture-proof polyethylene.
  • the polarizing plate provided with the antiglare hard coat layer made of the ionizing radiation-curable resin formed on the surface of the transparent sheet is provided with the antiglare hard coat.
  • the layer and the moisture-proof hard coat layer have a moisture permeability of 500 g / m 2 or less.
  • a UV curable resin 2 having the following composition was added to the triacetone resin phenolic resin [TAC 80m1 (Fuji Photo Film Co., Ltd., FT-UV-80)].
  • TAC 80m1 Fluji Photo Film Co., Ltd., FT-UV-80
  • the matted PET (Ra04, Sm: 47.5) is laminated as a shaping finolem.
  • the UV-curable resin was cured by irradiating two 160-WX mercury lamps from a distance of 15 cm as UV-curing conditions to cure the UV-curable resin under a condition of 10 mZ. Further, the shaped film was peeled off to obtain an anti-glare film.
  • the anti-glare finolem obtained in this way had no glare due to light reflection and was excellent in the brightness of the image.
  • the measuring methods and measuring instruments for the optical properties and surface roughness are as follows. The same applies to the embodiments described later.
  • Tri-acetyl cell mouth--S finorem TAC 80m
  • the anti-glare film of the following example was manufactured according to the following manufacturing conditions.
  • TAC triacetyl cellulose
  • V irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • TAC triacetylcellulose
  • UV irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • TAC triacetylcellulose
  • Thickness 80 / m
  • V irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • TAC triacetylcellulose
  • UV irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • TAC triacetylcellulose
  • Thickness 80 / m
  • TAC triacetylcellulose
  • PET poly(yester) (kneading matting agent)
  • E—130 6 ⁇ V irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • TAC triacetylcellulose
  • Thickness 80 / m
  • Drying time about lmin ⁇ ⁇ ⁇ ⁇ Film material PET (polyester) (kneading matting agent) Thickness 26 ⁇
  • Thickness 8 g / 7rf (DRY)
  • PET poly(polyester)
  • Thickness 25 jt / m
  • UV irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • Thickness 80 / m
  • PET poly(yester) (kneading matting agent)
  • Thickness 25 // m
  • UV irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • Thigh material TAC (triacetyl cellulose)
  • Thickness 80 t m
  • Coating method Matrix berth method
  • UV irradiation Lamp used High-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.)
  • TAC triacetylcellulose
  • Thickness 80 zm
  • Thickness 25 ⁇
  • Example 1 87.5 28.9 25.6 0.42 70.8
  • Example 2 87.0 30.1 24.6 0.462 70.7 Jonggyo 3 88.2 5.5 56.9 0.437 186.65
  • Difficult case 4 87.4 8.9 47.4 0.444 107.2
  • Example 5 88.9 3.9 68.4 0.291 122.01
  • Starvation case 6 88.5 5.7 88.0 0.417 156
  • Difficult 7 88.1 10.1 46.0 0.141 50.339
  • Difficult 8 86.7 31.5 23.5 0.50
  • Example 9 87.2 29.3 25.2 0.44 71.5
  • Example 10 88.9 18.0 47.9 0.18 70 Starvation 11 89.3 5.5 5.72.6 0.18 150.5

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Cette invention vise à améliorer les propriétés optiques d'un film anti-réfléchissant utilisé pour les surfaces d'écran de divers appareils, tels que machines de traitement de texte, ordinateurs, télévisions, tableaux de bord d'automobiles, et à rendre ces surfaces d'écran plus facile à voir. Ce film anti-réfléchissant pour écran comprend un film transparent, ainsi qu'une couche de résine du type à durcissement par rayonnement ionisant. Cette couche, qui est placée sur ledit film transparent, présente des caracteristiques optiques telles qu'une transmissivité de lumière totale égale ou supérieure à 85 %, un degré de trouble compris entre 3,0 et 35 % et une brillance à 60 degré égale ou inférieure à 90 %, ainsi qu'une rugosité de surface qui inclut une rugosité moyenne aux axes en surface comprise entre 0,05 et 0,6 νm et un écartement entre les irrégularités de surface compris entre 5 et 200 νm.
PCT/JP1995/000955 1994-05-18 1995-05-18 Film anti-reflechissant WO1995031737A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP6/127168 1994-05-18
JP12716894 1994-05-18
JP15542694 1994-06-15
JP6/155426 1994-06-15
JP6/167556 1994-06-28
JP16755694 1994-06-28

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WO1995031737A1 true WO1995031737A1 (fr) 1995-11-23

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