WO2000044841A1 - Film de protection de surface - Google Patents

Film de protection de surface Download PDF

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Publication number
WO2000044841A1
WO2000044841A1 PCT/JP2000/000406 JP0000406W WO0044841A1 WO 2000044841 A1 WO2000044841 A1 WO 2000044841A1 JP 0000406 W JP0000406 W JP 0000406W WO 0044841 A1 WO0044841 A1 WO 0044841A1
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WO
WIPO (PCT)
Prior art keywords
film
surface protective
protective film
polymer film
laminated
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PCT/JP2000/000406
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English (en)
Japanese (ja)
Inventor
Hiroyuki Nagahama
Toshiyuki Ohya
Seiichiro Yokoyama
Naonobu Oda
Original Assignee
Toyo Boseki Kabushiki Kaisha
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.)
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Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to JP2000596089A priority Critical patent/JP3518677B2/ja
Publication of WO2000044841A1 publication Critical patent/WO2000044841A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a surface protection film suitable for use as a protection film / separator of a component of a liquid crystal display device such as a polarizing plate or a retardation plate, particularly a surface protection film such as a synthetic resin plate.
  • a liquid crystal display device is generally manufactured by laminating a polarizing plate, a liquid crystal cell, and a polarizing plate from the backlight side. Further, various compensating plates such as a phase difference plate are inserted depending on the display mode, the viewing angle, and the like.
  • a method of attaching a polarizing plate with an adhesive layer or a retardation plate with an adhesive layer to an object is usually adopted.
  • the above-mentioned polarizing plate has a configuration in which a polarizing film is sandwiched with triacetyl cellulose, and usually has an adhesive layer for bonding on one side thereof.
  • Triacetylcellulose of the polarizing plate is provided with surface protection films on both sides for the purpose of preventing scratch resistance and moisture resistance from being inferior, damage during handling and a process for manufacturing a liquid crystal display device, or adhesion of dust.
  • a surface protection film having a release layer laminated on the pressure-sensitive adhesive layer side of the deflection plate is used, and a surface protection film having an adhesive layer laminated on the surface of the deflection plate opposite to the pressure-sensitive adhesive layer side is used.
  • a retardation film or the like is used for the purpose of preventing various compensators such as a retardation film from being damaged or adhering dust during handling or during the manufacturing process of the liquid crystal display device.
  • An adhesive layer for bonding is provided on one side of each compensator.
  • a surface protection film is provided on the outermost layers on both sides. A surface protection film having a release layer laminated on the pressure-sensitive adhesive layer side of the deflection plate is used, and a surface protection film having a pressure-sensitive adhesive layer laminated on the side opposite to the pressure-sensitive adhesive layer side of the deflection plate is used.
  • a surface protection film is required. The film is peeled and used.
  • thermocompression bonding type such as a polyethylene film, a polyethylene-vinyl acetate copolymer film, or a pressure-sensitive adhesive such as a polyester film provided with a pressure-sensitive adhesive layer is used.
  • Type is used as the surface protective film on which the pressure-sensitive adhesive layer is formed.
  • Examples of the surface protective film on which the pressure-sensitive adhesive layer is formed which is used for the above-mentioned polarizing plate and the like, include, for example, JP-A-9-111208, JP-A-54-1333578 As proposed in the official gazettes, etc., a surface protection film in which an adhesive layer is formed on a specific polyethylene resin, a polyethylene comprising a specific low-density polyethylene and a high-density polyethylene, and an ethylene-unsaturated polyester copolymer There has been proposed a laminated film or the like obtained by coextruding an adhesive resin layer made of a united product.
  • JP-A-6-148431 JP-A-6-164030 and the like
  • an optically isotropic base such as polycarbonate and polyarylate
  • a surface protective film or the like in which an adhesive resin layer is provided on one side of a sheet and a metal oxide is provided on the other side has been proposed.
  • a film obtained by applying a release agent such as silicone to at least one surface of a biaxially stretched film such as polyester or polypropylene is used.
  • the manufactured liquid crystal display device is inspected in a timely manner in order to evaluate display capability, hue, contrast, and the like.
  • conventionally used surface protection films have anisotropy in their base material, which hinders inspections involving optical evaluation of components to which such surface protection films are attached. Therefore, the surface protection film is peeled off and removed before the inspection, and a new surface protection film is applied again after the inspection. The reason for reapplying with a new surface protection film is that even if the surface protection film can be reapplied, the reapplying will impair the beauty.
  • Such a non-oriented film has a great advantage that it does not need to be peeled off during inspection because it has optical isotropy.However, it is difficult to suppress the orientation by ordinary methods such as melt extrusion. Since it is necessary to use a manufacturing method such as the casting method, and the base film itself becomes expensive, it is hardly used for surface protection films that are ultimately peeled off.
  • the present invention is intended to solve the above-mentioned drawbacks, and an object of the present invention is to provide a low-cost surface protection film that does not require peeling of the surface protection film during inspection, has good inspection properties, and is low in cost. It is assumed that. Disclosure of the invention
  • the present invention has been made in view of the above situation, and a surface protective film that can solve the above problems is as follows.
  • the first invention of the present invention is a surface protection film in which an adhesive layer is laminated on one surface of a polymer film, wherein the maximum distortion of the main orientation axis of the polymer film is 10 degrees or less. Characteristic surface protection film.
  • a second invention is a surface protection film in which a release layer is laminated on one surface of a polymer film, wherein the maximum distortion of the main axis of orientation of the polymer film is 10 degrees or less. Film.
  • a third invention is the surface protective film according to the first or second invention, wherein the polymer film has a retardation value of 1 OOOnm or more.
  • a contrast film represented by the following general formula (I)
  • Y 1 is the amount of transmitted light when the optical axes of the two polarizers are parallel, and a polymer film is inserted between the two polarizers
  • Y 2 is the two polarizers
  • the figure shows the amount of transmitted light when the optical axis of the polarizer is in a perpendicular state and a polymer film is inserted between the two polarizers.
  • a fifth invention is the surface protective film according to the first or second invention, wherein the polymer film has a heat shrinkage at 120 ° C. of 4% or less.
  • a sixth invention is the surface protective film according to the first or second invention, wherein the polymer film has a haze of 10% or less.
  • a seventh invention is a surface protection film, wherein the polymer film according to any one of the first and second inventions is a polyester film.
  • An eighth invention is a surface protection film, characterized in that the polyester film according to the seventh invention is made of polyethylene terephthalate or polyester mainly composed of the same.
  • a ninth invention is a surface protective film, wherein the polyester film according to the seventh invention comprises polylactic acid as a main constituent.
  • a tenth invention is the surface protection film according to the first invention, wherein an antistatic layer is laminated on the surface of the surface protection film opposite to the pressure-sensitive adhesive layer.
  • An eleventh invention is the surface protection film according to the first invention, wherein an antistatic layer is laminated between the pressure-sensitive adhesive layer and the polymer film of the surface protection film.
  • the 12th invention is the surface protection film according to the 2nd invention, wherein an antistatic layer is formed on the surface of the surface protection film opposite to the release layer.
  • a thirteenth invention is the surface protection film according to the second invention, wherein an antistatic layer is formed between the release layer and the polymer film of the surface protection film.
  • the release layer according to the second invention is a silicone resin, A surface protection film characterized in that at least one kind of resin is a main component.
  • a fifteenth invention is a surface protective film, wherein the silicone resin according to the fifteenth invention is a thermosetting silicone resin or a radiation curing silicone resin.
  • a sixteenth invention is the surface protective film according to the first or second invention, wherein the polymer film is a uniaxially stretched polymer film.
  • the surface protective film in the present invention is a surface protective film in which a pressure-sensitive adhesive layer or a release layer is stacked on one surface of a polymer film, and the polymer film has a maximum distortion of a main axis of 10 degrees.
  • the following surface protection film is provided.
  • These surface protective films can be manufactured by the following method. However, it is not limited to this method.
  • the polymer film in the present invention is a film obtained by subjecting an organic polymer to melt extrusion or solution extrusion, stretching in the longitudinal or width direction, cooling, and heat setting as necessary.
  • examples include polyethylene, polypropylene, polyethylene terephthalate, polyethylene mono 2,6-naphtholate, polypropylene terephthalate, polylactic acid, polyglycolic acid, poly (2-oxybutyric acid), nylon 6, nylon 4, nylon 6,6.
  • Nylon 12 Polyimide, Polyamide imide, Polyethersulfone, Polysulfone, Polyetheretherketone, Polycarbonate, Polyarylate, Polyacryl, Cellulose Probionate, Polyvinylchloride, Polyvinylidene chloride, Polyvinyl alcohol , Pollier (1) Terimide, polyphenylene sulfide, polyphenylene oxide, polystyrene, syndiotactic polystyrene, norpoleneene-based polymer, and the like. In addition, these organic polymers may be copolymerized with a small amount of another organic polymer or blended.
  • aromatic polyester films such as polyethylene terephthalate, polyethylene 1,2-naphtholate and polypropylene terephthalate, and aliphatic polyesters such as polylactic acid are preferably used.
  • polyethylene terephthalate is particularly low in impurities and has high transparency. It is most suitable for its overall performance including mechanical properties, surface smoothness, solvent resistance, scratch resistance, moisture impermeability, and cost.
  • the surface protective film of the present invention has been tested for optical evaluation of components such as a polarizing plate and a retardation plate of a liquid crystal display device such as display capability, hue, contrast, and optical defects, and is incorporated into the liquid crystal display device. At the time of removal. That is, it becomes unnecessary after the inspection is completed.
  • the main repeating unit which is biodegradable in the natural world, has a small amount of heat during combustion, does not damage the incinerator, has a low environmental load, and is excellent in transparency and mechanical strength, has the following general formula:
  • An aliphatic polyester film comprising a unit represented by 0—CHR—CO— (R is H or an alkyl group having 1 to 3 carbon atoms) is also suitable as the base film of the surface protective film of the present invention.
  • the aliphatic polyester having a repeating unit include polylactic acid, polyglycolic acid, and poly (2-oxybutyric acid). One or more of these are selected and used. When two or more kinds are used, a mixture or a copolymer may be used.
  • optical isomers such as L-integral, DL-integral and D-isomer, but any of these may be used, or two or more isomers may be mixed. It may be something.
  • the aliphatic polyester can be produced by a known method such as ring-opening polymerization using the corresponding dehydrated cyclic ester compound of monooxyacid. Among these aliphatic polyesters, polylactic acid is most preferred.
  • the polymer film can be obtained by forming a film by an ordinary method. Among them, a homopolymer or copolymer melt or solution is formed into a film by extrusion, calendaring, casting, or the like, and then vertically or horizontally by a roll method, tenter method, or tubular method. A method of uniaxially stretching in the direction is preferable. However, as long as the range of the film characteristics described in the present invention is satisfied, biaxial stretching may be performed.
  • the maximum distortion of the main axis of orientation of the polymer film is a numerical value of a phenomenon in which the direction of the main axis of orientation is bent in the film width direction due to heat shrinkage.
  • a phenomenon occurs in which the phase of light shifts due to a birefringence effect and light leaks to the analyzer side.
  • the maximum distortion of the main orientation axis of the polymer film needs to be 10 degrees or less. It is preferably at most 8 degrees, particularly preferably at most 5 degrees. If the maximum distortion of the main alignment axis is more than 10 degrees, the contrast of the specimen decreases during the test, which is not preferable.
  • the retardation value of the polymer film is preferably at least 1000 nm, particularly preferably at least 500 nm. If the retardation value is 100 nm or more, there is no problem in inspection. If the thickness is 500 nm or more, the interval between interference fringes is sufficiently widened in the visible light region, and thus it is more preferably optically isotropic.
  • the thickness of the polymer film is not particularly limited, it is appropriate to set the thickness to 300 ⁇ m or less in consideration of use and workability. If the thickness exceeds 300 m, the advantage of a thin polymer film is lost. Further, the polymer film may be not only a single layer but also a multilayer.
  • the biaxial refractive index anisotropy ( ⁇ ⁇ ⁇ ⁇ ).
  • a tensile film in which uniaxial stretching is reinforced is preferred.
  • the stretching tension in one axis direction is The biaxial refractive index anisotropy ( ⁇ ) can be increased by increasing the draw ratio or lowering the draw temperature so as to increase the draw ratio.
  • the polymer film serving as the base material of the surface protective film of the present invention preferably has a minimum value of 70 or more of its contrast (C) represented by the following general formula (I), more preferably Is 110 or more, particularly preferably 150 or more.
  • C its contrast
  • Is 110 or more particularly preferably 150 or more.
  • Polymer films with a minimum contrast value of less than 70 tend to be difficult to detect foreign substances in the specimen and confirm the display ability during the test. In practice, the minimum value of contrast should be 50 or more.
  • Y 1 is the amount of transmitted light when the optical axes of the two polarizers are parallel, and a polymer film is inserted between the two polarizers
  • Y 2 is the two polarizers
  • the figure shows the amount of transmitted light when the optical axis of the polarizer is in a perpendicular state and a polymer film is inserted between the two polarizers.
  • the minimum value of the contrast is measured by the following method. First, if the film is in the form of a roll, cut out a rectangle of 500 mm in the longitudinal direction and full width in the width direction. Then, as shown in FIG. 8, a square of 100 mm square in the width direction (tenter direction) including the same edge is cut out at three or more places including two vertexes of the rectangle and the center thereof.
  • 21 is the longitudinal direction
  • 22 is the width direction
  • 23 is the edge
  • 24 is the vertex
  • 25 is the center of the vertex.
  • the optical axes of the two polarizers in parallel state is placed in advance either to the polarizer support Npuruhoruda one you exactly parallel to the polarization direction and the bottom of the 1 0 0 mm square film sample 2
  • the amount of light transmitted through the two polarizers and the film sample is measured.
  • the amount of transmitted light when the optical axes of the two polarizers are set to be orthogonal is measured, and the contrast of each film sample is calculated according to the above formula (I).
  • the lowest value of the contrast for each film sample obtained in this way is defined as the “lowest value of contrast” here.
  • the film is stretched 90 degrees in the longitudinal direction before the heat-setting treatment after the transverse stretching. Relaxation of 1 to 10% at ⁇ 200 ° C , A method of heat setting at 140 to 250 ° C., a method of relaxing at 1 to 10% in the width direction after the heat setting, and the like.
  • the heat shrinkage at 120 ° C. of the polymer film of the present invention is preferably 4% or less. Particularly preferably, it is 1% or less. If the heat shrinkage at 120 ° C. is more than 4%, it is not preferable because flatness is disturbed when passing through a process involving heating such as formation of an adhesive layer or a release layer.
  • the haze of the polymer film is preferably 10% or less. It is more preferably at most 5%, particularly preferably at most 1%. If the haze is more than 10%, the light is scattered when the light passes through the polymer film, and the contrast is unfavorably reduced.
  • the method for producing a polymer film in the present invention is not particularly limited, but it is necessary to appropriately adjust the method according to the characteristics of the polymer used.
  • a polyethylene terephthalate film a polyethylene terephthalate film is melted, and a non-oriented polyethylene terephthalate film extruded into a sheet is stretched laterally with a tenter at a temperature equal to or higher than the glass transition temperature.
  • a method of performing a heat setting treatment is preferably from 80 to 130 ° C, particularly preferably from 90 to 120 ° C.
  • the stretching ratio is preferably 2.5 to 6.0 times, particularly preferably 3.0 to 5.5 times.
  • the stretching ratio is low, the haze becomes high, and the transparency of the film becomes poor.
  • the stretching tension is also small, so that the biaxial refractive index anisotropy ( ⁇ ⁇ ⁇ ⁇ ) is small. As a result, the retardation value becomes small, which is not preferable.
  • the relaxation treatment of the film in the longitudinal direction before the heat setting treatment after the transverse stretching is effective in reducing the decrease in the maximum distortion of the main orientation axis ⁇ contrast.
  • the temperature at the time of the relaxation treatment in the longitudinal direction is 90 to 20 (preferably in the range of TC, particularly preferably in the range of 120 to 180 ° C.
  • the amount of relaxation varies depending on the transverse stretching conditions. It is preferable to set the relaxation amount and the relaxation temperature so that the heat shrinkage at 4 ° C. becomes 4%.
  • the heat-setting temperature is preferably in the range of 130 to 250 ° C, particularly preferably in the range of 180 to 245 ° C.
  • the heat setting process is first performed at a fixed length.
  • the polymer film of the present invention can be surface-treated by a known method. For example, in the case of a film that has been subjected to corona discharge treatment (in air, nitrogen, carbon dioxide gas, etc.) or easy adhesion treatment, the adhesiveness to the coating layer, water resistance, chemical resistance, etc. are improved, so that preferable.
  • Various known methods can be used for the easy-adhesion treatment, and those obtained by applying various well-known easy-adhesives to the film after the film production process or after uniaxial or biaxial stretching are preferably used.
  • the polymer film of the present invention can contain a known additive as needed, in order to impart various functions, as long as the effects of the present invention are not impaired.
  • a known additive for example, inorganic and / or heat-resistant organic particles, lubricants, antiblocking agents, electrostatic adhesion promoters, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance improvers, etc. You may. However, since transparency is required for optical applications, it is preferable to minimize the content of the above additives in the film.
  • a layer having an adhesive property to an optical member for example, a heat-sensitive adhesive resin layer such as a polyester-based, a polyolefin-based, or a polyamide-based, an acrylic-based, a polyester-based, a urethane-based, or a polyether-based resin.
  • Hardening agents to resins having functional groups such as pressure-sensitive adhesive resin layers such as rubber-based and rubber-based resins, saturated polyester resins, polyurethane-based resins, polybutadiene polyols, polyolefin polyols, and functional group-containing acrylyl copolymers.
  • a plasticizer for example, 20% by weight or more
  • a plasticizer for example, 20% by weight or more
  • a plasticizer for example, 20% by weight or more
  • a saturated polyester resin film for example, 20% by weight or more
  • a film obtained by forming an ethylene-based resin, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, and other ethylene-based copolymers are formed. And the like. If rework is required, select an adhesive resin that has peelability. If permanent adhesion is required, select a resin that can provide strong adhesive or adhesive strength. The thickness of the adhesive resin layer is often set to about l to 50 // m.
  • the release layer includes a layer having a release property from the optical member, for example, a silicone resin, a fluororesin, or the like.
  • silicone resin those generally known as release agents can be used, and are selected from known ones described in “Silicone Material Handbook” (edited by Toray Dow Corning, Ltd., 1989.3). Can be used with Generally, a thermosetting or ionizing radiation curing type is used. As the thermosetting type, for example, a condensation reaction type and an addition reaction type can be used, and as the ionizing radiation curing type, any reaction type such as an ultraviolet ray or electron beam curing type can be used.
  • condensation reaction type silicone resin for example, a polydimethylsiloxane having a terminal OH group and a polydimethylsiloxane having a terminal H group (hydrogensilane) are used with an organic tin catalyst (for example, an organic tin acylate catalyst). And a condensation reaction to form a three-dimensional crosslinked structure.
  • an organic tin catalyst for example, an organic tin acylate catalyst
  • addition reaction type silicone resin examples include those which form a three-dimensional crosslinked structure by reacting a polydimethylsiloxane having a vinyl group introduced into a terminal with a hydrogen silane using a platinum catalyst.
  • UV-curable silicone resins are, for example, those that utilize the same radical reaction as ordinary silicone rubber crosslinking, those that introduce an acryl group and are photocured, and those that decompose onium salts with ultraviolet light.
  • a strong acid to generate a strong acid thereby cleaving the epoxy ring to crosslink, and a crosslink by addition reaction of thiol to vinyl siloxane.
  • Electron beams have higher energy than ultraviolet light, and radical crosslinking reaction occurs without using an initiator as in the case of ultraviolet curing.
  • the above-mentioned curable silicone resin preferably has a degree of polymerization of about 500 to 200,000, and particularly about 100,000 to 100,000. Specific examples thereof include Shin-Etsu Chemical Co., Ltd. KS-7 18,-7 7 4,-7 7 5,-7 7 8,-7 7 H, 1 8 3 0,- 835, 1 837, 1 838, 1 839, 1 841, 1 843, 1 847, 1 847 H, X-62-2418, 1 2422, 1 2125, -2492. -249 4, 1 5048,-470, 1 2366, 1 630, X-92-140, 1 12
  • the silicone resin described in JP-A-52-40918 can also be used. Further, one of these curable silicone resins may be used alone, or two or more thereof may be used in combination.
  • a known release resin can be used as the fluororesin.
  • a fluorine resin include a polymer (including an oligomer) composed of a fluorine-containing vinyl polymerizable monomer or a copolymer thereof, or a fluorine-containing vinyl polymerizable monomer and a fluorine atom.
  • Copolymers with at least one kind of vinyl polymerizable monomer containing no substituted alkyl group or functional group, or a mixture thereof and having 5 to 80 mol% of fluorine atoms Can be
  • polymer comprising the fluorine-containing vinyl polymerizable monomer examples include poly [2- (perfluorononenyloxy) ethyl methacrylate] and poly [2- (per Fluorononenyloxy) Ethyl atalylate], Poly [2- (Perfluorononenyloxybenzoyloxy) ethyl methacrylate], Poly [2— (Perfluorononenyloxy) [Xybenzoyloxy) ethyl acrylate], poly [2,2,2-trifluoroethyl methacrylate], poly [2,2,2-trifluoroethyl acrylate], poly [2,2,3 3, 3?
  • Ntafluo Methyl propyl methacrylate Poly [2.2,3,3.3-Pentafluoro mouth propyl acrylate], Poly [1-methyl-2,2,3,3,4,4-hexafluorobutyl methacrylate], Poly [1-Methyl-2,2,3,3,4,4-—Hexafluorobutyl acrylate], Poly [Perfluo-butyl methacrylate], Poly [Perfluoro-mouth butyl acrylate] ], Poly [perfluorohexyl vinyl ether], poly [ ⁇ , ⁇ ,) 3-trifluorostyrene], polyvinylidene fluoride, polyhexafluoropropylene, polytetrafluoroethylene, etc. Can be
  • Examples of the vinyl polymerizable monomer which is copolymerizable with the above-mentioned fluorine-containing vinyl polymerizable monomer and does not contain an alkyl group substituted with a fluorine atom, a functional group, and the like include a hydrocarbon-based vinyl polymerizable monomer, Examples of the compound include a hydrocarbon-based non-conjugated divinyl polymerizable monomer and a functional group-containing vinyl polymerizable monomer. Examples of the hydrocarbon-based vinyl polymerizable monomer include methyl acrylate and propyl acrylate.
  • hydrocarbon-based non-conjugated divinyl polymerizable monomers such as 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene and isoprene include, for example, ethylene glycol diatalylate, ethylene glycol Jim crete, propylene glycol Diol diacrylate, propylene glycol dimeth
  • N-butoxymethyl acrylamide diacetone acrylamide, methylol diacetone acrylamide, 2-hydroxyshethyl acrylate, 2-hydroxyshethyl methacrylate, hydroxypropyl acrylate, 3 —Chloro-2-hydroxypropyl methacrylate and the like, and are selected from these, but are not particularly limited.
  • the thickness of the release layer in the present invention is not particularly limited, but is preferably in the range of 0.05 to 5 ⁇ m. If the thickness of the coating film is thinner than this range, the release performance is reduced, and satisfactory performance cannot be obtained. Conversely, if the thickness of the coating film exceeds this range, curing takes a long time, which is not preferable in terms of production.
  • the release layer may contain known additives within a range that does not impair the object of the present invention, such as an antifoaming agent, a coating improver, a thickener, an antistatic agent, an antioxidant, an ultraviolet absorber, and a curing agent. , A dye or the like.
  • the method for forming the pressure-sensitive adhesive layer or the release layer of the present invention on the surface of the polymer film as the base film is not particularly limited, but a coating method is preferably used.
  • coating methods include air-coating, knife coating, rod coating, forward rotation roll coating, reverse roll coating, gravure coating, kiss coating, bead coating, and slit orifice coating. And the cast coat method.
  • Drying and / or curing (thermal curing, ionizing radiation curing, etc.) of the coating film of the pressure-sensitive adhesive layer or the release layer can be performed individually or simultaneously. If they are performed simultaneously, it is preferable to perform them at a temperature of 80 ° C. or higher.
  • the drying and curing conditions are preferably at 80 ° C. or more and 10 seconds or more. If the drying temperature is less than 80 ° C or the curing time is less than 10 seconds, the curing of the coating film is incomplete and the coating film tends to fall off, which is not preferable.
  • the surface protective film of the present invention is preferably provided with an antistatic layer for the purpose of suppressing generation of static electricity.
  • an antistatic resin composition for the antistatic layer, apply an antistatic resin composition. 406.
  • the antistatic resin composition needs to contain an antistatic agent, and the surface specific resistance of the antistatic layer is preferably set to 1 ⁇ 1 1 ⁇ or less. Further, it is preferable to select an antistatic agent so that the surface specific resistance value shows the surface specific resistance value not only on the coated surface but also on the opposite surface where the coating is not performed.
  • quaternary ammonium salts pyridinium salts, various cationic antistatic agents having a cationic group such as a primary to tertiary amino group, sulfonate groups, sulfate bases, phosphate bases, phosphonate bases
  • Various surface activities such as anionic antistatic agents having anionic groups such as amino acids, amphoteric antistatic agents such as amino acids and amino sulfates, and nonionic antistatic agents such as amino alcohols, glycerin and polyethylene glycol.
  • Formulation type antistatic agent furthermore, a high molecular weight antistatic agent having a high molecular weight of the above antistatic agent, and the like.They also have a tertiary amino group to a quaternary ammonium group, Monomers and oligomers polymerizable by ionizing radiation, for example, ⁇ , ⁇ -dialkylaminoalkyl (meth) acrylate monomers, Polymerizable antistatic agents such as quaternary compounds can also be used.
  • a binder is used to improve the strength of the coating of the antistatic layer, adhesion to the base film, water resistance, solvent resistance, blocking property, etc.
  • thermoplastic resin such as thermoplastic polyester resin, acrylic resin, polyvinyl resin, etc. and / or polymer compound such as thermosetting resin such as thermosetting acrylic resin, urethane resin, melamine resin, epoxy resin, etc. Is preferred.
  • a methylolated or alkylolated melamine-based, urea-based, glyoxal-based, acrylamide-based compound, an epoxy compound, and a polyisocyanate as a cross-linking agent.
  • the surface specific resistance of the antistatic layer can be arbitrarily set according to the purpose of use. For example, when ordinary dust does not adhere, it is about 1 X 1 ⁇ 1].
  • the method for forming the antistatic layer on the surface of the substrate film is not particularly limited, but a coating method is preferably used.
  • a coating method there are an advector coat method, a knife coat method, a rod coat method, a forward rotation roll coat method, a roll coat method, a gravure coat method, a kiss coat method, a bead coat method, T / JP00 / 00406 Slit orifice coat method, cast coat method and the like.
  • the drying temperature of the antistatic layer may be in the range of 60 to 150 ° C, preferably in the range of 80 to 130 ° C. If the drying temperature is lower than 60 ° C., the curing time is prolonged, and the productivity is undesirably reduced.
  • the antistatic layer is provided on the surface of the polymer film, but the pressure-sensitive adhesive and the release layer can be provided on the surface of the polymer film opposite to the surface on which the antistatic layer is formed, even if provided on the antistatic layer. Is also good.
  • the film shape is on a roll, cut out the entire width in the length direction of 1000 mm and the width direction.For a sheet-like sample, draw the rectangle with the largest area inscribed in the sample shape, and share two sides with the vertex of the rectangle 10 Omm A square is cut out from four vertices.
  • the major axis of orientation was determined by microwave, and when the molecular orientation angle of the first measured point was 0 degree, the maximum value was determined from the one with the largest difference in the orientation angle of the other three points, and the maximum value was defined as the maximum distortion of the major axis of orientation. .
  • a molecular orientation meter MOA-2001A manufactured by Kanzaki Paper Co., Ltd. was used.
  • the biaxial refractive index anisotropy ( ⁇ ) was determined by the following method. Using two polarizing plates, the orientation axis direction of the film was determined, and a 4 cm x 2 cm rectangle was cut out so that the orientation axis was almost perpendicular to obtain a measurement sample.
  • the biaxial refractive index of the sample which is almost perpendicular, is determined by an Abbe refractometer (ATAGO 4T manufactured by Atago Co., Ltd.), and the absolute value of the biaxial refractive index difference is determined by the refractive index anisotropy ( ⁇ ).
  • the thickness d (nm) of the film was measured using an electric micrometer (Miritron 1245D manufactured by Fine Lieuf), and the unit was converted to nm.
  • the film shape is on a roll, cut out the entire width in the length direction of 1000 mm and the width direction.For a sheet-like sample, draw the rectangle with the largest area inscribed in the sample shape, and share two sides with the vertex of the rectangle Cut a 10 Omm square from four vertices.
  • Example 1 A 10 Omm square film is placed between two polarizing plates arranged in the perpendicular direction, a fluorescent lamp is used as the light source from the bottom of the two polarizing plates, and the sample is inserted visually from the opposite direction. The change in the amount of transmitted light in each case was observed.
  • Example 1 A 10 Omm square film is placed between two polarizing plates arranged in the perpendicular direction, a fluorescent lamp is used as the light source from the bottom of the two polarizing plates, and the sample is inserted visually from the opposite direction. The change in the amount of transmitted light in each case was observed.
  • Polyethylene terephthalate was melt extruded through a film forming die onto a water-cooled rotating quenching drum to produce an unstretched film.
  • This unstretched film was stretched 3.7 times in the width direction at 90 ° C, and then annealed at 120 ° C for 10 seconds. After leaving the tenter, both ends of the film were trimmed at a position of 2 Omm from the end, and a portion having a small heat shrinkage was cut off. Subsequently, the film was heated to 100 ° C by a ceramic roll, and a 3% relaxation treatment was performed in the vertical direction while heating using four infrared heaters with a surface temperature of 700 ° C.
  • the maximum distortion of the orientation main axis is 5 degrees
  • the minimum value of the contrast is 94
  • the heat shrinkage at 120 ° C is 0.7%
  • the haze is 0.1%
  • the total light transmittance is 90%
  • the retardation value is 5100 nm.
  • a surface protection film was obtained in the same manner as in Example 1, except that only the thickness of the uniaxially stretched polyethylene terephthalate film was changed from 46 to 110 m.
  • the maximum distortion of the main orientation axis is 7 degrees
  • the minimum value of the contrast is 60
  • the heat shrinkage at 120 ° C is 1.0%
  • the haze is 0%. 1%
  • the total light transmittance was 90%
  • the retardation value was 1100 nm.
  • Example 3 In the same manner as in Example 1, a surface protection film having a pressure-sensitive adhesive layer laminated on one side was obtained. When the contrast of the surface protective film was evaluated, a slight difference in contrast was observed, but the film was practically usable.
  • Example 3 When the contrast of the surface protective film was evaluated, a slight difference in contrast was observed, but the film was practically usable.
  • Example 1 Example 1 was repeated except that polyethylene 1,2,6-naphthalate was used instead of polyethylene terephthalate as the polymer for the polymer film. 0 6
  • the maximum principal axis distortion is 6 degrees
  • the minimum contrast is 71
  • the heat shrinkage at 120 ° C is 0.9%
  • the haze is 0.1. %
  • the total light transmittance was 89%
  • the retardation value was 5200 nm.
  • Example 4 In the same manner as in Example 1, a surface protection film having a pressure-sensitive adhesive layer laminated on one side was obtained. When the contrast of this surface protective film was evaluated, the difference in contrast was small and good as in Example 1.
  • Example 4
  • Poly-L-lactic acid having a weight-average molecular weight of 200,000 was melt-extruded through a film forming die onto a water-cooled rotary quenching drum to produce an unstretched film.
  • the unstretched film was stretched 4 times in the width direction at 100 ° C, and then annealed at 120 ° C for 10 seconds. After exiting the tenter, both ends of the film were trimmed at 2 Omm from the ends, and sites with small heat shrinkage were cut off. Subsequently, the film was heated to 100 ° C by a ceramic roll, and further subjected to a 3% relaxation treatment in the longitudinal direction while heating using four infrared heaters having a surface temperature of 700 ° C.
  • the film was subjected to a 2% relaxation treatment while heating the film to 135 ° C with a ceramic aperture. Thereafter, both ends of the film were gripped with clips, heat-set at 155 ° C, and 3% relaxed in the width direction at 135 ° C. Thus, a uniaxially stretched poly-L-lactic acid film having a thickness of 46 was obtained.
  • Example 5 In the obtained uniaxially stretched poly-L-lactic acid film, the maximum distortion of the main orientation axis is 6 degrees, the minimum value of contrast is 78, the heat shrinkage at 120 ° C is 0.7%, the haze is 0.2%, The total light transmittance was 90% and the retardation value was 5000 nm.
  • a surface protection film having a pressure-sensitive adhesive layer laminated on one side was obtained. When the contrast of this surface protective film was evaluated, the difference in contrast was small and good as in Example 1.
  • Example 5 Example 5
  • Example 2 In the same manner as in Example 1, a uniaxially stretched polyethylene terephthalate film having a thickness of 46 m was obtained. On the obtained uniaxially stretched polyethylene terephthalate film, an ultraviolet-curable antistatic resin composition (manufactured by Dainichi Seika Kogyo Co., Ltd .: EXG 40-13 S-1) with a solid thickness of 5 m It applied so that it might become. The coating layer was irradiated with ultraviolet light to cure the coating layer, thereby laminating an antistatic layer on the film.
  • an ultraviolet-curable antistatic resin composition manufactured by Dainichi Seika Kogyo Co., Ltd .: EXG 40-13 S-1
  • the coating layer was irradiated with ultraviolet light to cure the coating layer, thereby laminating an antistatic layer on the film.
  • a pressure-sensitive adhesive layer was laminated on the surface of the uniaxially stretched polyethylene terephthalate film on which the antistatic layer was not laminated in the same manner as in Example 1, and a surface on which a pressure-sensitive adhesive layer was laminated on one surface and an antistatic layer was laminated on the other surface.
  • a protective film was obtained.
  • Polyethylene terephthalate was melt-extruded through a film forming die onto a water-cooled rotary quenching drum to produce an unstretched film.
  • This unstretched film was stretched 4.0 times at 90 ° C. in the width direction. Further, the film was heat-set in the width direction at 220 ° C., and then relatated at 200 ° C. by 4% to obtain a uniaxially stretched polyethylene terephthalate film having a thickness of 46 m.
  • the maximum distortion of the main orientation axis is 12 degrees
  • the minimum value of contrast is 22
  • the heat shrinkage at 120 ° C is 0.7%
  • the haze is 0.1%.
  • the total light transmittance was 90%
  • the retardation value was 5100 nm.
  • a surface protection film having an adhesive layer laminated on one surface was obtained in the same manner as in Example 1 except that this uniaxially stretched polyethylene terephthalate film was used. When the contrast of this surface protective film was evaluated, the difference in contrast was large, which was not preferable.
  • Comparative Example 2 Polyethylene terephthalate was melt-extruded through a film forming die onto a water-cooled rotary quenching drum to produce an unstretched film. The unstretched film was stretched 3.8 times in the width direction at 90 ° C. to obtain a uniaxially stretched polyethylene terephthalate film having a thickness of 20 ⁇ m.
  • the maximum distortion of the main orientation axis is 12 degrees
  • the minimum value of contrast is 20
  • the heat shrinkage at 120 ° C is 0.6%
  • the haze is 0.1%
  • the light transmittance was 90% and the retardation value was 800 nm.
  • Example 6 The procedure was performed in the same manner as in Example 1 except that this uniaxially stretched polyethylene terephthalate film was used, to obtain a surface protective film having an adhesive layer laminated on one side. When the contrast of this surface protection film was evaluated, light interference was observed, which was not preferable.
  • Example 6 The procedure was performed in the same manner as in Example 1 except that this uniaxially stretched polyethylene terephthalate film was used, to obtain a surface protective film having an adhesive layer laminated on one side. When the contrast of this surface protection film was evaluated, light interference was observed, which was not preferable.
  • Polyethylene terephthalate was melt-extruded through a film forming die onto a water-cooled rotary quenching drum to produce an unstretched film.
  • This unstretched film was stretched 3.2 times at 90 ° C in the width direction, and then annealed at 80 ° C for 10 seconds.
  • After leaving the tenter preheat the film using a ⁇ 5 ° C roll, and then install three infrared heaters with a diameter of 10 mm and a surface temperature of 700 ° C at a distance of 20 mm from the film. It was heated and stretched 3.0 times in the machine direction. After that, both ends of the film were trimmed, and portions where the heat shrinkage differs by more than 20% from the center of the film were cut off.
  • the film was heated to 100 ° C by a ceramic roll, and further subjected to a 7% relaxation treatment in the vertical direction while heating using four infrared heaters having a surface temperature of 700 ° C.
  • a 2% relaxation treatment was performed while heating the film between the ceramic rolls to 160 ° C by hot air.
  • both ends of the film are held with clips, subjected to a heat treatment at 235 ° C, reluctant such further cooled from 200 ° C to 120 e C, was 3% relaxation treatment in the transverse direction.
  • a biaxially stretched polyethylene terephthalate film having a thickness of 46 m was obtained.
  • a slight change in the amount of transmitted light was observed when the sample was inserted and when the sample was not inserted, but the sample was practically usable.
  • a uniaxially stretched polyethylene terephthalate film having a thickness of 46 m was obtained in the same manner as in Example 1 except that the heat setting temperature was changed from 235 ° C to 220 ° C.
  • the maximum distortion of the main orientation axis is 4 degrees
  • the minimum value of the contrast is 153
  • the heat shrinkage at 120 ° C is 0.8%
  • the haze is 0.1%
  • the total light transmission was 90% and the retardation value was 5100 nm.
  • Polyethylene terephthalate was melt-extruded through a film forming die onto a water-cooled rotary quenching drum to produce an unstretched film.
  • the unstretched film was stretched 4.0 times at 90 ° C in the width direction. Further, the film was heat-set in the width direction at 180 ° C, and subsequently subjected to a 4% relaxation treatment at 170 ° C to obtain a uniaxially stretched polyethylene terephthalate film having a thickness of 46.
  • Example 9 In the obtained uniaxially stretched polyethylene terephthalate film, the maximum distortion of the orientation main axis was 5 degrees, the minimum value of contrast was 94, the heat shrinkage at 12 CTC was 1.0%, the haze was 0.1%, and the total The light transmittance was 90% and the retardation value was 5100 nm. Further, in the same manner as in Example 1, a surface protective film having an adhesive layer laminated on one side was obtained. The testability of the polarizing plate using this surface protective film was good. Example 9
  • Example 10 In Example 1, except that the film thickness was changed from 46 ⁇ m to 110 1m and the heat setting temperature was changed from 235 ° C to 220 ° C, the thickness was 110 ⁇ m Of a uniaxially stretched polyethylene terephthalate film was obtained.
  • the maximum strain of the main axis of orientation of the obtained axially stretched polyethylene terephthalate film was 4 degrees, the minimum value of the contrast was 145, the heat shrinkage at 120 ° C was 1.0%, the haze was 0.2%, The total light transmittance was 90% and the retardation value was 11000 nm.
  • a surface protective film having a pressure-sensitive adhesive layer laminated on one surface was obtained in the same manner as in Example 1. The testability of the polarizing plate using this surface protective film was good.
  • Example 10 Example 10
  • Example 2 In the same manner as in Example 1, except that polyethylene 1,2-naphthalate was used instead of polyethylene terephthalate and the heat setting temperature was changed from 235 ° C to 220 ° C, 46 uniaxially stretched polyethylene terephthalate films were obtained.
  • the obtained uniaxially stretched polyethylene terephthalate film has a maximum orientation principal axis of 4 degrees, a minimum contrast of 160, a heat shrinkage of 0.9% at 120 ° C, a haze of 0.1%, and all rays.
  • the transmittance was 89% and the retardation value was 5200 nm.
  • Example 1 a surface protective film having an adhesive layer laminated on one side was obtained. The testability of the polarizing plate using this surface protective film was good.
  • a quaternary ammonium salt type cationic polymer compound manufactured by Nitto Boseki Co., Ltd .: PAS 10L
  • SUMI MALM—40W manufactured by Sumitomo Chemical Co., Ltd.
  • Paint 6 Epoxy-modified silicone (Shin-Etsu Chemical
  • the solution was applied at a coating amount of Ag Zm 2 (coating amount base), heated and dried at 120 ° C. for 1 minute, and cured to form an antistatic layer.
  • an adhesive layer was laminated on the surface of the uniaxially stretched polyethylene terephthalate film on which the antistatic layer was not laminated in the same manner as in Example 1, an adhesive layer was laminated on one surface, and an antistatic layer was laminated on the other surface. A surface protection film was obtained.
  • Example 11 a pressure-sensitive adhesive layer was laminated on the surface of the uniaxially stretched polyethylene terephthalate film on which the antistatic layer was laminated in the same manner as in Example 1, and the antistatic layer and the adhesive were laminated on one surface in this order. A protective film was obtained.
  • Example 7 an addition reaction type silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .; 3-7778, solid content: 30% dissolved in toluene) was used as a release agent instead of the ethylene vinyl acetate acetate-based adhesive-containing coating solution. 100 parts by weight) and 1 part by weight of a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .; PL-50T) are dissolved in toluene, and a 3% by weight total toluene solid solution (solvent) is dissolved. 6 g / m 2 (coating liquid base) using a coating liquid for mold layer), heat-dry at 120 ° C for 1 minute, and carry out addition polymerization reaction. To produce a surface protective film. The testability of the polarizing plate using this surface protective film was good. 0/00406 Example 14
  • a protective film was obtained. The testability of the polarizing plate using this surface protective film was good. The surface protective film did not generate static electricity when peeled off, and had good adhesion with little dust.
  • Example 16 The same procedure as in Example 12 was carried out except that a UV-curable silicone resin (X-62-5048, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the addition-reaction silicone resin as the release agent. A surface protective film having a release layer laminated thereon was obtained. The testability of the polarizing plate using this surface protection film was good.
  • a UV-curable silicone resin X-62-5048, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 13 instead of a coating solution containing an addition-reaction-type silicone resin as a release agent, a fluorine-based solvent (FC-77 “Fluorinert” manufactured by 3M) was used as a diluting solvent, which was used as a fluorine-containing resin.
  • FC-77 Fluorinert
  • a fluoroacrylic resin manufactured by Neos Corp .: RBX-725NF “Frerelease”
  • a fluorine-based oil manufactured by DuPont; 157FS-M "Crytotus
  • a coating solution having a concentration of 3.0% by weight was applied to a solid thickness of 0.4 m and dried by heating at 120 ° C for 1 minute to obtain a surface protective film having a release layer laminated on one side. .
  • the testability of the polarizing plate using this surface protective film was good.
  • Example 11 A main component of the addition-reaction-type silicone resin similar to that of Example 13 was formed on the surface of the -axis-stretched polyethylene terephthalate obtained by laminating the antistatic layer obtained in 1 where the antistatic layer was not laminated. A release layer as a component was laminated, and a surface protective film was obtained in which an antistatic layer was laminated on one side and a release layer was laminated on the other side. The testability of the polarizing plate using this surface protective film was good. In addition, the surface protective film did not generate static electricity when it was peeled off, and was good with little adhesion of dust. « ⁇ ⁇
  • Example 17 a release layer mainly composed of an addition reaction type silicone resin similar to that of Example 13 was laminated on the surface of the uniaxially stretched polyethylene terephthalate on which the antistatic layer was laminated, and charged on one side. A surface protection film laminated in the order of the prevention layer and the release layer was obtained. The testability of the polarizing plate using this surface protective film was good. The surface protective film did not generate static electricity when peeled off, and had good adhesion with little dust. Comparative Example 3
  • Polyethylene terephthalate was melt-extruded through a film forming die onto a water-cooled rotary quenching drum to produce an unstretched film.
  • This unstretched film was stretched 4.0 times at 90 ° C. in the width direction. Further, the film was thermally fixed in the width direction at 255 ° C., and subsequently subjected to a 4% relaxation treatment at 200 ° C. to obtain a uniaxially stretched polyethylene terephthalate film having a thickness of 46 ⁇ m.
  • a surface protection film having a pressure-sensitive adhesive layer laminated on one side was obtained in the same manner as in Example 1 except that the obtained uniaxially stretched polyethylene terephthalate film was used.
  • Polyethylene terephthalate was melt-extruded through a film forming die onto a rotating quenching drum cooled with water cooling water to produce an unstretched film.
  • This unstretched film was stretched 3.2 times at 90 ° C in the longitudinal direction, then stretched 3.5 times at 90 ° C in the width direction, and heat-fixed at 220 ° C, thickness of 50 m.
  • a biaxially stretched polyethylene terephthalate film instead of the uniaxially stretched polyethylene terephthalate film, A surface protection film having a pressure-sensitive adhesive layer laminated on one surface was obtained in the same manner as in Example 1 except that the biaxially stretched polyethylene terephthalate film obtained in Example No. 0/00406 was used.
  • the maximum distortion of the main orientation axis is 27 degrees
  • the minimum value of contrast is 2
  • the heat shrinkage at 120 ° C is 0.6%
  • the haze is 0.
  • the light transmittance was 1%
  • the total light transmittance was 90%
  • the retardation value was 900 nm.
  • This surface protective film had a large contrast difference in the width direction, and light interference was observed. Therefore, the testability of the polarizing plate using the surface protective film was poor.
  • the surface protective film of the present invention is characterized in that, by using a polymer film having a maximum distortion value of a specific orientation main axis as a base film, optical evaluation (for example, components of a liquid crystal display device such as a polarizing plate and a retardation plate) is performed. Inspection of the contrast, display ability, hue, optical defects, etc.) of the protective film can be performed without peeling off the protective film, and the defect can be seen more easily. The cost can be reduced by using an inexpensive resin with excellent overall performance, such as polyethylene terephthalate.
  • FIG. 1 is a cross-sectional view schematically showing one example of the surface protective film of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing one example of the surface protective film of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing one example of the surface protective film of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing one example of the surface protective film of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing one example of the surface protective film of the present invention.
  • FIG. 6 is a cross-sectional view schematically showing one example of the surface protective film of the present invention.
  • FIG. 7 is a cross-sectional view schematically showing an example in which the surface protective film of FIGS. 1 and 4 is bonded to a polarizing plate as an example of an optical member.
  • FIG. 8 is a schematic diagram of a sampling method for evaluating the lowest contrast of a polymer film>.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un film de protection de surface comportant un film polymère, et une couche d'adhésif autocollant ou une couche antiadhésive formée sur une face de celui-ci. Le film polymère présente une déformation maximale dans l'axe d'orientation principal égale ou inférieure à 10 degrés. Le film de protection de surface convient pour protéger, par exemple, une plaque de résine synthétique, et convient spécialement pour protéger une surface d'un élément constituant d'un affichage à cristaux liquides, telle une plaque polarisante ou une plaque de phase. Ce film de protection de surface est utile car il n'a pas besoin d'être enlevé pour permettre une inspection du produit protégé, le film présentant une efficacité d'inspection satisfaisante, et il est en outre bon marché.
PCT/JP2000/000406 1999-01-27 2000-01-27 Film de protection de surface WO2000044841A1 (fr)

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WO2004049021A1 (fr) * 2002-11-25 2004-06-10 Mitsubishi Polyester Film Corporation Film de protection de la surface d'un element optique
WO2005109051A1 (fr) * 2004-05-11 2005-11-17 Nitto Denko Corporation Pellicule de protection de polarisant, plaque de polarisation et écran
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JP2003027019A (ja) * 2001-07-23 2003-01-29 Hitachi Chem Co Ltd 光学シート保護用粘着フィルム
WO2003107049A1 (fr) * 2002-06-18 2003-12-24 日東電工株式会社 Plaque de polarisation munie d'une couche de compensation optique et dispositif d'affichage d'images
US7126754B2 (en) 2002-06-18 2006-10-24 Nitto Denko Corporation Polarization plate with optical compensation layer and image display device
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