JP2005241793A - Storage box having stand, production method and storage method of optical film, optical film, polarizing plate and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a storage box having stand for a long-size film stock of an optical film wound like a roll, which causes no deflection and sticking upon the storage or transfer and hardly produces coating irregularities when forming a functional thin film thereon, to provide a production method and a storage method of optical film using the storage box, and to provide the optical film, a polarizing plate and a display device . <P>SOLUTION: The storage box is provided with the stand having a means that rotates the film stock of transparent plastic film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a storage box having a gantry, a method for manufacturing and storing an optical film, and an optical film, a polarizing plate, and a display device, and more particularly, a gantry for a long roll of an optical film that is wound into a roll. The present invention relates to a storage box having, a manufacturing method and a storage method of an optical film using the storage box, an optical film, a polarizing plate, and a display device.

  In addition to the CRT, various display devices such as a liquid crystal television, a plasma display (PDP), and an organic EL display have been developed, and their screen sizes are increasing. With an increase in screen size and image quality, an optical film on which an antireflection layer or the like is formed is attached to the front surface of a display device in order to improve visibility. In addition, such a large-screen display device is easily scratched because it may be directly touched by hands or touched by objects. Therefore, an antireflection film with a hard coat layer in which a hard coat layer is usually formed on a support for preventing scratches and an antireflection layer or the like is formed thereon has been used.

  As the antireflection film, a wide film having a size of 1000 mm or more, and further 1400 mm or more is required due to the large screen. However, when it becomes wider due to the increase in size as described above, uneven color and periodic unevenness occur in the reflection performance, coloring degree, phase difference performance, visual field expansion performance, etc. There is a need for a highly uniform optical film that is free from differences between the outside and inside the winding, between the center and the end in the width direction, and between lots.

  Conventionally, when handling long-rolled plastic film substrates, rolls wound around the core can be tightened and preserved by providing portions that are bulkier than the film surface called knurling or embossing on both sides of the film. A method for preventing time folding or the like from occurring is known (for example, see Patent Documents 1 and 2).

However, even if these measures are taken, if the plastic film substrate is wide or the winding length is long, the plastic film substrate is likely to be unwound due to its own weight, and bends and sticks during storage and transport. May occur. Moreover, it turned out that there exists a problem that an application | coating nonuniformity tends to arise when transferring such a plastic film base material and providing a functional thin film on it.
Japanese Patent Laid-Open No. 2002- 211803 Japanese Patent No. 3226190

  Accordingly, an object of the present invention is to prevent the occurrence of deflection and sticking during storage or transfer, and to prevent uneven coating when a functional thin film is provided thereon, and to roll an optical film original roll wound up in a roll shape. An object of the present invention is to provide a storage box having a mounting base, an optical film manufacturing method and storage method using the storage box, an optical film, a polarizing plate, and a display device.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A storage box having a gantry comprising means for rotating a transparent plastic film original.

(Claim 2)
The storage box having a gantry according to claim 1, further comprising means for rotating the transparent plastic film raw material once or more in two weeks.

(Claim 3)
The transparent plastic film original fabric is a cellulose ester film having a film width of 1.35 m or more and a thickness of 25 μm to 110 μm, and at least both end portions are provided with thick films or uneven bands. A storage box having the mount according to claim 1.

(Claim 4)
A method for producing an optical film, comprising: providing a hard coat layer on a transparent plastic film raw material rotated during storage in a storage box having the mount according to any one of claims 1 to 3.

(Claim 5)
Furthermore, an antistatic layer is provided, The manufacturing method of the optical film of Claim 4 characterized by the above-mentioned.

(Claim 6)
Furthermore, an antireflection layer is provided, The manufacturing method of the optical film of Claim 4 or 5 characterized by the above-mentioned.

(Claim 7)
The optical film manufactured by the method for manufacturing an optical film according to any one of claims 4 to 6 is stored in a storage box having the mount according to any one of claims 1 to 3. And storage method of optical film.

(Claim 8)
An optical film manufactured by the method for manufacturing an optical film according to any one of claims 4 to 6.

(Claim 9)
An optical film stored by the optical film storage method according to claim 7.

(Claim 10)
A polarizing plate comprising the optical film according to claim 8.

(Claim 11)
A display device comprising the polarizing plate according to claim 10.

  According to the present invention, there is no deflection or sticking during storage or transfer, and when a functional thin film is provided thereon, coating unevenness is unlikely to occur, and a base for a long-rolled optical film substrate wound in a roll shape , A manufacturing method and a storage method of an optical film using the storage box, and an optical film, a polarizing plate, and a display device can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The present invention is characterized in that the transparent plastic film original fabric is stored in a storage box having a gantry characterized by having means for rotating the transparent plastic film original fabric, and the original fabric is rotated during the storage. .

  Hereinafter, the present invention will be described in detail.

  Long-rolled plastic film base material is used after heat treatment to increase the film strength of the layer after film formation or after providing a functional thin film on the film, and further after providing a functional thin film. The roll wound around the plastic core is rotated while being wound. Although there is no restriction | limiting in particular in rotation speed, It is preferable to rotate 1 rotation or more at least for 2 weeks. It is more preferable for obtaining the effect of the present invention to rotate more than once per week, more preferably more than once per day. Furthermore, when performing the said heat processing, it is preferable to increase a rotation speed, and a continuous or intermittent rotation may be sufficient.

  A storage box having a dedicated rotating mount is provided to rotate the long optical film roll wound around the core. When performing the heat treatment, it is more preferable to set an optical film roll on a dedicated frame having a heat-resistant rotation function and rotate the heat treatment in the heating chamber during the heat treatment.

  FIG. 1 shows a sectional view of a cart having a rotation function. In FIG. 1, an optical film 23 wound around a winding core 22 is wound in a roll shape and stored in a box 21. Both ends of the core of the roll are supported by bearings 24, and one end of the core has a mechanism for transmitting rotation from the drive motor M through the drive roller 25. The box body 21 may have a lid body 26.

  In the case of intermittent rotation, the stop time is preferably within 10 hours, the stop position is preferably made uniform in the circumferential direction, and the stop time is within 10 minutes. More preferred. Most preferred is continuous rotation.

  As for the rotation speed in continuous rotation, the time required for one rotation is preferably 10 hours or less, and if it is early, it becomes a burden on the apparatus, so the range of 15 minutes to 2 hours is substantially preferable.

  In the case of a dedicated stand having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, rotation is effective as a countermeasure against black bands that occur when the storage period is long. Function.

  When the roll is rotated, there is a possibility that the film may be damaged, and it is necessary to cover the film with the lid body 26 or to perform it in a clean room.

  In the present invention, the optical functional functional layer is continuously transported to a long roll plastic film to coat the optical functional functional layer, but before or after the coating step, at least one thick film or It is preferable to include a step of providing an uneven belt (also referred to as knurling). In particular, it is preferably provided at both ends of the film.

  The thick film or the uneven band is preferably provided so that its height is higher in the range of 3 to 50 μm with respect to the film surface, and the center line average roughness of the uppermost layer of the functional thin film to be coated is 0.00. When the thickness is 05 μm or less, it is preferable that the thick film or the uneven band is provided so as to be higher in the range of 2 to 30 μm with respect to the surface height of the uppermost layer.

  The surface roughness referred to here is defined by JIS B 0601, and the center line average roughness is preferably measured by an optical interference type surface roughness measuring instrument, for example, measured using RST / PLUS manufactured by WYKO. I can do it. The center line average roughness of 0.05 μm or less is a surface state where the surface is glossy, and the color unevenness and period are compared with the antiglare surface (center line average roughness of 0.1 to 2.0 μm). Even if there is very little unevenness, it is easy to see, or because the surface unevenness is small, uneven color and periodic unevenness are likely to occur due to the difference between the part that closely adheres between the laminated films when it is rolled, and the like It is estimated to be. The thick film or the concavo-convex-shaped band is more preferably raised in the range of 2 to 15 μm with respect to the surface height of the uppermost layer.

  FIG. 2 is a cross-sectional view showing the relationship between the thickness of a thick film or uneven band and the thickness of the film. In the figure, (a) is an uneven band 2 provided at the end of a transparent plastic film base material 1 (thickness d) so as to be higher in one direction by a1 with respect to the film surface, (b) Similarly, it represents that the uneven band 3 is provided higher in both directions by a1 + a2 with respect to the film surface. In the present invention, either method (a) or (b) may be used.

  These bands are preferably provided at both ends of the film substrate, but some bands may be further provided between the two bands at both ends, and the number of bands is 1 to 2 per 1 m of film width. It is preferable that

  These thick film bands may be formed by applying a resin to the surface of the film substrate, or may be provided by adhering a film having a specified thickness. The uneven belt may be formed by an embossing roller.

  The embossing width is preferably 5 to 40 mm, more preferably 7 to 15 mm. It is preferable that embossing is applied to the 0 to 50 mm portion from the end of the film, and the form of embossing is not limited, but the number of embossing processed in one place may be one or two or more. It doesn't matter. It is particularly preferable that it is made at both ends.

The ratio of the area of the portion observed as the protrusion of each embossed line to the entire embossed part is preferably about 15 to 50%, and when the protrusions included in each of these lines are discontinuous, The number is preferably about 10 to 30 per cm ² .

  Embossing can usually be performed by pressing an embossed ring engraved on the film on a back roll of metal or rubber. Processing can be performed at room temperature, but it is preferable to process at Tg + 20 ° C. or higher and melting point (Tm) + 30 ° C. or lower.

  These bands are preferably provided at the same time as the production of the transparent plastic film substrate, and are formed by pressing the embossed portions at both ends again by being sandwiched when the substrate is stretched. Alternatively, a method of providing a new band after excising the sandwiched embossed portion may be used.

  An optical film coated with a functional thin film having these bands is wound into a roll shape, and it is preferably subjected to a heat treatment for 3 days or more at 42 ° C. or higher in a state of being wound in a roll shape at a temperature of 50 It is preferable that the temperature is in the range of from 120 ° C. to 120 ° C., and the period is preferably from 3 days to 30 days.

  In order to stably perform the heat treatment, it is necessary to perform in a place where the temperature and humidity can be adjusted, and it is preferable to perform in a heat treatment chamber such as a clean room without dust.

  When winding the optical film coated with the functional thin film having these bands into a roll, the wound core may be of any material as long as it is a cylindrical core, but preferably Is a hollow plastic core, and the plastic material may be any heat-resistant plastic that can withstand the heat treatment temperature, such as phenol resin, xylene resin, melamine resin, polyester resin, epoxy resin, etc. Resin. A thermosetting resin reinforced with a filler such as glass fiber is preferable.

  The number of windings to these winding cores is preferably 100 windings or more, more preferably 500 windings or more, the winding thickness is preferably 5 cm or more, and the width of the film substrate is 80 cm or more. It is preferably 1 m or more.

  The optical film according to the present invention is an optical film having a functional thin film on a transparent plastic film substrate.

  The transparent plastic film substrate used in the present invention is at least one selected from cellulose ester resin, polyester resin, polycarbonate resin, allyl carbonate resin, polyethersulfone resin, polyacrylate resin, norbornene resin, and acrylic styrene resin. In view of optical uniformity, cellulose ester resins and polycarbonate resins are more preferable, and cellulose ester resins are particularly preferable.

  Examples of the transparent plastic film used in the present invention include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene films, polypropylene films, polycycloolefin films, cellophane, cellulose acetate films, cellulose acetate butyrate films, and cellulose acetate phthalate films. , Cellulose acetate propionate film, cellulose triacetate, cellulose ester film such as cellulose nitrate or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film , Cycloolefin Rimmer film (eg, ARTON (manufactured by JSR), ZEONEX, ZEONOR (manufactured by ZEON)), polymethylpentene film, polyetherketone film, polyethersulfone film, polysulfone film, polyetherketoneimide film, polyamide film And acrylic film or polyacrylate film.

  In the present invention, cellulose ester films such as cellulose acetate propionate film and cellulose triacetate film (TAC film) (for example, Konica Minolta Op KONICA MINOLTATAC KC4UX2MW, KC8UX2MW, KC4UY, KC8UY, KC5UN, KC12UR, KC8UCR3 etc. are preferably used), cycloolefin polymer film, polycarbonate film, polyester film or polyacrylic film are preferred in terms of transparency, mechanical properties, no optical anisotropy, etc., especially cellulose ester film, cycloolefin polymer A film is preferred, and a cellulose ester film is particularly preferred. These resin films may be films formed by a melt casting method or a solution casting method.

  Moreover, in this invention, the film which laminated | stacked these resin may be sufficient, and the film which mixed may be sufficient, and the resin layer and the inorganic layer may be applied to these base materials according to the use.

(Cellulose ester film)
Among the films described above, cellulose esters particularly preferably used are cellulose triacetate and cellulose acetate propionate. Further, from the viewpoint of base strength, cellulose acetate having a polymerization degree of 250 to 400 and a bound acetic acid amount of 54.0 to 62.5% is preferably used, and the weight average molecular weight is preferably 70000 to 120,000, more preferably 80000 to 100,000. preferable. More preferred is cellulose triacetate with a bound acetic acid content of 58-62.5%. A film prepared by mixing cellulose acetate propionate or cellulose diacetate from 1:99 to 99: 1 with this cellulose acetate is also preferably used.

  The ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 1.0 to 5.0, and particularly preferably 1.4 to 3.0.

  As the cellulose triacetate used in the present invention, either cellulose triacetate synthesized from cotton linter or cellulose triacetate synthesized from wood pulp can be used alone or in combination. In case of film formation by casting, if peelability from the belt or drum becomes a problem, it is preferable to use a large amount of cellulose triacetate synthesized from a cotton linter that has good peelability from the belt or drum. . When cellulose triacetate synthesized from wood pulp is mixed and used, the ratio of cellulose triacetate synthesized from cotton linter is preferably 40% by mass or more, and the effect of releasability becomes remarkable, more preferably 60% by mass or more. Most preferably, it is used alone.

  About these cellulose esters, many things are known about the manufacturing method of cellulose ester by casting, the additive of cellulose ester, etc., additives, such as a mat agent, a plasticizer, and UV absorber, Production methods are described in, for example, Japanese Patent Application Laid-Open No. 10-237186, Japanese Patent Application Nos. 11-238290 and 11-353162, and these techniques can be used. Moreover, the cellulose acylate film described in JP-A-2002-179701 and 2002-241512 is also preferably used as the cellulose ester film used in the present invention.

  The long film of the present invention specifically shows a film of about 100 to 5000 m, with a width of 1.35 m or more, preferably 1.35 to 4 m, and a film thickness of 25 μm to 110 μm, preferably 35 to 70 μm. A long film is preferably used. Usually, it is of the form provided in roll form. Further, the long film of the present invention is particularly preferably provided with the above-described thick film or uneven band.

  The optical film according to the present invention has a functional thin film on these transparent plastic film substrates. The functional thin film includes antireflection, antiglare, infrared absorption, ultraviolet absorption, antistatic, and electromagnetic wave shielding. It is a thin film having functions such as improvement of scratch resistance, improvement of antifouling property, phase difference for optical compensation, field of view enlargement and the like. In particular, the optical film according to the present invention is used by being affixed to the surface of a large display device, and is preferably a functional thin film mainly intended for antireflection.

A preferred example of a layer structure mainly composed of antireflection is shown below.
Film substrate / hard coat layer / low refractive index layer film substrate / hard coat layer / high refractive index layer / low refractive index layer film substrate / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index Layer film substrate / antiglare layer / high refractive index layer / low refractive index layer film substrate / electromagnetic wave blocking layer / medium refractive index layer / high refractive index layer / low refractive index layer film substrate / antistatic layer / hard coat Layer / medium refractive index layer / high refractive index layer / low refractive index layer antistatic layer / film substrate / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer film substrate / antistatic layer / Medium refractive index layer / high refractive index layer / low refractive index layer / antifouling layer film substrate / infrared absorption / electromagnetic wave blocking layer / medium refractive index layer / high refractive index layer / low refractive index layer film substrate / antiglare layer / High refractive index layer / Low refractive index layer / High refractive index layer / Low refractive index layer If the reflectance can be reduced by optical interference For example, it is not limited to only these layer configurations. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment. In addition, each of the above layers generally has the functions of anti-glare, infrared absorption, ultraviolet absorption, antistatic, electromagnetic wave blocking, abrasion resistance improvement, and antifouling improvement, and each layer functions for each purpose. It is possible to contain a conventionally known compound for imparting.

  Further, as a thin film for optical compensation, liquid crystal polymers described in JP-A-3-9326, JP-A-3-291601, JP-A-5-215922, JP-A-8-50206, JP-A-2002-139622 Further, it is possible to provide a function of enlarging the phase difference and the viewing angle by a thin film mainly composed of a polymerizable rod-shaped compound or discotic compound, and it is also preferable to combine it with a functional thin film for preventing reflection.

(Hard coat layer)
It is preferable to provide a hard coat layer (hereinafter also referred to as a clear hard coat layer) on the substrate. The hard coat layer is preferably an actinic radiation curable resin layer that is cured by actinic radiation such as ultraviolet rays. An antireflection layer and an antireflection film excellent in scratch resistance can be obtained by forming each constituent layer mainly composed of a metal oxide on the resin layer cured with ultraviolet rays.

  The hard coat layer used in the present invention is preferably a hard coat layer containing an actinic radiation curable resin and fine particles.

  Examples of the fine particles include inorganic particles and organic particles.

  Examples of inorganic fine particles that can be used in the present invention include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, antimony oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, and clay. , Calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate, or a composite oxide thereof.

  Of these, silicon oxide, titanium oxide, tin oxide, indium oxide, ITO, zirconium oxide, antimony oxide, or a composite oxide thereof is preferably used.

  Organic fine particles include poly (meth) acrylate resins, silicon resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used. It is particularly preferable to contain conductive fine particles.

  Fine particles having a particle diameter of 1 nm to 10 μm are used, and particles of 5 nm to 5 μm are particularly preferable. Particularly preferably, it contains particles of 5 nm to 1 μm. A combination of fine particles having different compositions, particle sizes, and refractive indexes can also be used. For example, silicon oxide and zirconium oxide or silicon oxide and ITO fine particles can be used in combination.

  The actinic radiation curable resin refers to a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. For example, a component containing a monomer having an ethylenically unsaturated double bond is preferably used and cured by irradiating an active ray such as an ultraviolet ray or an electron beam to form a hard coat layer. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and reacted to form an oligomer. The thing as described in 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. I can list them.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. For example, commercially available products such as Irgacure 184 and Irgacure 907 (manufactured by Ciba Specialty Chemicals) are preferably used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. As monomers having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyl dimethyl diacrylate, the above-mentioned trimethylolpropane Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB Corporation); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), DPHA (manufactured by Nippon Kayaku Co., Ltd.) or the like can be appropriately selected and used.

  Specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  In addition, for adjusting the refractive index, hard coat coating solutions containing ultrafine zirconium oxide dispersions Desolite Z-7041 and Desolite Z-7042 (manufactured by JSR Corporation) are also used alone or other ultraviolet curable resins, etc. It can be added to and mixed with.

  The actinic radiation curable resin used in the present invention can be cured by irradiation with actinic rays such as electron beams or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used. In the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. .

  The proportion of the actinic radiation curable resin composition and the fine particles is desirably blended so as to be 0.1 to 40 parts by mass with respect to 100 parts by mass of the resin composition.

(Refractive index of hard coat layer)
The refractive index of the hard coat layer according to the present invention is 1.5 to 2.0, more preferably 1.6 to 1.8. The refractive index of the cellulose ester film used as the transparent support is about 1.5. When the refractive index of the hard coat layer is too small, the antireflection property is lowered. Furthermore, when this is too large, the color of the reflected light of the antireflection film becomes strong, which is not preferable. The refractive index of the hard coat layer according to the present invention is particularly preferably in the range of 1.60 to 1.70 from the viewpoint of optical design for obtaining a low reflective film. The refractive index of the hard coat layer can be adjusted depending on the refractive index and content of the fine particles to be added.

(Hard coat layer thickness)
The film thickness of the hard coat layer according to the present invention is the average film thickness of 10 portions of the resin part of the hard coat layer when the cross-section is observed with an electron microscope, and the film thickness of the present invention is sufficient. From the viewpoint of imparting properties, the hard coat layer preferably has a thickness of 0.5 μm to 10.0 μm, and more preferably 1.0 μm to 8.0 μm. The hard coat layer may be composed of two or more layers.

(Haze of hard coat layer)
The haze value of the hard coat layer is preferably 1 to 30%, and particularly preferably 3 to 15%. If the haze is small, the effect of preventing reflection is insufficient, and if the haze value is large, scattering on the surface and inside is too strong, which causes problems such as a decrease in image sharpness and whitening, which is not preferable.

  Here, the haze can be measured according to ASTM-D1003-52.

  Means for adjusting the haze value of the hard coat layer according to the present invention to a preferred range include the above-mentioned particles, fine particles, or solvent-soluble resins (for example, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate). A preferable example is a rate, an acrylic resin, etc.).

  These hard coat layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, the dose of active ray is a 0.5 J / cm ² or less, preferably 0.1 J / cm ² or less.

  The irradiation time for obtaining the irradiation amount of active rays is preferably about 0.1 second to 1 minute, and more preferably 0.1 to 10 seconds from the viewpoint of the curing efficiency or work efficiency of the curable resin.

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or the biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  Examples of the organic solvent for the hard coat layer coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents can be appropriately selected or used by mixing them. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  Further, it is particularly preferable to add a silicon compound to the coating liquid for the hard coat layer. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1000 to 100000, preferably 2000 to 50000. If the number average molecular weight is less than 1000, the drying property of the coating film decreases, and conversely, the number average When the molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, are preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  As the coating method of the hard coat layer coating solution, the above-described methods can be used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm, as the wet film thickness.

(Antistatic layer)
It is also preferable to provide an antistatic layer together with a hard coat layer on the substrate. The method for forming the antistatic layer is not particularly limited, and can be provided by the atmospheric pressure plasma CVD method as described above, and as described in JP-A No. 2000-352620, an ion conductive material or a conductive material can be used. It can also be provided by applying a layer containing conductive fine particles. In this case, examples of the ion conductive material include ionic polymer compounds, and examples of the conductive fine particles include metal oxides. Preferably, a composition comprising the conductive fine particles, the ionic polymer compound, and an organic solvent is applied by a known coating method so that the dry film thickness is 0.1 to 10 μm. The conductive inorganic fine particles include tin oxide, indium oxide, zinc oxide, and titanium nitride. Tin oxide and indium oxide are particularly preferred. The inorganic fine particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom.

(Transparent conductive layer)
As the transparent conductive layer, tin oxide (SnO ₂ or the like), indium oxide, antimony oxide, zinc oxide (ZnO), cadmium oxide, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), In ₂ O ₃ − Examples thereof include metal oxides such as a ZnO-based amorphous oxide film, and metal films such as gold, silver, copper, aluminum, tin, and nickel. Among them, tin-doped indium oxide (ITO) is preferable in terms of electrical characteristics and light transmittance. The method for forming the transparent conductive layer is not particularly limited, and examples thereof include a sputtering method, a vacuum deposition method, an ion plating method, a low pressure plasma CVD method, a coating method, and an atmospheric pressure plasma CVD method. The thickness of the transparent conductive layer is preferably such that electrical conductivity is exhibited and transparency is maintained, and the surface sheet resistance is 100Ω / □ or less and the light transmittance is 85% or more. The thickness is preferably 30 nm to 200 nm.

(Electromagnetic shielding layer)
As the electromagnetic shielding layer, the above transparent conductive layer can be used. For example, JP-A-10-98292 discloses an electromagnetic shielding film using an In ₂ O ₃ —ZnO-based amorphous oxide film. Regarding the electromagnetic wave shielding function, there is a relationship between the resistance value of the transparent conductive layer and the shielding function, as shown in the following equation.

Electromagnetic wave shielding effect (dB) = 20 × Log (Ei / Et)
In the equation, Ei is the electric field intensity of the electromagnetic wave incident on the electromagnetic shielding material, and Et is the electric field intensity transmitted through the electromagnetic shielding material.

Therefore, in order to obtain a good electromagnetic shielding effect, the sheet resistance is desirably a resistance value of 100Ω / □ or less. More preferably, the resistance value is 50Ω / □ or less. In addition, the anti-reflection film has a gas barrier between the anti-reflection layer and the base material or on the back surface of the surface having the anti-reflection layer for the purpose of improving air resistance and water vapor resistance (hereinafter collectively referred to as gas barrier properties). A layer can be provided. Examples of the gas barrier layer material include a method of laminating a polyvinyl alcohol resin, a polyvinylidene chloride resin, a transparent epoxy resin, and the like (JP 61-41122 A, JP 3-9323 A), SiO ₂ , SiO _x , There is a method of providing an inorganic oxide layer such as Al ₂ O _x (Japanese Patent Laid-Open No. 61-183810). The inorganic oxide layer is produced by a vapor deposition film forming method such as a sputtering method, a vacuum deposition method, an ion plating method, a low pressure plasma CVD method, or an atmospheric pressure plasma CVD method. The thickness of the inorganic oxide layer is preferably in the range of 5 nm to 100 nm. If the film thickness is less than 5 nm, pinholes are likely to occur, and the gas barrier properties are likely to be lowered. On the other hand, if the film thickness is larger than 100 nm, the flexibility is lowered and the transparency is also lowered.

(Anti-fouling layer)
As described above, an antifouling layer can be provided on the surface of the antireflection layer in order to improve the antifouling property. The method of providing the antifouling layer is not particularly limited, and can be provided by atmospheric pressure plasma CVD as described above, and a fluorinated silane coupling agent is applied on the antireflection layer by a coating apparatus such as a micro gravure coater. It can also be provided by drying. As a commercial item of the said fluorine-type silane coupling agent, the coating agent "KP-801M" by Shin-Etsu Chemical Co., Ltd. can be mentioned, for example.

  JP-A-6-122778 discloses a fluoroalkylsilazane water-repellent layer using a vacuum deposition method, and JP-A-6-122778 discloses a water-repellent layer formed using a plasma CVD method. No. 8-209118 discloses an antifouling layer comprising a mixture of a fluorine compound and an organopolysiloxane, and JP-A-9-61605 discloses an antifouling layer using a fluorine compound having a flexible molecular structure having an ether bond. Is disclosed.

(Anti-curl layer)
When surface processing is performed only on one side of the film substrate, or when different types or different levels of surface processing are performed on both sides, a curling phenomenon that the film is rounded easily occurs. Curling is inconvenient and difficult to handle when using this to produce a polarizing plate.

  In order to prevent curling, an anti-curl layer can be provided on the opposite side of the hard coat layer. That is, the degree of curling is balanced by imparting the property of curling with the surface provided with the anti-curl layer inside. The anti-curl layer is preferably applied also as a blocking layer. In this case, the coating composition can contain the above-mentioned inorganic fine particles and / or organic fine particles for imparting a blocking preventing function. (This layer is also referred to as a backcoat layer.) The order of applying the anti-curl layer is to apply an optical functional layer (for example, an antistatic layer, a hard coat layer, or an optical interference layer) on the opposite side of the substrate. Although it may be before or after the coating, it is desirable to coat it first when the anti-curl layer also serves as an anti-blocking layer.

  As a method for forming these functional thin films, various methods such as a coating method, vacuum deposition, plasma CVD method, and sputtering method can be used. Preferably, a coating solution in which inorganic fine particles are dispersed in a binder solution is applied. Thus, the method of forming the antireflection laminate is a preferable method with high productivity.

As described above in the layer configuration of the functional thin film, as the antireflection layer, a metal oxide film or an organic polymer film having a different refractive index such as SiO ₂ , TiO ₂ , ZrO ₂ , Y ₂ O ₃ or the like can be used. Usually, it is formed by laminating four layers, but it may be a low refractive index film having a single layer and a refractive index of 1.25 or less.

  Examples of the configuration include two layers of a high refractive index layer / low refractive index layer from the transparent plastic film substrate side, and three layers having different refractive indexes, a medium refractive index layer (from a transparent substrate or a hard coat layer). In which the refractive index is high and the refractive index is lower than that of the high refractive index layer) / high refractive index layer / low refractive index layer, etc., and more antireflection layers are laminated. Proposed. Among these, it is most preferable to apply a medium refractive index layer / a high refractive index layer / a low refractive index layer in this order on a substrate having a hard coat layer in view of durability, optical characteristics, cost, productivity, and the like. is there.

  A high refractive index layer (which may be provided with a middle refractive layer) on the substrate surface, and a low refractive index layer are laminated in order toward the air, and the optical film thickness of the high refractive index layer and the low refractive index layer with respect to the wavelength of light. An optical interference layer produced by setting to a certain value to form an antireflection laminate is particularly preferred as the antireflection layer, and the refractive index and film thickness can be calculated and calculated by measuring the spectral reflectance.

  The level of the refractive index is almost determined by the metal or compound contained therein. For example, Ti is high, Si is low, F-containing compounds are further low, and the refractive index is set by such a combination.

  Hereinafter, as one of the methods for forming an antireflection layer by a coating method preferably used in the present invention, a high refractive index layer (or medium refractive index layer) is formed using an active energy ray reactive metal alkoxide compound. The method to do is described.

  The high refractive index layer preferably used in the present invention is selected from a metal alkoxide having no active energy ray-reactive group and a hydrolyzate thereof as at least one of the multilayer antireflection layers on the transparent plastic film substrate. A high refractive index composition containing at least one active energy ray-reactive metal alkoxide compound represented by general formula (I) described later and an active energy ray-reactive compound excluding the compound of general formula (I) After coating on the transparent plastic film substrate, the coating film is irradiated with active energy rays to form a high refractive index layer having an arbitrary refractive index.

Any metal selected from metal alkoxides and partial hydrolysates thereof used in the high refractive index layer of the present invention, and active energy ray-reactive metal alkoxide compounds of the general formula (I) to be described later It is the same, and the metals include Al, Si, Ti, V, Ni, Cu, Zn, Y, Ga, Ge, Zr, In, Sn, Sb, Sr, La, Ta, Tl, W, Ce, and Nd. Can be mentioned. Any of the metal compounds of the active energy ray-reactive metal alkoxide compound of the general formula (I) described later is useful for changing the refractive index of the layer containing them, particularly by ultraviolet irradiation. Preferred metals are Al, Si, Ti, V, Zn, Y, Zr, In, Sn, Sr, Ta, Tl, W, and Ce. Particularly preferred metals that easily change the refractive index are Ti, Zr, Tl, (as in-Sn complex) an in, a Sr (as Sr-TiO ₂ complex).

  The active energy dose required for changing the refractive index used in the present invention, particularly the ultraviolet irradiation amount, may be approximately the same as the irradiation amount for reacting and curing the ultraviolet reactive compound described below. Moreover, it is possible also by plasma irradiation, heat processing, etc. as active energy.

  As a metal alkoxide which does not have an active energy ray reactive group used for this invention, although a C1-C10 thing is good, Preferably it is C1-C4. The hydrolyzate of metal alkoxide reacts like -metal atom-oxygen atom-metal atom when the alkoxide group is hydrolyzed to form a crosslinked structure and form a hardened layer.

Examples of metal alkoxides having no active energy ray reactive group used in the present invention; Al alkoxides include Al (O—CH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (Oi−) _{C 3 H 7) 3, Al} (O-n-C 4 H 9) 3; examples of _{Si, Si (OCH 3) 4,} Si (OC 2 H 5) 4, Si (O-i-C 3 H ₇ ) ₄ , Si (Ot-C ₄ H ₉ ) ₄ ; Examples of Ti include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H _7). ) ₄ , Ti (Oi-C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ 2 to 10-mer, Ti ( O-i-C ₃ H ₇ ) ₄ di- to 10-mer, Ti (On-C ₄ H ₉ ) ₄ di- to 10-mer, examples of V include VO (OC ₂ H ₅ ) ₃ ; As an example of Zn, Zn (OC ₂ H ₅ ) ₂ ; Y as an example Y (OC ₄ H ₉ ) ₃ ; Zr as examples, Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (On-C ₃ H ₇ ) ₄ , Zr (Oi-C ₃ H ₇ ) ₄ , Zr (Oi-C ₄ H ₉ ) ₄ , Zr (On-C ₄ H ₉ ) ₄ dimer to 10-mer; is, in (O-n-C 4 H 9) 3; examples of Sn is, Sn (O-n-C 4 H 9) 4, as an example of Ta is _{Ta (OCH 3) 5, Ta} (O- _{n-C 3 H 7) 5} , Ta (O-i-C 3 H 7) 5, Ta (O-n-C 4 H 9) 5; examples of W _{are, W (OC 2 H 5)} 6; Examples of Ce include Ce (OC ₃ H ₇ ) ₃ . These can be used alone or in combination of two or more. Among them, Ti (O-n-C 3 H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H _{7) 4} 2-10 mer, Ti (O-n-C 4 H 9) 4 2-10 mer; Zr (O-i-C 3 H 7) 4, Zr (O-n-C 4 _{H 9) 4; Si (OC} 2 H 5) 4, Si (O-i-C 3 H 7) 4 are particularly preferred.

  Further, the metal alkoxide may be used after being hydrolyzed (partially or completely hydrolyzed), and can be obtained, for example, by hydrolyzing the metal alkoxide in an organic solvent in the presence of an acidic catalyst or a basic catalyst. . Examples of the acidic catalyst include mineral acids such as nitric acid and hydrochloric acid, and organic acids such as oxalic acid and acetic acid, and examples of the basic catalyst include ammonia.

  The layer containing the metal alkoxide compound used in the present invention is one in which the metal alkoxide itself is self-condensed to be crosslinked and network-bonded. Catalysts and curing agents can be used to promote the reaction. These include metal chelate compounds, organometallic compounds such as organic carboxylates, organosilicon compounds having amino groups, photoacid generators, etc. There is. Particularly preferable among these catalysts or curing agents are an aluminum chelate compound and an acid generator (photoacid generator) by light. Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate and aluminum trisethyl. Acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetonate, etc. Examples of other photoacid generators include benzyltriphenylphosphonium hexafluorophosphate and other Examples thereof include phosphonium salts and salts of triphenylphosphonium hexafluorophosphate.

  For the coating composition containing a metal alkoxide having no active energy ray-reactive group and / or a hydrolyzate thereof, a chelate compound is added after reacting with a β-diketone for the storage stability of the coating solution. , A stable coating composition can be obtained. Specific examples of this β-diketone include methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetylacetone, and the like. Ethyl acetoacetate. β-diketone is used in a molar ratio of 0.5 to 2 with respect to the metal alkoxide or a hydrolyzate thereof, and a more preferable range is 0.8 to 1.2.

  The active energy ray-reactive compounds excluding the compound represented by the following general formula (I) preferably used for the high refractive index layer of the present invention are a polymerizable vinyl group, allyl group, acryloyl group, methacryloyl group, isopropenyl group, What has two or more polymeric groups, such as an epoxy group, and forms a crosslinked structure or network structure by active energy ray irradiation is preferable. Among these active groups, an acryloyl group, a methacryloyl group or an epoxy group is preferable from the viewpoint of polymerization rate and reactivity, and a polyfunctional monomer or oligomer is more preferable.

  Examples of the active energy ray-curable resin having an acrylic group or a methacryl group include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin. I can list them.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, JP-A-59-151110).

  An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaerythritol.

  In order to initiate photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound, the active energy ray-reactive compound alone is initiated. However, since the polymerization induction period is long or the initiation of polymerization is delayed, It is preferable to use a sensitizer or a photoinitiator, whereby the polymerization can be accelerated. Known photosensitizers and photoinitiators can be used. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, tetramethyluram monosulfide, thioxanthone, and derivatives thereof.

  In the case of an active energy ray-reactive compound having an epoxy acrylate group, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used for the active energy ray-reactive compound is sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet-reactive compound, Preferably it is 1-10 mass parts. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the present invention, an active energy ray reactive epoxy resin is also preferably used. Active energy ray reactive epoxy resins include aromatic epoxy compounds (polyglycidyl ethers of polyhydric phenols), such as hydrogenated bisphenol A or glycidyl ethers of bisphenol A and epichlorohydrin, epoxy novolac resins, aliphatic epoxies. Examples of the resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, and typical examples thereof , Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Ripropylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, diglycerol triglycidyl ether , Diglycerol tetraglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of sorbitol, cycloaliphatic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3 ′ , 4'-Epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) 5,5-spiro-3 ', 4'-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) ) Adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) dicyclopentadiene diepoxide, di (3 , 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, tri (2-hydroxyethyl) isocyanurate triglycidyl ether, polyglycidyl acrylate, polyglycidyl methacrylate, glycidyl acrylate or a copolymer of glycidyl methacrylate and other monomers, poly-2-glycidyloxyethyl acrylate, poly-2- Examples include glycidyloxyethyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl acrylate or a copolymer of 2-glycidyloxyethyl methacrylate and other monomers, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like. Or an addition polymer obtained by combining two or more of them individually. The present invention is not limited to these compounds but includes compounds inferred from these compounds.

  In the active energy ray-reactive compound epoxy resin, in addition to those having two or more epoxy groups in the molecule, monoepoxide can be blended and used according to desired performance.

  The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

  Silver ethyl sulfonate, silver polyborate and the like can also be preferably used.

  Useful active energy ray-reactive epoxy resins polymerize a compound that releases a substance that initiates cationic polymerization upon irradiation with active energy rays, using a photopolymerization initiator or a photosensitizer. A group of double salts with onium salts that release Lewis acids that are cationically polymerized by irradiation is particularly preferred.

  A typical example is a compound represented by the following general formula (III).

General formula (III)
[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{+ w} [MeX _v ] ^−w
Wherein the cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion. The value obtained by subtracting the valence of the central atom Me from v is w.

Specific examples of the anion [MeX _v ] ^-w of the above general formula include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₄ ⁻ ), hexafluoroantimonate (SbF ₄ ⁻ ), hexafluoroarsenate. (AsF ₄ ⁻ ), hexachloroantimonate (SbCl ₄ ⁻ ) and the like.

Further formula MeX _v (OH) ^- anions can also be used. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic haloniums described in JP-A-50-151996, JP-A-50-158680 and the like are particularly effective. Salt, VIA group aromatic onium salts described in JP-A-50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56- 149402, 57-192429, etc., oxosulfoxonium salts described in JP-B-49-17040, etc., aromatic diazonium salts described in US Pat. No. 4,139,655, etc. A thiopyrilum salt is preferred. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the active energy ray-curable resin composition useful in the present invention, the polymerization initiator is generally preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable epoxy resin (prepolymer). More preferably, it is added in the range of 1 to 10 parts by mass. An epoxy resin can also be used in combination with the urethane acrylate type resin, polyether acrylate type resin, and the like. In this case, it is preferable to use an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator in combination.

In the active energy ray curable resin-containing layer used in the present invention, a binder such as a known thermoplastic resin, thermosetting resin or hydrophilic resin such as gelatin can be mixed with the active energy ray curable resin. . These resins preferably have a polar group in the molecule, and examples of the polar group include —COOM, —OH, —NR ₂ , —NR ₃ X, —SO ₃ M, —OSO ₃ M, —PO ₃ M ₂ , —OPO ₃ M (wherein M represents a hydrogen atom, an alkali metal or an ammonium group, X represents an acid forming an amine salt, R represents a hydrogen atom or an alkyl group), and the like. .

  Next, the active energy ray-reactive metal alkoxide compound of the general formula (I) used in the present invention will be described.

Formula (I)
M (R ₁ ) _m (R ₂ ) _n (OR ₃ ) _p
Here, O is an oxygen atom, R ₁ is an active energy ray reactive group, and represents a group having a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, a methacryloyl group, or an epoxy group, and R ₂ has 1 carbon atom. Represents an aliphatic hydrocarbon group having ˜4, R ₃ represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, m + n + p = q, q is a metal valence, and q−1 ≧ m ≧ 1, q−1 ≧ p ≧ 1, q−1 ≧ n ≧ 0, and m, n, and p represent positive integers.

R ₁ of the active energy ray-reactive metal alkoxide compound of the general formula (I) is an active energy ray-reactive group having an unsaturated double bond functional group, and among them, an acryloyl group, A methacryloyl group or an epoxy group is preferred from the viewpoint of reactivity. In addition, an epoxy group that is not affected by oxygen during the reaction is particularly preferred. The R ₃ O alkoxy group reacts in a chain fashion to the metal oxide while undergoing hydrolysis, like the metal alkoxide having no active energy ray reactive group.

  The active energy ray-reactive metal alkoxide compound reacts with the metal alkoxide compound having no active energy ray-reactive group while undergoing hydrolysis, and is incorporated into a metal oxide matrix to be bonded and crosslinked.

  On the other hand, the active energy ray-reactive group of the active energy ray-reactive metal alkoxide compound and the other active energy ray-reactive compound are also polymerized by the active energy ray to form a cross-linking bond with each other.

  Both of these crosslinks have a synergistic effect and the layer containing them has a very high hardness. These crosslinked structures are considered to be in a hybrid state in which an inorganic oxide and an organic polymer are bonded together. Such a hybrid state is different from a state in which a metal oxide and an organic substance coexist, and is integrated so that the hardness is high and phase separation hardly occurs. Therefore, it is easy to form a uniform coating film, and it is possible to solve problems such as insufficient hardness, white turbidity, and a decrease in transmittance.

  The active energy ray reactive group may be directly bonded to the metal, may be bonded through an oxygen atom, or may be bonded through an oxyalkyl group.

  Specific examples of the active energy ray reactive metal alkoxide include vinyltrimethoxytitanium, vinyltri (β-methoxy-ethoxy) titanium, divinyloxydimethoxytitanium, glycidyloxyethyltriethoxytitanium, γ-acryloyloxypropyltri- n-propyltitanium, γ-methacryloyloxy-n-propyltri-n-propyltitanium, di (γ-acryloyloxy-n-propyl) di-n-propyltitanium, acryloyloxydimethoxyethyltitanium, vinyltrimethoxyzircon, di Vinyloxydimethoxyzircon, acryloyloxyethyltriethoxyzircon, γ-acryloyloxy-n-propyltri-n-propylzircon, γ-methacryloyloxy-n-propyltri-n-propylzircon, di (γ Acryloyloxy-n-propyl) di-n-propylzircon, acryloyloxydimethoxyethylzircon, vinyldimethoxythallium, vinyldi (β-methoxy-ethoxy) thallium, divinyloxymethoxythallium, acryloyloxyethyldiethoxythallium, γ-acryloyl Oxy-n-propyldi-n-propylthallium, γ-methacryloyloxy-n-propyldi-n-propylthallium, di (γ-acryloyloxy-n-propyl) -n-propylthallium, acryloyloxymethoxyethylthallium, vinyltri Methoxysilane, vinyltri (β-methoxy-ethoxy) silane, divinyloxydimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethyl Rutriethoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy-n-propyltri-n-propylsilane, γ-methacryloyloxy-n-propyltri-n-propylsilane, di (γ-acryloyloxy-n- Propyl) di-n-propylsilane, acryloyloxydimethoxyethylsilane, and the like.

  Active energy rays for reactive groups of active energy ray-reactive compounds other than the active energy ray-reactive group of the general formula (I) and active energy ray-reactive compounds preferably used for the high refractive index layer of the present invention. The behavior of photopolymerization due to the above is almost the same, and the same photosensitizers and photoinitiators for the active energy ray compounds except for the general formula (I) are used.

The active energy ray can be used without limitation as long as it is an energy source that activates the compound by ultraviolet rays, electron rays, γ rays, etc., but ultraviolet rays and electron rays are preferable, and handling is particularly simple and high energy can be easily obtained. In this respect, ultraviolet rays are preferable. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is 50 mJ / m ² or more, preferably 100 mJ / cm ² or more, and more preferably 400 mJ / cm ² or more. The ultraviolet rays may be irradiated to the multilayer antireflection layer one by one or after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers. In this case, it is efficient to carry out under the condition that the oxygen concentration is 0.5% or less, which is preferable in terms of curing speed.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  Plasma treatment can also be used in the same way. Those that perform the plasma treatment continuously are preferred, and examples of these apparatuses include those described in Japanese Patent Application No. 11-143206. The plasma processing time varies depending on the conditions and cannot be generally specified. However, the plasma processing conditions include plasma processing gas conditions (gas type, gas concentration, gas filling conditions, pressure, etc.), electric field strength, discharge conditions, and the like. . These can be appropriately controlled.

  In general, reactive gases such as hydrogen, oxygen, nitrogen, carbon dioxide, and fluorine-containing compound gases are effective as the processing gas.

In the plasma generation method, in the vacuum plasma discharge treatment, it is necessary to introduce the reaction gas so as to keep the atmosphere in the range of 6.6 to 2.7 × 10 ³ Pa. In order to increase the processing speed, it is preferable to adopt a high output condition on the high voltage side as much as possible for the counter electrode. However, if the electric field strength is excessively increased, the substrate may be damaged.

  When plasma discharge is performed near atmospheric pressure, an inert gas such as helium or argon is required, and the proportion of the reactive gas is 60% or more, which is stable between the electrodes unless the proportion of the inert gas is increased. Discharge does not occur. In this case as well, it is preferable to increase the ratio of the reaction gas and to adopt a high output condition in order to increase the processing speed. However, if the electric field strength is increased too much, the substrate is damaged.

  However, when a pulsed electric field is applied between the counter electrodes even in the vicinity of the atmospheric pressure to generate plasma, the inert gas is not necessarily required, and the reaction gas concentration can be increased. This makes it possible to greatly increase the reaction rate.

  The pulse voltage waveform in the present invention may be, for example, a pulse waveform described in FIGS. 1A to 1D of JP-A-10-130851. However, the shorter the pulse rise time and fall time, the more efficiently the ionization of the gas during plasma generation. In particular, the pulse rise time and fall time are preferably 40 ns to 100 μs. If it is less than 40 ns, it is not practical, and if it exceeds 100 μs, the discharge state tends to shift to an arc and becomes unstable. More preferably, it is 50 ns to 5 μs. Here, the rise time refers to the time during which the voltage change is positive continuously, and the fall time refers to the time during which the voltage change is negative continuously. Furthermore, modulation may be performed using pulses having different pulse waveforms, rise times, and frequencies. Such modulation is suitable for high speed continuous surface treatment.

  The frequency of the pulse electric field is preferably 1 kHz to 100 kHz. If it is less than 1 kHz, the process takes too much time, and if it exceeds 100 kHz, arc discharge tends to occur. In addition, the time during which one pulse electric field is applied is preferably 1 μs to 1000 μs. If it is less than 1 μs, the discharge becomes unstable, and if it exceeds 1000 μs, it tends to shift to arc discharge. More preferably, it is 3 μs to 200 μs. The time during which one pulse electric field is applied refers to a continuous ON time of one pulse in a pulse electric field consisting of repetition of ON and OFF.

  The magnitude of the voltage applied to the counter electrode is appropriately determined, but it is preferable that the electric field strength be in the range of 1 to 100 kV / cm when applied to the electrode. If it is less than 1 kV / cm, it takes too much time to process, and if it exceeds 100 kV / cm, arc discharge tends to occur. Moreover, the processing speed increases as the value increases, but damages the substrate if it is increased too much. Further, a pulse electric field on which direct current is superimposed may be applied.

  Solvents used in the present invention are alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene and xylene; ethylene glycol, propylene glycol, Glycols such as xylene glycol; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol; N-methylpyrrolidone, dimethylformamide, water, etc. Alternatively, two or more types can be mixed and used. Among them, when a solvent having a carbonyl group such as ketones, for example, acetone, methyl ethyl ketone, cyclohexanone, and alcohols having 4 or less carbon atoms such as methanol, ethanol, n-propanol, isopropanol, and n-butanol are used in combination, ultraviolet irradiation amount, etc. This is particularly preferable because the amount of active energy can be reduced and productivity can be improved.

  In addition to the active energy ray, heat treatment is given as one that imparts active energy. The heat treatment is preferably performed at 70 ° C. or higher for 30 seconds or longer and 10 minutes, more preferably 30 seconds or longer and 5 minutes.

  Further, an antireflection layer is produced by coating a low refractive index layer composition containing a low refractive index substance and an organic solvent on the high refractive index layer. Moreover, you may use the active energy ray reactive compound quoted in the high refractive index layer for these compositions.

  The low refractive index layer as the outermost layer contains the following low refractive index material containing fluorine atoms or silicon atoms in order to lower the refractive index of the layer.

The low refractive index substance is at least one compound selected from a fluorine-containing resin, a compound formed from a silicate oligomer, and a compound formed from a SiO ₂ sol and a reactive organosilicon compound. In particular, JP-A-7-126552. No. 7-188582, No. 8-48935, No. 8-100036, No. 9-220791, No. 9-272169, etc. are preferably used.

  Examples of the fluorine-containing resin that can be preferably used in the present invention include a polymer mainly containing a fluorine-containing unsaturated ethylenic monomer component and a fluorine-containing epoxy compound.

  Examples of fluorine-containing unsaturated ethylenic monomers include fluorine-containing alkenes, fluorine-containing acrylic esters, fluorine-containing methacrylate esters, fluorine-containing vinyl esters, fluorine-containing vinyl ethers, and the like. Fluoroethylene, trifluorochloroethylene, vinylidene fluoride, vinyl fluoride, trifluoropropylene, heptafluoropropylene, hexafluoropropylene, 2-bromo-3,3,3-trifluoroethylene, 3-bromo-3,3- Difluoroethylene, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 3,3,4,4,5,5,6,6,7,7,8,8 , 8-tridecafluoro-1-octene, 4-ethoxy-1,1,1-trifluoro-3-butene-2- , Pentadecafluorooctyl acrylate, tetrafluoro-3- (heptafluoropropoxy) propyl acrylate, tetrafluoro-3- (pentafluoroethoxy) propyl acrylate, tetrafluoro-3-trifluoromethoxypropyl acrylate, undecafluorohexyl acrylate , Nonafluoropentyl acrylate, octafluoropentyl acrylate, pentafluoropyrrolyl acrylate, 2-heptafluorobutoxyethyl acrylate, 2,2,3,4,4,4-hexafluorobutoxy acrylate, trifluoroethyl acrylate, 2- ( 1,1,2,2-tetrafluoroethoxy) ethyl acrylate, trifluoroisopropyl methacrylate, (2,2,2-trifluoro-1- Til) ethyl methacrylate, 2-trifluoroethoxyethyl acrylate, trifluoroethyl methacrylate, 2-trifluoromethyl-3,3,3-trifluoropropyl acrylate, 3-trifluoromethyl-4,4,4-trifluorobutyl Acrylate, 1-methyl-2,2,3,3,3-pentafluoropropyl acrylate, 1-methyl-2,2,3,3,4,4,4-heptaurobutyl acrylate, 2,2,2 -Trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,4 , 4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,5,5,5-nonafluoropentyl acrylate, 2,2,3,3,4,4,5,5,6 , 6,6-undecafluorohexyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl acrylate, 2,2,3,3 , 4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl acrylate, 3,3,4,4,5,5,6,6,7,7,8 , 8,8-tridecafluorooctyl acrylate, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nona Decafluorodecyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10 Heptadecafluorodecyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,4,4,4- Hexafluorobutyl acrylate (the above acrylate may be methacrylate or α-fluoro acrylate), vinyl trifluoroacetate, vinyl-2,2,2-trifluoropropionate, vinyl-3,3,3,2,2. 2-heptabtylate, 2,2,2-trifluoroethyl vinyl ether, 1- (trifluoromethyl) ethenyl acetate, allyl trifluoroacetate, allyl-1,1,2,2-tetrafluoroethyl ether, allyl- 1,2,3,3,3-hexafluoropropyl ether, ethyl- 4,4,4-trifluorocrotonate, isopropyl-2,2,2-trifluoroethyl fumarate, isopropyl-2,2,2,3,3,3-pentafluoropropyl fumarate, isopropyl-2,2 , 3,3,4,4,4-heptafluorobutyl fumarate, isopropyl-2,2,3,3,4,4,5,5,5-nonapropylpentyl fumarate, isopropyl-2,2,3 , 3,4,4,5,5,6,6,6-undecafluorohexyl fumarate, isopropyl-2,2,3,3,4,4,5,5,6,6,7,7, 7-tridecafluoroheptyl fumarate, isopropyl-2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl fumarate, isopropyl 3,3,4,4,5,5 6,6,7,7,8,8,8-tridecafluorooctyl fumarate, isopropyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8 , 9,9,10,10,10-nonadecafluorodecyl fumarate, isopropyl-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10,10-heptadecafluorodecyl fumarate, isopropyl-2-trifluoromethyl-3,3,3-trifluoropropyl fumarate, isopropyl-3-trifluoromethyl-4,4,4-trifluorobutyl fumarate Isopropyl-1-methyl-2,2,3,3,3-pentafluoropropyl fumarate, isopropyl-1-methyl-2,2,3,3,4,4,4-heptafluorooctyl fumarate, tert -Butyl 2,2,3,3,3-pentylfluoropropyl hemalate, tert-butyl-2,2,3,3,4,4,4-heptadurorobutyl fumarate, tert-butyl-2,2,3 , 3,4,4,5,5,5-nonafluoropentyl fumarate, tert-butyl-2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl fumarate Tert-butyl-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl fumarate, tert-butyl-2,2,3,3 , 4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl fumarate, tert-butyl-3,3,4,4,5,5,6,6 7,7,8,8,8-tridecafluorooctyl fumarate, tert-butyl- 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl fumarate, tert-butyl 3, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl fumarate, tert-butyl-2-trifluoromethyl-3 , 3,3-trifluoropropyl fumarate, tert-butyl-3-trifluoromethyl-4,4,4-trifluorobutyl fumarate, tert-butyl-1-methyl-2,2,3,3,3 -Fluorine-containing unsaturated ethylenic monomers such as pentylfluoropropyl fumarate and tert-butyl-1-methyl-2,2,3,3,4,4,4-heptafluorobutyl fumarate However, it is not limited to these. Further, the copolymerization partner monomer may or may not contain fluorine.

  Monomers that can be copolymerized with the fluorine-containing monomer include, for example, ethylene, propylene, butene, vinyl acetate, vinyl ethyl ether, vinyl ethyl ketone, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl-α-fluoroacrylate, ethyl-α-fluoroacrylate, propyl-α-fluoroacrylate, butyl-α-fluoroacrylate, cyclohexyl-α-fluoroacrylate, hexyl- α-fluoroacrylate, benzyl-α-fluoroacrylate, acrylic acid, methacrylic acid, α-fluoroacrylic acid, styrene, styrenesulfonic acid, etc. It may be polymerized, but is not limited to these.

  The refractive index of the single resin of the fluorine-containing ethylenically unsaturated monomer is in the range of about 1.33 to 1.42, and the refractive index of the single resin polymer of the monomer not containing fluorine that can be copolymerized. The ratio is 1.44 or more, and these can be copolymerized at an arbitrary ratio to be used as a fluorine-containing resin having a desired refractive index. Also, the fluorine-containing resin of the present invention and a fluorine-free resin can be arbitrarily selected. However, the fluorine content of the low refractive index material of the present invention is preferably 50% by mass or more, and varies depending on the material, but is particularly preferable. Is 60-90 mass%. In the case of a fluorine-containing polymer, if the fluorine content is in such a range, it has good solubility in an organic solvent, so that it is not only easy to process but also has excellent adhesion to the underlying substrate and layer. A layer with high transparency and low refractive index can be obtained.

  As the polymerization initiator for polymerizing the fluorine-containing alkene, acrylate, vinyl ester, vinyl ether or the like used in the present invention, a normal radical polymerization initiator can be used. Specific examples of polymerization initiators include azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobisvaleronitrile, benzoyl peroxide, t-butyl hydroperoxide, cumene peroxide , Organic peroxide radical polymerization initiators such as diacyl peroxide, inorganic radical polymerization initiators such as ammonium persulfate and potassium persulfate, redox such as hydrogen peroxide-ferrous ammonium sulfate, ammonium persulfate-sodium metasulfite Various radical polymerization initiators such as system polymerization initiators can be mentioned, and these can be used to carry out known radical polymerization such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or radiation polymerization. At this time, the reaction temperature is preferably 10 to 100 ° C., and the reaction time is preferably 1 to 100 hours. The number average molecular weight of the fluorine-containing resin thus obtained is desirably 1000 to 300,000.

  The fluorine-containing epoxy resin as the fluorine-containing resin of the present invention can be obtained, for example, by reacting the following epoxy compound by a conventional method.

  Examples of the fluorine-containing epoxy compound of the present invention include 2,4,4-trifluoro-1,2-butanediol diglycidyl ether, 4,4,4-trifluoro-1,2-diol diglycidyl ether, 5,5,5-pentafluoro-1,2-pentanediol diglycidyl ether, 4,4,5,5,6,6,6-hexafluoro-1,2-hexanediol diglycidyl ether, 4,4, 5,5,6,6,7,7,7-nonafluoro-1,2-heptanediol diglycidyl ether, 4,4,5,5,6,6,7,7,8,8,8-undeca Fluoro-1,2-octanediol diglycidyl ether, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1,2-nonanediol diglycidyl Ether 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1,2-decanediol diglycidyl ether, 4,4,5,5 6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-1,2-undecanediol diglycidyl ether, 4,4,5,5,6 , 6,7,7,8,8,9,9,10,10,11,11,12,12,12-nonadecafluoro-1,2-dodecadiol diglycidyl ether, 4,4,5,5 , 6,6,7,7,8,8,9,9,10,10,11,12,12,13,13,13-eicosafluoro-1,2-tridecanedioldiglycidyl ether, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 1 , 12, 13, 13, 14, 14, 14-tricosafluoro-1,2-tetradecanediol diglycidyl ether, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10 , 11,11,12,12,12-heptadecafluoro-1,2-tetradecanediol diglycidyl ether, 4-trifluoromethyl-5,5,5-trifluoro-1,2-heptanediol diglycidyl ether, 5-trifluoromethyl-6,6,6-trifluoro-1,2-octanediol diglycidyl ether, 6-trifluoromethyl-4,4,5,5,6,6,7,7,7-octyl Fluoro-1,2-nonanediol diglycidyl ether, 8-trifluoromethyl-4,4,5,5,6,6,7,7,8,8,9,9,9-dodecafluoro-1 , 2-nonanediol diglycidyl ether, 10-trifluoromethyl-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-hexa Decafluoro-1,2-dodecanediol diglycidyl ether, 12-trifluoromethyl-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11 , 12, 12, 13, 13, 13-eicosafluoro-1,2-tetradecanediol diglycidyl ether, 3-perfluorocyclopentyl-1,2-propanediol diglycidyl ether, 3-perfluorocyclohexyl-1,2-propane Diol diglycidyl ether, perfluorocycloheptyl-1,2-propanediol diglycidyl ether, perfluorocyclooctyl- , 2-propanediol diglycidyl ether; examples of the fluorine-containing alkane-terminated diol glycidyl ether include 2,2,3,3-tetrafluoro-1,4-butanediol diglycidyl ether, 2,2,3,3,4 , 4,5,5-octafluoro-1,6-hexanediol diglycidyl ether, and the like, but are not limited thereto. In addition to these, a small amount of an epoxy compound containing no fluorine may be used so that the refractive index does not increase so much. Although there is no restriction | limiting in the structure of the fluorine-containing epoxy compound used here, it is better that there is little use of the epoxy compound which has a benzene nucleus which raises a refractive index, or an alicyclic epoxy compound.

  Another preferred low refractive index material is a compound formed from a silicate oligomer. As a compound formed from a silicate oligomer, it is a compound formed from the silicate oligomer shown by the following general formula (II).

  Here, g is an integer of 1 to 20, R is hydrogen, an alkyl group having 1 to 4 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, A fluorine-containing cycloalkyl group having 3 to 6 carbon atoms or a phenyl group, and each R may be the same group or different groups.

  Examples of the silicate oligomer used for the compound formed from the silicate oligomer represented by the general formula (II) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetra-2. , 2,2-trifluoroethoxysilane, tetra-2-fluoroethoxysilane, tetra-2,2,3,3-tetrafluoro-1-propoxysilane, tetra-1,1,1,3,3,3 -Hexafluoro-2-propoxysilane, tetra-2,2,3,3,3-pentafluoro-1-propoxysilane, tetra-1,3-difluoro-2-propoxysilane, tetra-2,2 , 3,3,4,4,4-heptafluoro-1-butoxysilane, tetra-2,2,3,4, , 4-hexafluoro-1-butoxysilane, it can be mentioned tetra-cyclohexyloxy silane or tetraphenoxysilane like, silicate oligomer is obtained by these hydrolysis.

  As described above, a hydrolyzate cured by a method such as adding a solvent to a hydrolyzate obtained by adding a catalyst and water to tetraalkoxysilane and then adding a curing catalyst and water is obtained. As such a solvent, it is preferable to use one or two kinds of methanol and ethanol because it is inexpensive and the properties of the resulting film are excellent and the hardness is good. Although isopropanol, n-butanol, isobutanol, octanol, and the like can be used, the hardness of the obtained film tends to be low. The amount of the solvent is 50 to 400 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the partial hydrolyzate.

  Examples of the curing catalyst include acids, alkalis, organic metals, metal alkoxides, and the like, but acids such as acetic acid, maleic acid, oxalic acid, and fumaric acid are preferably used. The addition amount is 1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate. The amount of water added may be an amount that is at least the amount that the partial hydrolyzate can theoretically hydrolyze to 100%, and an amount equivalent to 100 to 300%, preferably an amount equivalent to 100 to 200% should be added. . Further, in the present invention, the aging step sufficiently proceeds the hydrolysis and condensation of the tetraalkoxysilane, and the properties of the obtained film are excellent. For the aging, the oligomer liquid may be allowed to stand, and the standing time is sufficient for the above-mentioned crosslinking to proceed to a sufficient extent to obtain the desired film characteristics, and specifically, depending on the type of catalyst used. However, for hydrochloric acid, 1 hour or more at room temperature, for maleic acid, several hours or more, particularly preferably about 8 hours to 1 week is sufficient, usually about 3 days. The time required for aging also affects the ambient temperature, and it may be better to take a means of heating to around 20 ° C. in extremely cold regions. In general, ripening progresses quickly at high temperatures, but when heated to 100 ° C. or higher, gelation occurs. Therefore, heating up to 50 to 60 ° C. is appropriate. In addition to the above, these silicate oligomers are modified products modified with organic compounds (monomers, oligomers, polymers) having functional groups such as epoxy groups, amino groups, isocyanate groups, and carboxyl groups. However, it can be used alone or in combination with the above silicate oligomer.

In this way, the silicate oligomer represented by the general formula (II) is obtained, SiO ₂ content in the silicate oligomer 1% to 100% is preferably desired to be 10 to 99%. When the SiO ₂ content is less than 1%, the durability cannot be improved and the effects of the present invention are not exhibited.

  The method for forming a silicon layer from these silicate oligomers is not particularly limited, but for example, a solvent that does not inhibit the optical performance of the silicate oligomer such as alcohol (methanol, ethanol, isopropanol, etc.), ethyl acetate, butyl acetate, acetic acid. Cellosolve, methyl glycol acetate, methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylene chloride, toluene, xylene, mineralum spirit, cresol, xylenol, furfural, etc., dilute the silicate oligomer with these, bar coater, roll coater The substrate may be coated and heat-treated by a known method such as a gravure coater, reverse coater or lip coater.

Further preferred low refractive index material, a compound formed from the reactive organic silicon compound SiO ₂ sol, using a sol solution containing a reactive organic silicon compound SiO ₂ sol, the SiO ₂ gel film A low refractive index layer is formed. The SiO ₂ sol is prepared by dissolving silicon alkoxide in an organic solvent suitable for coating and adding a certain amount of water to perform hydrolysis. A preferred example of the silicon alkoxide used for forming the SiO ₂ sol is shown in the following general formula (IV).

Formula (IV)
(R ′) _r Si (OR ″) _s
Here, R ′ and R ″ each represent an alkyl group having 1 to 10 carbon atoms, and may be the same or different. R + s is 4, and r and s are each an integer. Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, tetrapentaethoxysilane, Tetrapentaisopropoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-t-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane , Methyl tributoxysila , Dimethyl Meki silane, dimethyl diethoxy silane, dimethyl methoxy silane, dimethyl silane, dimethyl propyl silane, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane and the like.

A SiO ₂ sol can be obtained by dissolving the alkyl silicon alkoxide or silicon alkoxide in a suitable solvent. Examples of the solvent used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate, and butyl acetate, aromatic hydrocarbons such as ketones, esters, halogenated hydrocarbons, toluene, xylene, and the like. Or a mixture thereof. Alkyl silicon alkoxide or silicon alkoxide is converted into SiO ₂ produced as a result of 100% hydrolysis and condensation in the solvent so that the concentration is 0.1% by mass or more, preferably 0.1 to 10% by mass. Dissolve. If the concentration of the SiO ₂ sol is less than 0.1% by mass, the formed sol film cannot sufficiently exhibit the desired characteristics, while if it exceeds 10% by mass, it becomes difficult to form a transparent homogeneous film. Moreover, in this invention, if it is less than the above solid content, it is also possible to use an organic substance and an inorganic binder together.

  Water beyond the amount required for hydrolysis is added to this solution, and stirring is performed at a temperature of 15 to 35 ° C., preferably 22 to 28 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours. In the hydrolysis, it is preferable to use a catalyst. As these catalysts, acids such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid are preferable. These acids can be added as an aqueous solution of about 0.001 to 40.0 mol / l, preferably about 0.005 to 10.0 mol / l, and the water in the aqueous solution can be used as water for hydrolysis.

If in the present invention, but is intended to use an organic reactive silicon compound to the SiO ₂ sol or a compound obtained by adding a partial hydrolyzate thereof as a low refractive index material, coated by SiO ₂ sol, A film that is very weak, easily cracked, and needs to fix the SiO ₂ film is required. In the present invention, by using a reactive organosilicon compound together, SiO _{2 is} also bonded by crosslinking to form a strong film, and the obtained SiO ₂ sol is a colorless and transparent liquid with a pot life of about 1 month. It is a stable solution. The SiO ₂ sol has good wettability with respect to the substrate and is excellent in coating property.

  The reactive organosilicon compound has a molecular weight of 3000 having a plurality of groups (active energy ray reactive groups) that are reactively crosslinked by heat or ionizing radiation, for example, a polymerizable double bond group, in addition to the reactive organosilicon compound. The following organic reactive compounds are preferred. Such a reactive organosilicon compound may be one end vinyl functional polysilane, both end vinyl functional polysilane, one end vinyl functional polysiloxane, both end vinyl functional polysiloxane, or a vinyl functional polysilane obtained by reacting these compounds. Or the following compounds such as vinyl functional polysiloxane,

Others, vinyltrimethoxysilane, vinyltri (β-methoxy-ethoxy) silane, divinyloxydimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethyltriethoxysilane, glycidyloxyethyltri Ethoxysilane, γ-acryloyloxy-n-propyltri-n-propylsilane, γ-methacryloyloxy-n-propyltri-n-propylsilane, di (γ-acryloyloxy-n-propyl) di-n-propylsilane And acryloyloxydimethoxyethylsilane.

The reactive organosilicon compound as described above is preferably used at a ratio of about 0.1 to 50 parts by mass per 100 parts by mass of the SiO ₂ sol (solid content).

Various additives can be added to the sol solution. As the additive, a curing agent that promotes film formation is used. Examples of these curing agents include organic acid solutions such as acetic acid and formic acid of organic acid metal salts such as sodium acetate and lithium acetate. The concentration of the organic solvent solution is about 0.01 to 0.1% by mass, and the amount added to the sol solution is about 0.000 as the organic acid salt with respect to 100 parts by mass of SiO ₂ present in the sol solution. A range of about 1 to 1 part by mass is preferred.

  Furthermore, although the gel film finally obtained is used as a low refractive index layer of an antireflection film, it may be necessary to adjust the refractive index. For example, a fluorine-based organosilicon compound can be added to lower the refractive index, an organosilicon compound can be added to increase the refractive index, and a boron-based organic compound can be added to further increase the refractive index. Specifically, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, alkyltrialkoxysilane, Colcoat 40 (manufactured by Colcoat), MS51 (manufactured by Mitsubishi Chemical), Snowtex (manufactured by Nissan Chemical Co., Ltd.) ), Etc., ZAFLON FC-110, 220, 250 (manufactured by Toa Gosei Chemical Co., Ltd.), sexual coat A-402B (manufactured by Central Glass Co., Ltd.), heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane And fluorine compounds such as trifluorooctyltrimethoxysilane and trifluoropropyltrimethoxysilane, and boric acid compounds such as triethyl borate, trimethyl borate, tripropyl borate and tributyl borate. These additives may be added during the preparation of the sol, or may be added after the formation of the sol. By using these additives, during the hydrolysis of the alkyl silicon alkoxide or silicon alkoxide, or after that, it reacts with the silanol group, and more uniformly reacts to obtain and form a more uniform and transparent sol solution. The refractive index of the gel film can be changed within a certain range.

Next, a low refractive index layer containing at least one low refractive index material selected from the fluorine-containing resin, a compound formed from a silicate oligomer, and a compound formed from a SiO ₂ sol and a reactive organosilicon compound (the above-mentioned (Provided on the high refractive index layer of the present invention) may be added with the active energy ray-reactive compounds mentioned for the high refractive index layer. Of these, epoxy-based active energy ray-reactive compounds are preferably used.

  The epoxy-based active energy ray-reactive compound is a compound having two or more epoxy groups in the molecule and capable of releasing cationic polymerization as an initiator by irradiation with active energy rays as described above.

As useful thing of an epoxy type active energy ray reactive compound,
(A) Glycidyl ether of bisphenol A (this compound is obtained by reaction of epichlorohydrin and bisphenol A, and is obtained as a mixture having different degrees of polymerization);
(B) A compound having a glycidyl ether group at the terminal by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A;
(C) glycidyl ether of 4,4'-methylenebisphenol;
(D) epoxy compound of phenol formaldehyde resin of novolac resin or resol resin;
(E) A compound having an alicyclic epoxide. For example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) ) Pimelate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1 -Methyl-cyclohexylmethyl-3 ', 4'-epoxy-1'-methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3', 4'-epoxy-6'-methyl-1 ' -Cyclohexanecarboxyle DOO, 2- (3,4-epoxycyclohexyl-5 ', 5'-spiro-3 ", 4" - epoxy) cyclohexane - meta - dioxane;
(F) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl phthalate;
(G) Diglycidyl ether of glycol, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) diglycidyl Ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether;
(H) glycidyl esters of polymeric acids, such as polyglycidyl esters of polyacrylic acid, polyester diglycidyl esters;
(L) Glycidyl ethers of polyhydric alcohols, such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether;
(Nu) The diglycidyl ether of 2-fluoroalkyl-1,2-diol is the same as the compound examples given for the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index substance;
Examples of (l) fluorine-containing alkane-terminated diol glycidyl ether include the same compound examples as those given for the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index substance. The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with active energy rays, and particularly preferably a cation by irradiation. It is a group of double salts of onium salts that release Lewis acids capable of initiating polymerization. Since these are the same as those in the general formula (III), they are omitted here.

  These active energy ray-reactive compounds are cured by application of ultraviolet rays, active energy rays such as an electron beam, plasma treatment, or thermal energy similar to those described for the high refractive index layer. Is the same.

  It is also preferable to use organic and inorganic fine particles in the antireflection layer.

  The inorganic fine particles used in the low refractive index layer preferably have a refractive index of 1.05 to 1.80, and more preferably 1.20 to 1.35.

  The inorganic fine particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.80.

  Amorphous particles are preferably used as the inorganic fine particles, preferably made of a metal oxide, nitride, sulfide or halide, and particularly preferably a metal oxide. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferred. In the low refractive index layer, Mg, Ca, B, and Si are more preferable, and an inorganic compound containing two kinds of metals may be used. A particularly preferable inorganic compound is silicon dioxide, that is, silica. The high refractive index layer includes titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Titanium oxide, tin oxide and indium oxide are particularly preferred.

  The average particle size of the inorganic fine particles is preferably 0.001 to 0.2 μm, and more preferably 0.005 to 0.05 μm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible. The addition amount of the inorganic fine particles is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and particularly preferably 10 to 50% by mass with respect to the total mass of the low refractive index layer.

The primary particles of the inorganic fine particles preferably have a weight average diameter of 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the inorganic fine particles in the coating layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and most preferably 10 to 80 nm. preferable. The average particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  It is also preferable to use the inorganic fine particles after surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Silane coupling treatment is particularly effective when the inorganic fine particles are silica.

  Further, it is also preferable that the low refractive index layer contains polymer organic fine particles having a low refractive index. The refractive index is preferably 1.05 to 1.40, more preferably 1.20 to 1.35.

  Low-refractive inorganic and organic fine particles are known to have a low refractive index as fine particles by utilizing the air refractive index of 1.00 by having a void air space in the particles. It is preferable to use it for the refractive index layer. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

  The antireflection layer can be formed as described above.

  In this invention, you may have an anti-glare layer on a transparent plastic film base material as a functional thin film. The antiglare layer has a structure in which fine particles are contained in the layer in order to develop an antiglare function by scattering light on the surface of the antiglare layer by providing a structure having irregularities on the surface.

  Preferred configurations for these layers are as shown below.

  This is a silicon oxide particle having a film thickness of 0.5 μm or more and 5.0 μm or less and an average particle diameter of 1.1 to 2 times the film thickness and silicon oxide fine particles having an average particle diameter of 0.005 μm or more and 0.1 μm or less. Is a layer containing, for example, diacetylcellulose in a binder, which can exhibit an antiglare function.

  “Particles with an average particle size of 0.25 μm or more and 10 μm or less” are those that exhibit the anti-glare function on the surface of a liquid crystal screen using this by being present on the outermost surface of the protective film for polarizing plate, An average particle diameter of 0.25 μm to 10 μm.

  Examples of the “particles” include inorganic particles and organic particles, such as metal oxides, metal oxynitrides, metal nitrides, organic polymers, and liquid crystal compounds. Examples of inorganic particles that can be used in the present invention include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.

  Organic particles include poly (meth) acrylate resins, silicon resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used.

  Among these, silicon oxide such as silica is particularly preferably used to achieve the antiglare property which is one of the objects of the present invention. As the silicon oxide particles preferably used here, ultrafine hydrated silicic acid produced by a wet method is preferred among synthetic amorphous silicas because of its great effect of reducing the glossiness. The wet method is a method in which sodium silicate is reacted with mineral acid and salts in an aqueous solution, and examples thereof include silicia manufactured by Fuji Silysia Chemical Co., Ltd. and Nippon Sil E manufactured by Nippon Silica Co., Ltd.

  The antiglare layer also preferably uses an actinic radiation curable resin as a binder, and the active oxide curable resin layer containing silicon oxide particles or silicon oxide fine particles is formed by irradiation with active energy rays after coating. From the viewpoint that the mechanical strength of the polarizing plate surface can be increased, an antiglare layer using an active energy ray-curable resin as a binder is more preferable.

  The active energy ray-curable resin that can be used in the present invention may be a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams described in the antireflection layer.

  The thickness of the functional thin film is preferably in the range of 0.01 to 100 μm.

<Polarizer>
A polarizing plate using the optical film of the present invention will be described.

  The polarizing plate can be produced by a general method. Using a fully saponified polyvinyl alcohol aqueous solution on at least one surface of a polarizing film prepared by subjecting the back surface side of the antireflection film of the present invention to alkali saponification treatment and immersing and stretching the treated antireflection film in an iodine solution It is preferable to stick them together. The antireflection film may be used on the other surface, or the retardation film prepared by the method of the present invention may be used, or another polarizing plate protective film may be used. As the polarizing plate protective film used on the back side, KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR3 (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used as commercially available cellulose ester films. In contrast to the antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, an optical compensation having a phase difference of 20 to 70 nm and Rt of 70 to 400 nm. The film is preferably a film, and particularly preferably a cellulose ester film according to the present invention subjected to a stretching treatment. These can be produced, for example, by the methods described in JP-A-2002-71957, paragraph numbers [0014] to [0078] and JP-A-2003-170492, paragraphs [0064] to [0252]. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in paragraph numbers [0033] to [0053] of JP-A-2003-98348. By using it in combination with the antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  A conventional polarizing plate using an antireflection film is inferior in flatness, and when a reflected image is seen, fine wavy unevenness is observed and glare is also seen. In addition, as a result of the durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness increased. On the other hand, the polarizing plate using the antireflection film of the present invention has excellent flatness and glare. There are few. In addition, even in a durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness does not increase, and even with a polarizing plate having an optical compensation film on the back side, viewing angle characteristics after the durability test It was possible to provide good visibility without fluctuation.

<Display device>
By incorporating the antireflection film and polarizing plate of the present invention into a display device, various display devices with excellent visibility can be produced. In the antireflection film of the present invention, the polarizing plate is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. It is preferably used in the LCD of the type. Further, the antireflection film of the present invention has remarkably little color unevenness and glaring of the reflected light of the antireflection layer, and is excellent in flatness, such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. It is preferably used for various display devices. In particular, a large-screen display device with a screen of 30 or more types, particularly 30 to 54 types, has less color unevenness, glare and wavy unevenness, and has an effect that eyes are not tired even during long-time viewing.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the embodiments of the present invention are not limited to these examples.

Example 1
First, a cellulose ester film was produced by the method shown below.

<Cellulose ester film>
(Silicon dioxide dispersion A)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare silicon dioxide dispersion dilution A.

(Preparation of inline additive solution A)
Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 11 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 5 parts by weight 100 parts by weight of methylene chloride Dissolved and filtered.

To this, 36 parts by mass of silicon dioxide dispersion diluent A was added with stirring, and the mixture was further stirred for 30 minutes, and then cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 6 masses. The mixture was added with stirring, and further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution A.

(Preparation of dope solution A)
Cellulose ester (cellulose triacetate synthesized from linter cotton)
100 parts by mass (Mn = 148000, Mw = 310000, Mw / Mn = 2.1, acetyl group substitution degree 2.9)
Trimethylolpropane tribenzoate 5.0 parts by weight Ethylphthalylethyl glycolate 5.5 parts by weight Methylene chloride 440 parts by weight Ethanol 40 parts by weight The above is put into a sealed container, heated and dissolved with stirring, and Azumi filter paper ( Azumi filter paper No. 24, and the dope liquid A was prepared. Add 2 parts by mass of filtered in-line additive liquid A to 100 parts by mass of filtered dope liquid A, mix thoroughly with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then belt cast Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 120%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 40 ° C., slit to 1650 mm width, and then stretched 1.1 times at 120 ° C. in the TD direction (direction perpendicular to the film transport direction). The residual solvent amount when starting stretching with a tenter was 30%. Thereafter, drying is completed while transporting the heating zones of 110 ° C. and 120 ° C. with many rolls, slitting to a width of 1400 mm, no knurling as shown in Table 1, or a width of 15 mm at both ends of the film and an average height of 10 μm. The cellulose ester films 1 to 7 were obtained by winding a hollow plastic core: FRP outer diameter 6 inches (hereinafter, inch represents 2.54 cm) and inner diameter 5 inches. The draw ratio in the MD direction (the same direction as the film transport direction) immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.00 times. The residual solvent amount of the wound cellulose ester film was 0.1%, the average film thickness was 70 μm, and the winding number was 3000 m.

  The obtained cellulose ester films 1 to 7 were loaded in a storage box having a mount shown in FIG. Subsequently, the cellulose ester film was rotated under the conditions shown in Table 1.

<Evaluation>
(Deflection, sticking)
Roll-like cellulose ester films 1 to 7 are stored in a warehouse of 30 ° C. to 40 ° C. and 65% RH to 85% RH for one month, and the state of winding after the lapse of one month is visually observed. The rank was evaluated.

◎: Deflection, sticking, etc. are not recognized in the roll ○: Slight deflection is observed in the roll, but no sticking is observed △: Weak deflection is observed in the roll, and some sticking is also observed ×: Table 1 shows the results of the evaluation described above, in which strong deflection is observed in the roll and sticking is also observed.

  From the above table, it can be seen that the original film of the cellulose ester film of the present invention is improved in bending and sticking, and the properties are further improved by knurling the film edge. In particular, good results were obtained by shortening the period of rotation.

Example 2
The cellulose ester film original fabric produced in Example 1 was fed out, and an antireflection film roll having an antireflection layer having a winding number of 3000 m was produced as follows. The refractive index and film thickness of the antireflection layer were measured by the following methods.

<Measurement of refractive index and film thickness>
The refractive index and film thickness of each layer are determined from the measurement result of the spectral reflectance of the spectrophotometer for the sample in which each layer is coated alone. The spectrophotometer uses U-4000 type (manufactured by Hitachi, Ltd.), and after roughening the back side of the measurement side of the sample, light absorption treatment is performed with black spray to prevent reflection of light on the back side. Then, the reflectance in the visible light region (400 to 700 nm) is measured under the condition of regular reflection at 5 degrees.

<Preparation of antireflection layer>
(Preparation of hard coat film)
The following hard coat layer composition (C-1) was applied to one side of the cellulose ester film prepared in Example 1 so that the coating width was 1300 mm and the dry film thickness was 3.5 μm, and dried at 80 ° C. for 1 minute. did. Next, it was cured under a condition of 150 mJ / cm ^{2 with} a high-pressure mercury lamp (80 W) to produce a hard coat film having a hard coat layer. The refractive index of the hard coat layer was 1.50.

<Hard coat layer composition (C-1)>
Dipentaerythritol hexaacrylate monomer 108 mass parts Dipentaerythritol hexaacrylate dimer 36 mass parts Dipentaerythritol hexaacrylate trimer or higher component 36 mass parts Diethoxybenzophenone (UV photoinitiator) 18 mass parts Propylene glycol 180 parts by mass of monomethyl ether 120 parts by mass of ethyl acetate (production of medium refractive index layer film)
On the hard coat layer of the hard coat film, the following medium refractive index layer composition (M-1) was applied by an extrusion coater and dried for 1 minute at 80 ° C. and 0.1 m / second. At this time, a non-contact floater was used until completion of touch drying (a state where the coated surface was touched with a finger and felt dry). As the non-contact floater, a horizontal floater type air tumbler manufactured by Belmatik was used. The static pressure in the floater was set to 9.8 kPa, and the floater was lifted uniformly in the width direction of about 2 mm and conveyed. After drying, a medium refractive index layer film having a medium refractive index layer was produced by curing by irradiating ultraviolet rays with 130 mJ / cm ² using a high pressure mercury lamp (80 W).

<Medium Refractive Index Layer Composition (M-1)>
Tetra (n) butoxytitanium 51 parts by mass Dimethylpolysiloxane (KF-96-1000CS manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by mass γ-methacryloxypropyltrimethoxysilane (KBE503 manufactured by Shin-Etsu Chemical Co., Ltd.)
26 parts by mass Acrylic resin (BR-102 manufactured by Mitsubishi Rayon Co., Ltd.) 9 parts by mass Propylene glycol monomethyl ether 150 parts by mass Isopropyl alcohol 2950 parts by mass Methyl ethyl ketone 500 parts by mass The thickness of the medium refractive index layer of this medium refractive index layer film 1 Was 77 nm and the refractive index was 1.70.

(Preparation of high refractive index layer film)
On the medium refractive index layer film, the following high refractive index layer composition (H-1) was applied by an extrusion coater and dried for 1 minute at 80 ° C. and 0.1 m / second. At this time, a non-contact floater was used until completion of touch drying (a state where the coated surface was touched with a finger and felt dry). The non-contact floater was made to have the same conditions as the medium refractive index layer film 1. After drying, a high-pressure mercury lamp (80 W) was used to cure by irradiating with ultraviolet rays of 130 mJ / cm ² to produce a high refractive index layer film having a high refractive index layer.

<High refractive index layer composition (H-1)>
95 parts by mass of tetra (n) butoxytitanium dimethylpolysiloxane (KF-96-1000CS manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by mass of γ-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)
5 parts by mass Propylene glycol monomethyl ether 1750 parts by mass Isopropyl alcohol 3450 parts by mass Methyl ethyl ketone 600 parts by mass The thickness of the high refractive index layer of this high refractive index layer film was 68 nm and the refractive index was 1.91.

(Production of low refractive index layer film)
On the high refractive index layer film, the following low refractive index layer composition (L-1) was applied by an extrusion coater and dried for 1 minute under the conditions of 80 ° C. and 0.1 m / second. At this time, a non-contact floater was used until completion of touch drying (a state where the coated surface was touched with a finger and felt dry). The non-contact floater was under the same conditions as the medium refractive index layer film. After drying, the film was cured by irradiating with ultraviolet rays of 130 mJ / cm ² using a high-pressure mercury lamp (80 W) and further thermally cured at 120 ° C. for 5 minutes to produce an antireflection film having a low refractive index layer.

<Preparation of tetraethoxysilane hydrolyzate A>
Tetraethoxysilane hydrolyzate A was prepared by mixing 25 g of tetraethoxysilane and 222 g of ethanol, adding 54 g of a 1.5% by weight aqueous solution of citric acid monohydrate, and stirring for 3 hours at room temperature. did.

<Low refractive index layer composition (L-1)>
Tetraethoxysilane hydrolyzate A 103 parts by mass γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical KBM503)
1 part by weight Linear dimethyl silicone-EO block copolymer (Nippon Unicar FZ-2207) 0.1 part by weight Propylene glycol monomethyl ether 270 parts by weight Isopropyl alcohol 270 parts by weight The thickness of the low refractive index layer of this antireflection film The thickness was 93 nm and the refractive index was 1.44.

  Antireflection films 1 to 7 were produced using cellulose ester films 1 to 7 as described above.

<Evaluation>
(Evaluation of visual unevenness)
Using the obtained antireflection film, a sample having a full width in the width direction x 50 cm in the longitudinal direction was subjected to a light absorption treatment using a black spray on the back surface, and the reflection of the fluorescent lamp was observed from the front surface. The coating unevenness was visually evaluated.

A: Unevenness is not recognized at all O: Slight unevenness is observed Δ: Unevenness is observed ×: Unevenness is clearly recognized.

  The obtained results are shown in Table 1.

  It is apparent that the antireflection film of the present invention is excellent in visual unevenness when an antireflection layer is provided.

Example 3
The antireflection film rolls 1 to 7 produced in Example 2 are loaded on the gantry shown in FIG. 1, and the roll film is heated from room temperature (23 ° C.) to 65 ° C. at a rate of 21 ° C./day. This was carried out for 2 days, then kept at 65 ° C. and left for 7 days, and further returned to room temperature over 2 days at a temperature drop rate of 21 ° C./day. At that time, the roll was continuously rotated at a speed of 1 rotation per hour.

  When the wound shape of the obtained antireflection film roll was evaluated in the same manner as in Examples 1 and 2, the antireflection film roll of the present invention was free from winding deflection, sticking, and visual unevenness.

Example 4
When lots whose production dates were changed with the same roll as the sample produced in Example 3 were subjected to the same heat treatment as in Example 3 and the same evaluation was performed, it was confirmed that there was almost no variation between the lots.

Sectional drawing of the mount which has a rotation function, and its storage box is shown. It is sectional drawing which shows the relationship between the thickness of a thick film or an uneven | corrugated shaped belt | band | zone, and the thickness of a film.

Explanation of symbols

1 Transparent plastic film substrate 2, 3 Thick film or uneven band

Claims (11)

A storage box having a gantry comprising means for rotating a transparent plastic film original. The storage box having a gantry according to claim 1, further comprising means for rotating the transparent plastic film raw material once or more in two weeks. The transparent plastic film original fabric is a cellulose ester film having a film width of 1.35 m or more and a thickness of 25 μm to 110 μm, and at least both end portions are provided with thick films or uneven bands. A storage box having the mount according to claim 1. A method for producing an optical film, comprising: providing a hard coat layer on a transparent plastic film raw material rotated during storage in a storage box having the mount according to any one of claims 1 to 3. Furthermore, an antistatic layer is provided, The manufacturing method of the optical film of Claim 4 characterized by the above-mentioned. Furthermore, an antireflection layer is provided, The manufacturing method of the optical film of Claim 4 or 5 characterized by the above-mentioned. The optical film manufactured by the method for manufacturing an optical film according to any one of claims 4 to 6 is stored in a storage box having the mount according to any one of claims 1 to 3. And storage method of optical film. An optical film manufactured by the method for manufacturing an optical film according to any one of claims 4 to 6. An optical film stored by the optical film storage method according to claim 7. A polarizing plate comprising the optical film according to claim 8. A display device comprising the polarizing plate according to claim 10.

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