WO2019098159A1 - Method for manufacturing polarizing plate, method for manufacturing liquid crystal display device, and optical film - Google Patents
Method for manufacturing polarizing plate, method for manufacturing liquid crystal display device, and optical film Download PDFInfo
- Publication number
- WO2019098159A1 WO2019098159A1 PCT/JP2018/041863 JP2018041863W WO2019098159A1 WO 2019098159 A1 WO2019098159 A1 WO 2019098159A1 JP 2018041863 W JP2018041863 W JP 2018041863W WO 2019098159 A1 WO2019098159 A1 WO 2019098159A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optical film
- group
- film
- polarizing plate
- temporary support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a method of manufacturing a polarizing plate, a method of manufacturing a liquid crystal display, and an optical film.
- Optical films are used for various applications, for example, for polarizing plates.
- a polarizing plate is used as a member such as a liquid crystal display (LCD) or an organic electroluminescence (organic EL) display (OLED), and plays an important role in the display performance.
- a general polarizing plate has a configuration in which an optical film is bonded to one side or both sides of a polarizer in which a dichroic dye such as iodine complex is adsorbed and oriented to a polyvinyl alcohol (PVA) resin.
- PVA polyvinyl alcohol
- Patent Document 1 a coating film is provided on a temporary support, and a polarizer is attached to the coating film, and then the coating film having a thickness of less than 10 ⁇ m is attached by peeling the temporary support from the coating film. A method of making combined polarizers is described.
- Patent Document 1 describes a coated film mainly composed of a cycloolefin polymer, and according to the study of the present inventors, a coated film having excellent releasability from a temporary support and having low birefringence is disclosed.
- the coating film can not follow the elongation due to the moisture absorption of the PVA-based resin forming the polarizer. , It was found that there is an event that the polarizing plate breaks down.
- the characteristic function of the film largely depends on the main material of the film, but the main material is not necessarily able to cope with the deformation of the PVA-based resin under high temperature and high humidity, and is rather disadvantageous in many cases.
- the problem to be solved by the present invention is a method of manufacturing a polarizing plate capable of suppressing breakage failure under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device. It is an object of the present invention to provide a method of manufacturing a liquid crystal display device, and an optical film capable of suppressing a breakdown failure of a polarizing plate under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device.
- the optical film of the present invention contains a component having extensibility, and when the optical film of the present invention is used for a polarizing plate, the optical film of the present invention follows the elongation of the polarizer under high temperature and high humidity. It is thought that the failure of the polarizing plate can be suppressed by the extension of the optical film.
- the present invention which is a specific means for solving the above-mentioned subject is as follows.
- the optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
- the optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film;
- the thickness of the optical film is 4 to 10 ⁇ m,
- the elongation at break of the optical film is 2.5% or more in an environment of 25 ° C.
- the manufacturing method of the polarizing plate whose arithmetic mean roughness of the surface of the side which forms the said optical film of the said temporary support body is 40 nm or less.
- the manufacturing method of the liquid crystal display device which has the process of bonding together the said optical film side of the polarizing plate manufactured by the manufacturing method as described in ⁇ 1> or ⁇ 2> on the liquid crystal cell side.
- An optical film comprising a copolymer containing a structural unit derived from butadiene, and a polyester-based additive,
- the content of the copolymer containing a structural unit derived from butadiene is 25 to 45% by mass with respect to the total solid content of the optical film
- the content of the polyester-based additive is 0.1 to 10% by mass with respect to the total solid content of the optical film
- the thickness of the optical film is 4 to 10 ⁇ m
- the optical film whose breaking elongation of the said optical film is 2.5% or more in a 25 degreeC environment in the sample of thickness 30 micrometers and width 10 mm.
- ⁇ 5> The optical film as described in ⁇ 4> containing styrene resin.
- a method of manufacturing a polarizing plate capable of suppressing breakage failure under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device a method of manufacturing a liquid crystal display device having the above polarizing plate, and The optical film which can suppress the destructive failure of a polarizing plate under high humidity, and can suppress a brightness nonuniformity when it applies to an image display can be provided.
- the manufacturing method of the polarizing plate of the present invention is A step of forming a coating layer on a temporary support and drying to form a transfer film having an optical film formed on the temporary support, Attaching a polarizer to the air interface side surface of the optical film in the transfer film; It is a manufacturing method of the polarizing plate which has the process of exfoliating the above-mentioned temporary support from the above-mentioned transfer film,
- the optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
- the optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film;
- the thickness of the optical film is 4 to 10 ⁇ m,
- the elongation at break of the optical film is 2.5% or more in an environment of 25 ° C.
- the optical film of the present invention is An optical film comprising a copolymer containing a structural unit derived from butadiene, and a polyester-based additive,
- the content of the copolymer containing a structural unit derived from butadiene is 25 to 45% by mass with respect to the total solid content of the optical film
- the content of the polyester-based additive is 0.1 to 10% by mass with respect to the total solid content of the optical film
- the thickness of the optical film is 4 to 10 ⁇ m
- optical film of the present invention can be used in various applications.
- using as a structural member of a polarizing plate is mentioned.
- the optical film of the present invention can be used as a member constituting a polarizing plate, it can be used as a film for protecting a polarizer (also referred to as "polarizing plate protective film").
- polarizing plate protective film also referred to as "polarizing plate protective film”. It is preferable to use as a polarizing plate protective film of the side located in the display apparatus side through an adhesive especially.
- the breakage failure of the polarizing plate can be suppressed under high temperature and high humidity.
- the polarizing plate using the optical film of the present invention is preferably placed under conditions of 60 ° C. and 90% relative humidity as high-temperature and high-humidity conditions, for example.
- the destruction of the polarizing plate is caused by the fact that the polarizing plate protective film is destroyed by the fact that the PVA-based resin, which is a polarizer, absorbs moisture and elongates under high temperature and high humidity, and simultaneously extends from under room temperature due to temperature rise. Become. This destruction may occur when the polarizing plate protective film becomes thin, specifically 10 ⁇ m or less.
- the optical film of the present invention has the property of having a breaking elongation at 25 ° C. of 2.5% or more (that is, having high extensibility) in a sample form having a thickness of 30 ⁇ m and a width of 10 mm.
- the optical film of the present invention is used as a polarizing plate protective film to suppress destruction of the polarizing plate under high temperature and high humidity.
- the breaking elongation is 3.0% or more, and further preferably 3.5% or more.
- the upper limit of the elongation at break is not particularly limited, but is preferably 25% or less.
- the elongation at break is measured in a dry state (25 ° C., relative humidity 60%) using a sample having a thickness of 30 ⁇ m, a width of 10 mm, and a length of 120 mm.
- a tensile testing machine Tensilon RTC-1210A (Orientech Co., Ltd.)
- the breaking elongation is measured at a tension rate of 300 mm / min and a load cell 50N setting. The above measurement is carried out 5 times, and the results of 3 times excluding the maximum value and the minimum value are averaged to give a breaking elongation.
- the film thickness of the optical film in the present invention is 4 to 10 ⁇ m, it was decided to measure the elongation at break of a 30 ⁇ m-thick sample so that the test can be stably carried out in the measurement of the elongation at break.
- the sample with a thickness of 30 ⁇ m can be formed, for example, by using a coating composition for producing an optical film, adjusting to a thickness of 30 ⁇ m and laminating an optical film less than 30 ⁇ m, etc. It can be made.
- the optical film of the present invention can contain appropriately selected components having extensibility.
- the components having extensibility include ABS resin (acrylonitrile-butadiene-styrene resin), SB resin (styrene-butadiene resin), isoprene resin, butadiene resin, isobutyene-isobutene resin, polyether-urethane resin , Silicone resins, and the like.
- the above resin may be appropriately hydrogenated.
- the optical film of the present invention preferably contains, as a component having extensibility, a copolymer including a structural unit derived from butadiene.
- the optical film of the present invention preferably contains an ABS resin or an SB resin, and more preferably contains an SB resin.
- the SB resin that can be used for the optical film of the present invention is not particularly limited, but specifically, commercially available ones can be used.
- TR2000, TR2003, TR2250 all manufactured by JSR Corporation
- Clearene 210M, 220M, 730V above, Denka Co., Ltd. product
- Asaflex 800S, 805, 810, 825, 830, 840 aboveve, Asahi Kasei Co., Ltd. product
- Eporex SB2400, SB2610, SB2710 aboveve, Sumitomo Chemical Co., Ltd.) Inc.
- the optical film of the present invention preferably contains 15 to 95% by mass, more preferably 20 to 50% by mass of the component having extensibility in the total solid content of the optical film, and still more preferably 25 It is to contain up to 45% by mass.
- the total solid of an optical film means all the components except a solvent among the components contained in an optical film.
- the optical film of the present invention preferably comprises 25 to 45% by mass, more preferably 25 to 40% by mass, of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film. It is further more preferable that the content be 30% by mass.
- the component having extensibility itself preferably has an elongation at break of 10% or more at 25 ° C. in a sample form having a thickness of 30 ⁇ m and a width of 10 mm consisting of 100 wt% of the component having extensibility by itself And 20% or more is more preferable.
- the optical film of the present invention can include, in the method of producing a polarizing plate of the present invention, a component for controlling the releasability in the step of peeling from the temporary support.
- a component for controlling the releasability can be appropriately selected.
- the optical film of the present invention preferably has a component for controlling the releasability from the polyester-based polymer film, as it is preferable to use a polyester-based polymer film as a temporary support as described later.
- a component for controlling the releasability it is preferable to use a polyester-based additive.
- the polyester-based additive can be obtained by a known method such as dehydration condensation reaction of polybasic acid and polyhydric alcohol, or addition of dibasic acid anhydride to polyhydric alcohol and dehydration condensation reaction, and preferably It is a polycondensed ester formed from a dibasic acid and a diol.
- the weight average molecular weight (Mw) of the polyester-based additive is preferably 500 to 50000, more preferably 750 to 40000, and still more preferably 2000 to 30000.
- the weight average molecular weight of the polyester-based additive is preferably 500 or more in view of brittleness and wet heat durability, and is preferably 50000 or less in view of compatibility with the resin.
- the weight average molecular weight of polyester type additive measured the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of standard polystyrene conversion on condition of the following.
- Mn is a number average molecular weight of standard polystyrene conversion.
- GPC gel permeation chromatograph (HLC-8220GPC manufactured by Tosoh Corp .; column; guard column HXL-H manufactured by Tosoh Corp.) TSK gel G7000HXL, two TSK gel GMHXL, TSK gel G2000HXL sequentially, eluent: tetrahydrofuran , Flow rate: 1 mL / min, sample concentration: 0.7 to 0.8 mass%, sample injection amount: 70 ⁇ L, measurement temperature: 40 ° C., detector; differential refraction (RI) meter (40 ° C.), standard substance; Co., Ltd. TSK standard polystyrene)
- dicarboxylic acid As a dibasic acid which comprises a polyester type additive, dicarboxylic acid can be mentioned preferably.
- dicarboxylic acids include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and aromatic dicarboxylic acids or a mixture of aromatic dicarboxylic acids and aliphatic dicarboxylic acids can be preferably used.
- aromatic dicarboxylic acids aromatic carboxylic acids having 8 to 20 carbon atoms are preferable, and aromatic dicarboxylic acids having 8 to 14 carbon atoms are more preferable.
- aromatic dicarboxylic acids having 8 to 14 carbon atoms are more preferable.
- it is selected from phthalic acid, isophthalic acid, and terephthalic acid Preferably, at least one of them is used.
- aliphatic dicarboxylic acids aliphatic dicarboxylic acids having 3 to 8 carbon atoms are preferable, and aliphatic dicarboxylic acids having 4 to 6 carbon atoms are more preferable.
- succinic acid, maleic acid, adipic acid, and glutar acid are preferable.
- At least one selected from acids is preferable, and at least one selected from succinic acid and adipic acid is more preferable.
- diol which comprises a polyester type additive aliphatic diol, an aromatic diol, etc. are mentioned, Especially aliphatic diol is preferable.
- aliphatic diols aliphatic diols having 2 to 4 carbon atoms are preferable, and aliphatic diols having 2 to 3 carbon atoms are more preferable.
- Examples of aliphatic diols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol and the like, which may be used alone. Or it can use together and use two or more types.
- the polyester-based additive is particularly preferably a compound obtained by condensing an aliphatic diol with at least one selected from phthalic acid, isophthalic acid and terephthalic acid.
- the end of the polyester based additive may be sealed by reacting with a monocarboxylic acid.
- a monocarboxylic acid used for sealing aliphatic monocarboxylic acids are preferable, acetic acid, propionic acid, butanoic acid, benzoic acid and derivatives thereof are preferable, acetic acid or propionic acid is more preferable, and acetic acid is most preferable.
- polyester-based additives examples include ester-based resin polyester resin (for example, LP050, TP290, LP035, LP033, TP217, TP220) manufactured by Japan Synthetic Chemical Industry Co., Ltd., ester-based resin Byron manufactured by Toyobo Co., Ltd. (for example, Byron 245) , Byron GK 890, Byron 103, Byron 200, Byron 550, Byron GK 880, Byron GK 680), and the like.
- ester-based resin polyester resin for example, LP050, TP290, LP035, LP033, TP217, TP220
- ester-based resin Byron manufactured by Toyobo Co., Ltd.
- Byron 245 for example, Byron 245
- the content of the component (preferably a polyester-based additive) for controlling the releasability from the substrate is 0.1% by mass or more based on the total solid content of the optical film
- the content is 0.15% by mass or more, and more preferably 0.2% by mass or more.
- the content of the component (preferably a polyester-based additive) for controlling the releasability from the substrate is preferably 10% by mass or less, and 8% by mass or less, based on the total solid content of the optical film
- the content is more preferably 7.5% by mass or less. The above range is preferable from the viewpoint of obtaining appropriate adhesion together with the releasability from the base material.
- the optical film in the present invention can contain at least one leveling agent. Thereby, in the process of forming an application layer on a temporary support and drying to produce a transfer film having an optical film, film thickness unevenness and the like caused by drying variation due to local distribution of drying wind is suppressed. And improve the repelling of the coated material.
- the leveling agent for example, at least one leveling agent selected from silicone-based leveling agents and fluorine-based leveling agents can be used.
- the leveling agent is preferably an oligomer or a polymer rather than a low molecular weight compound.
- the leveling agent moves quickly on the surface of the applied coating film and becomes unevenly distributed, and the leveling agent will be unevenly distributed on the surface even after drying of the coated film, so a film to which the leveling agent is added Surface energy is reduced by the leveling agent.
- the surface energy of the film is preferably low from the viewpoint of preventing film thickness nonuniformity, repelling, and nonuniformity.
- the silicone-based leveling agent include polymers or oligomers having a plurality of dimethylsilyloxy units as repeating units and having a substituent at the terminal and / or side chain.
- the polymer or oligomer containing dimethylsilyloxy as a repeating unit may contain structural units other than dimethylsilyloxy.
- the substituents may be the same or different and are preferably a plurality.
- Preferred examples of the substituent include groups containing a polyether group, an alkyl group, an aryl group, an aryloxy group, a cinnamoyl group, an oxetanyl group, a fluoroalkyl group, a polyoxyalkylene group, and the like.
- the number average molecular weight of the silicone leveling agent is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, particularly preferably 1,000 to 30,000, and 1,000 to 20,000. Most preferably.
- a preferable silicone type leveling agent as a commercially available silicone type leveling agent which does not have an ionizing radiation curing group, Shin-Etsu Chemical Co., Ltd. X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015. X22176DX, X22-176F, X224272, KF8001, X22-2000, etc .; FM4421, FM0425, FMDA26, FS1265 etc. made by Chisso Corporation; BY16-750, BY16880, BY16848, SF8427, made by Toray Dow Corning Corporation.
- TSF series manufactured by Momentive Performance Materials Japan Ltd. (TSF 4460, TSF 4440, TSF 4445, TSF 4446, TSF 4453, TSF 4452, TSF 4730, TSF 4770, etc.), FGF 502, SILWET series (SILWETL 77, SILWETL 2 780, SILWETL 7608, SILWETL 7001, SILWETL 7002 SILWETL7600, SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, S LWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720) is not limited thereto but can be exemplified.
- UVHC1105, UVHC8550 etc. made from can be mentioned, it is not limited to this.
- the fluorine-based leveling agent comprises a fluoroaliphatic group and a hydrophilic group which contributes to the affinity to various compositions such as coating and molding materials when, for example, this leveling agent is used as an additive.
- These compounds are compounds having the same molecule, and such compounds can be generally obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a hydrophilic group.
- Representative examples of the monomer having a hydrophilic group, which is copolymerized with the monomer having a fluoroaliphatic group include poly (oxyalkylene) acrylate, poly (oxyalkylene) methacrylate and the like.
- Megafac series MCF 350-5, F 472, F 476, F 445, F 444, F 443, F 178, F 470, F 475, F 479, manufactured by DIC Corporation as having no ionizing radiation curing group.
- Neos Co., Ltd.'s lidagent series (FTX 218, 250, 245 M, 209 F, 222 F, 245 F, 208 G, 218 G, 240 G, 206 D, 240 D, etc.) and having an ionizing radiation curing group, Optool DAC manufactured by Daikin Industries, Ltd .; Defensor series manufactured by DIC (TF 3001, TF 3000, TF 3004, TF 3028, TF3). 27, TF3026, TF3025, etc.), RS series (RS71, RS101, RS102, RS103, RS104, RS105, etc.) are exemplified but not limited thereto.
- the leveling agent is preferably contained in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, in the total solid content of the optical film. It is most preferable to contain 1.0% by mass.
- the optical film of the present invention can be obtained by drying a coated layer formed by applying a composition for forming an optical film.
- the composition for optical film formation can contain a solvent (solvent).
- the solvent preferably, an organic solvent
- the solvent can dissolve or disperse the material for forming the optical film, can easily form a uniform surface state in the coating step and the drying step, can ensure the liquid storage property, and is moderately saturated It can select suitably from a viewpoint of having steam pressure etc.
- organic solvent examples include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate Methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, acetic acid Propyl, methyl propionate, ethyl propionate, ⁇ -butyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxya
- the above solvents it is preferable to use at least one selected from dimethyl carbonate, methyl acetate, ethyl acetate, methyl ethyl ketone, acetyl acetone, acetone, toluene and xylene, and it is more preferable to use any of dimethyl carbonate, ethyl acetate and toluene Preferably, it is particularly preferred to use ethyl acetate.
- the solid concentration of the composition for forming an optical film is in the range of 5 to 80% by mass, more preferably 6 to 75% by mass, and still more preferably 7 to 70% by mass It is.
- the optical film of the present invention can contain other components from the viewpoint of improving other performances.
- characteristic values other than those described above are not particularly limited, and performance equivalent to that of a general known polarizing plate protective film can be appropriately mounted. It is preferable to appropriately have the performance required for a so-called inner film disposed between the liquid crystal panel and the liquid crystal panel.
- Specific property values can include haze related to display characteristics, light transmittance, spectral characteristics, wet heat durability of retardation, etc., and dimensional changes associated with wet heat thermos related to mechanical characteristics and polarizing plate processing suitability Rate, glass transition temperature, equilibrium moisture absorption rate, moisture permeability, contact angle, etc. can be mentioned.
- the optical film of the present invention in order to appropriately impart the required performance to the above-mentioned so-called inner film, it is preferable to include the polymer resin described below.
- the polymer resin is not particularly limited. Specific examples include cyclic olefin resins, styrene resins, polyester resins, polycarbonate resins, vinyl resins, polyimide resins, polyarylate resins, etc., and cyclic polyolefin resins and styrene resins And from the viewpoint of appropriately imparting the performance required for the inner film.
- cyclic olefin resin As an example of cyclic olefin resin, it is a thermoplastic resin which has a unit of a monomer which consists of cyclic olefins, such as norbornene and a polycyclic norbornene monomer, for example, and is also called thermoplastic cyclic olefin resin.
- the cyclic olefin resin may be a hydrogenated product of the above ring-opening polymer of cyclic olefin or ring-opening copolymer using two or more cyclic olefins, cyclic olefin, chain olefin, vinyl It may be an addition polymer with an aromatic compound having a polymerizable double bond such as a group. A polar group may be introduced into the cyclic olefin resin.
- the protective film is made of a copolymer of a cyclic olefin and an aromatic compound having a chain olefin and / or a vinyl group
- ethylene, propylene and the like are used as the chain olefin
- an aromatic having a vinyl group As the group compound, styrene, ⁇ -methylstyrene, nuclear alkyl substituted styrene and the like are used.
- the unit of the cyclic olefin monomer may be 50 mol% or less, preferably about 15 to 50 mol%.
- the unit of the monomer comprising the cyclic olefin may be relatively small as described above. it can.
- the unit of monomers consisting of chain olefins is usually 5 to 80 mol%
- the unit of monomers consisting of aromatic compounds having a vinyl group is usually 5 to 80 mol%.
- any commercially available product can be used.
- TOPAS manufactured by TOPAS ADVANCED POLYMERS GmbH, Germany, and sold by Polyplastics Co., Ltd. in Japan, from JSR Co., Ltd.
- Arton sold, "ZEONOR” (ZEONOR) sold by Nippon Zeon Co., Ltd.
- Apel sold by Mitsui Chemical Co., Ltd. (all of which are listed above) Trade name) etc.
- the resin containing 50 mass% or more of styrene monomers is said.
- the styrenic monomer refers to a monomer having a styrene skeleton in its structure.
- styrenic resins may be homopolymers of styrene or derivatives thereof, and binary or higher copolymers of styrene or derivatives thereof with other copolymerizable monomers.
- a styrene derivative is a compound in which another group is bound to styrene, and examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, Alkylstyrene such as p-ethylstyrene, hydroxystyrene, hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, styrene such as p-chlorostyrene, hydroxyl group, alkoxy group, carboxyl group, halogen at benz
- the styrenic resin is preferably a homopolymer of styrene (that is, polystyrene).
- the styrenic resin is a copolymer of styrene or a styrene derivative and at least one monomer selected from acrylonitrile, maleic anhydride, methyl methacrylate and butadiene. It is preferable to be combined.
- polystyrene Although various things can be used as a polystyrene, It is preferable that it is GPPS grade. In general, GPPS grade polystyrene is due to its high transparency. Examples of the index indicating the degree of polymerization of polystyrene include a melt mass flow rate measured by melt flow, a melt volume flow rate, and a weight average molecular weight (Mw) measured by gel permeation chromatography.
- Mw weight average molecular weight
- the melt mass flow rate is 18 g / 10 min or less, the degree of polymerization of polystyrene is high, which is advantageous for suppressing the breakage failure of the polarizing plate.
- the polystyrene used in the present invention preferably has a Mw of 180000 or more. More preferably, it is 350000 or more. When Mw is 180,000 or more, the degree of polymerization of polystyrene is high, which is advantageous for suppressing the breakage failure of the polarizing plate.
- Preferred polystyrenes include CR-3500, CR-4500, CR-2600, XC-315, XC-515 manufactured by DIC Corporation, HF77, 679, SGP-10 manufactured by PS Japan Co., Ltd., G200C, G210C manufactured by Toyo Styrene Co., Ltd. , G320C, HRM12, HRM26, HRM48N, and the like, but it is not limited thereto.
- styrene resins include those obtained by copolymerizing styrene monomer components with other monomer components.
- alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methyl phenyl methacrylate, isopropyl methacrylate, etc .
- methyl acrylate, ethyl acrylate, Unsaturated carboxylic acid alkyl ester monomers such as alkyl acrylates such as butyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate; methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid
- Unsaturated carboxylic acid monomers such as cinnamic acid
- unsaturated dicarboxylic acid anhydride monomers which are anhydrides such as maleic anhydride, itaconic acid, ethyl maleic acid, methyl
- the styrene-based resin that can be suitably used in the present invention may be a styrene / acrylonitrile copolymer, a styrene / methacrylic acid copolymer, or a styrene / maleic anhydride copolymer because the heat resistance is high. .
- the optical film of the present invention contains the acrylic resin.
- the copolymer proportion of acrylonitrile in the copolymer is preferably 1 to 40% by mass.
- a further preferred range is 1 to 30% by mass, and a particularly preferred range is 1 to 25% by mass.
- the proportion of the acrylonitrile copolymer in the copolymer is 1 to 40% by mass, it is preferable because the transparency is excellent.
- the copolymer proportion of methacrylic acid in the copolymer is preferably 0.1 to 50% by mass.
- a more preferable range is 0.1 to 40% by mass, and a further preferable range is 0.1 to 30% by mass.
- the copolymer ratio of methacrylic acid in a copolymer is 0.1 mass% or more, and excellent in transparency if it is 50 mass% or less, it is preferable.
- the proportion of maleic anhydride copolymer in the copolymer is preferably 0.1 to 50% by mass.
- a more preferable range is 0.1 to 40% by mass, and a further preferable range is 0.1% to 30% by mass.
- the maleic anhydride content in a copolymer is 0.1 mass% or more, and since it is excellent in transparency if it is 50 mass% or less, it is preferable.
- the styrene resin plural kinds of resins having different compositions, molecular weights and the like can be used in combination.
- the styrenic resin can be obtained by a known anionic, bulk, suspension, emulsification or solution polymerization method.
- the unsaturated double bond of the benzene ring of the conjugated diene or the styrene monomer may be hydrogenated.
- the hydrogenation rate can be measured by nuclear magnetic resonance (NMR).
- polycarbonate resin examples include polycarbonate, a polycarbonate containing a structural unit in which bisphenol A is fluorene-modified, and a polycarbonate containing a structural unit in which bisphenol A is 1,3-cyclohexylidene-modified.
- vinyl resins include polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polyvinyl alcohol and the like.
- the content of the polymer resin is preferably 5 to 55% by mass, more preferably 5 to 45% by mass, with respect to the total solid content of the optical film.
- the content is further preferably 35% by mass, particularly preferably 7 to 30% by mass, and most preferably 10 to 25% by mass.
- ⁇ Adhesive improvement component of optical film to polarizer> By including an adhesive property improvement component of the optical film to the polarizer as another component, in the polarizing plate having the optical film of the present invention, the adhesion of the optical film to the polarizer can be improved.
- the optical film of the present invention is a copolymer comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) as an adhesive property improving component of the optical film to a polarizer. It may contain a crosslinking reaction product derived from coalescence (hereinafter also referred to as “copolymer (a)”) and / or copolymer (a). The optical film of the present invention may contain only one of either the copolymer (a) or the crosslinking product derived from the copolymer (a), or may contain both of them. Good.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 2 represents an alkyl group having at least one fluorine atom as a substituent
- —Si (R a3 ) (R a4 L represents a group containing O-
- at least one divalent linking group selected from the group consisting of R a3 and R a4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
- R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group
- R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group
- R 11 and R 12 may be linked.
- X 1 represents a divalent linking group.
- R 1 in the general formula (I) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms More preferred is a hydrogen atom or a methyl group.
- R 2 in the general formula (I) is preferably an alkyl group (fluoroalkyl group) having at least one fluorine atom as a substituent, and is preferably a fluoroalkyl group having 1 to 20 carbon atoms, and 1 to 18 carbon atoms Is more preferably a fluoroalkyl group, and more preferably a fluoroalkyl group having 2 to 15 carbon atoms.
- the number of fluorine atoms in the fluoroalkyl group is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.
- -O (C O)-is a group on R 1 side
- the divalent aliphatic chain group represented by L an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
- the divalent aliphatic cyclic group represented by L is preferably a cycloalkylene group having 3 to 20 carbon atoms, and more preferably a cycloalkylene group having 3 to 15 carbon atoms.
- the repeating unit represented by the general formula (I) is particularly preferably a repeating unit represented by the following general formula (III), from the viewpoint of the surface uneven distribution advantageous to the adhesion and the radical polymerization property.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- ma and na each independently represent an integer of 1 to 20
- X represents a hydrogen atom or a fluorine atom.
- R 1 in the general formula (III) is the general formula (I) in the same meaning as R 1, and preferred ranges are also the same.
- Ma and na in the general formula (III) each independently represent an integer of 1 to 20. From the viewpoint of surface uneven distribution advantageous for adhesion and easiness of raw material acquisition and production, ma in general formula (III) is preferably an integer of 1 to 8, and an integer of 1 to 5 More preferable. Also, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, still more preferably an integer of 2 to 10, and most preferably an integer of 5 to 7.
- X in the general formula (III) represents a hydrogen atom or a fluorine atom, preferably a fluorine atom.
- the repeating unit represented by the general formula (I) or (III) can be obtained by polymerization of a monomer, and preferred monomers include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-Pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ) Ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate ) Acrylate, 2- (perfluoro-7-methyloctyl) ethy
- R 2 in the general formula (I) has a repeating unit (polysiloxane structure) containing a siloxane bond represented by —Si (R a3 ) (R a4 ) O—.
- R a3 and R a4 may each independently have an alkyl group which may have a substituent (preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent) or a substituent Represents an aryl group.
- the copolymer (a) is preferably a graft copolymer in which a polysiloxane structure is introduced into the side chain.
- the compound having a siloxane bond for obtaining the graft copolymer is more preferably a compound represented by the following general formula (IV).
- R a3 and R a4 each independently represent an alkyl group, a haloalkyl group or an aryl group.
- the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.
- a methyl group, an ethyl group and a hexyl group can be mentioned.
- the haloalkyl group is preferably a fluorinated alkyl group having 1 to 10 carbon atoms.
- trifluoromethyl group and pentafluoroethyl group can be mentioned.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms.
- a phenyl group and a naphthyl group can be mentioned.
- R a3 and R a4 are preferably a methyl group, a trifluoromethyl group or a phenyl group, and a methyl group is particularly preferable.
- R a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R a5 is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- nn is preferably 10 to 1000, more preferably 20 to 500, and still more preferably 30 to 200.
- the nn R a3 's in the general formula (IV) may be the same or different, and the nn R a4' s may be the same or different.
- one end (meth) acryloyl group-containing polysiloxane macromer for example, Silaprene 0721, 0725 (all trade names, manufactured by JNC Co., Ltd.), AK-5, AK-30, AK-32 (all trade names, manufactured by Toa Gosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701 IE, X-22-164B, X- 22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. be able to.
- Silaprene 0721, 0725 all trade names, manufactured by JNC Co., Ltd.
- AK-5 AK-30
- AK-32 all trade names, manufactured by Toa Gosei Co., Ltd.
- KF-100T for example, Silaprene 0721
- the copolymer (a) has a repeating unit represented by the general formula (II) in addition to the repeating unit represented by the above general formula (I).
- the repeating unit represented by the general formula (II) has a strong interaction with a hydroxyl group. That is, when an adhesive layer having a hydroxyl group is provided on the surface of the coating solution after applying the coating solution of the composition for forming an optical film on the substrate, part of the repeating unit represented by the general formula (II) or The entire interaction with the hydroxyl group causes the copolymer (a) to diffuse and be adsorbed to the adhesive layer interface having the hydroxyl group and the inside of the adhesive layer.
- the copolymer (a) having the repeating unit represented by the general formula (II) added to the coating solution is an optical film, an adhesive layer, and A copolymer having the same chemical structure as that of the general formula (II) or a derivative having a structure in which the repeating unit represented by the general formula (II) is reacted with the hydroxyl group of the adhesive layer (crosslinking reaction Exist as As such, since the copolymer having the repeating unit represented by the general formula (II) interacts with the adhesive layer, regardless of the ratio of the copolymer present in the adhesive layer and / or the optical film. The adhesion between the optical film containing the copolymer (a) and the adhesive layer can be enhanced.
- R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group
- R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group
- R 11 and R 12 may be linked.
- X 1 represents a divalent linking group.
- R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms More preferred is a hydrogen atom or a methyl group.
- the substituted or unsubstituted aliphatic hydrocarbon group represented by R 11 and R 12 in the general formula (II) includes a substituted or unsubstituted alkyl group, an alkenyl group and an alkynyl group.
- Specific examples of the above alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group and hexadecyl group.
- alkenyl group examples include linear or branched such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like And cyclic or cyclic alkenyl groups.
- alkynyl group examples include ethynyl group, 1-propynyl group, 1-butynyl group, 1-octynyl group and the like.
- a substituted or unsubstituted R 11 and R 12 represent each, specific examples of the aryl group include phenyl group. Further, those in which 2 to 4 benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated 5-membered ring form a condensed ring can be mentioned, and specific examples thereof include a naphthyl group, an anthryl group, A phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group, a pyrenyl group etc. are mentioned.
- a hydrogen on a heteroaromatic ring containing one or more hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom Included are those in which one atom is removed to form a heteroaryl group.
- heteroaromatic ring containing one or more hetero atoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole Thiazole, Thiadiazole, Indole, Carbazole, Benzofuran, Dibenzofuran, Thianaphtene, Dibenzothiophene, Indazole Benzimidazole, Anthranil, Benzisoxazole, Benzoxazole, Benzothiazole, Purine, Pyridine, Pyridazine, Pyrimidin, Pyrazine, Triazine, Quinoline, Acridine, Isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine and the like can be mentioned.
- R 11 and R 12 may be linked, and in this case, R 11 and R 12 each independently represent an alkyl group or an aryl group, which are preferably linked to each other, R More preferably, 11 and R 12 are alkyl groups, which are linked to each other.
- R 11 , R 12 and X 1 may be optionally substituted by one or more substituents.
- substituents include monovalent nonmetallic atomic groups other than hydrogen atoms, and are selected from, for example, the following Substituent Group Y.
- Substituent group Y Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, aryldithio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ally N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acy
- R 11 and R 12 in general formula (II) each independently represent a hydrogen atom or an alkyl group, or are both alkyl groups and are preferably bonded to each other to form a ring, R 11 and R 12 It is preferred that both are hydrogen atoms, or are both alkyl groups and bonded to each other to form a ring.
- the repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (V).
- the adhesion improvement by the repeating unit represented by the general formula (V) is presumed to be due to the effect of bringing the polarity close to the adhesive layer having a hydroxyl group.
- R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group
- R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group
- R 11 and R 12 may be linked.
- X 12 preferably contains 1 to 5 aromatic rings, more preferably 2 to 4 aromatic rings, and most preferably 2 to 3 aromatic rings.
- Each preferred range of R 10, R 11 and R 12 in the general formula (V) are the same as R 10, R 11 and R 12 in the general formula (II).
- the repeating unit represented by Formula (II) or (V) is more preferably a repeating unit represented by the following Formula (VI).
- R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group
- R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group
- R 11 and R 12 may be linked.
- R 10 in formula (VI), R 11 and R 12 are the same as R 10, R 11 and R 12 in the general formula (II).
- the repeating units represented by the general formulas (II), (V) or (VI) can be obtained by polymerization of monomers. Specific examples of preferable monomers giving the repeating unit represented by the general formula (II), (V) or (VI) are shown, but not limited thereto.
- the copolymer (a) optionally has a repeating unit (other repeating units) other than the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) It may be done.
- Acrylic esters Methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2- Acryloyl oxyethyl succinate, 2-carboxyethyl acrylate, etc.
- Methacrylic acid esters Methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxye
- Acrylamides Acrylamide, N-alkyl acrylamide (having 1 to 3 carbon atoms as alkyl, such as methyl, ethyl and propyl), N, N-dialkyl acrylamide (having 1 to 6 carbons as alkyl), N-hydroxyethyl-N-methyl acrylamide, N-2-acetamidoethyl-N-acetyl acrylamide and the like.
- Methacrylamides Methacrylamide, N-alkyl methacrylamide (having 1 to 3 carbon atoms as alkyl, such as methyl, ethyl and propyl), N, N-dialkyl methacrylamide (having 1 to 6 carbons as alkyl) N-hydroxyethyl-N-methyl methacrylamide, N-2-acetamidoethyl-N-acetyl methacrylamide and the like.
- Allylic compound Allyl esters (eg allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate etc.), allyloxyethanol etc.
- Allyl esters eg allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate etc.
- Vinyl ethers Alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.
- Alkyl vinyl ethers eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxye
- Vinyl esters Vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl- ⁇ -phenyl butyrate, vinyl cyclohexyl carboxylate and the like.
- Itaconic acid dialkyls Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.
- Dialkyl esters or monoalkyl esters of fumaric acid dibutyl fumarate and the like.
- crotonic acid As monomers giving other repeating units, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene, 4-vinylbenzoic acid, styrene macromer (AS-6S manufactured by Toagosei Co., Ltd.), methyl methacrylate Macromer (AA-6 manufactured by Toa Gosei Co., Ltd.) may also be mentioned. It is also possible to convert the structure of the polymer after polymerization by polymer reaction.
- the copolymer (a) preferably has a thermally crosslinkable group.
- the thermally crosslinkable group is a group which causes a crosslinking reaction by heating to crosslink, and specific examples thereof include a carboxyl group, an oxazoline group, a hydroxyl group, an isocyanate group, a maleimide group, an acetoacetoxy group, an epoxy group, amino and the like. It can be mentioned.
- the copolymer (a) preferably contains a repeating unit having a thermally crosslinkable group.
- the copolymer (a) is particularly preferably thermally crosslinked with other compounds contained in the optical film, in particular, a styrenic resin.
- the copolymer (a) can be immobilized on the surface of the optical film by the copolymer (a) and the styrenic resin each having a thermally crosslinkable group which is mutually reactive, and the optical film and the other films can be immobilized. It is possible to develop higher adhesion with layers, membranes, films or other articles.
- the content of the repeating unit represented by the general formula (I) in the copolymer (a) is preferably 5 to 95% by mass, and 8 to 90% by mass, based on the total mass of the copolymer (a) Is more preferable, and 10 to 85% by mass is more preferable.
- the content of the repeating unit represented by the general formula (II) in the copolymer (a) is preferably 0.5 to 80% by mass, based on the total mass of the copolymer (a), and 1 to 75 % By mass is more preferable, and 2 to 70% by mass is even more preferable.
- the content of the repeating unit having a thermally crosslinkable group in the copolymer (a) is preferably 0.5 to 80% by mass, and preferably 1 to 75% by mass, based on the total mass of the copolymer (a). More preferably, 2 to 70% by mass is more preferable.
- the weight average molecular weight (Mw) of the copolymer (a) is preferably 1000 to 200000, more preferably 1800 to 150000, still more preferably 2000 to 150000, particularly preferably 2500 to 140000, and very preferably 20000 to 120000.
- the number average molecular weight (Mn) of the copolymer (a) is preferably 500 to 160000, more preferably 600 to 120000, still more preferably 600 to 100000, particularly preferably 1000 to 80000, and very preferably 2000 to 60000.
- the dispersion degree (Mw / Mn) of the copolymer (a) is preferably 1.00 to 18.00, more preferably 1.00 to 16.00, still more preferably 1.00 to 14.00, and 1.
- the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography (GPC) under the following conditions.
- GPC gel permeation chromatography
- the copolymer (a) can be synthesized by a known method.
- the optical film of the present invention may or may not contain the copolymer (a), but when it is contained, the copolymer (a) does not impair the function of the optical film,
- the content is preferably 0.0001 to 40% by mass.
- the content is more preferably 0.001 to 20% by mass, and still more preferably 0.005 to 10% by mass.
- An adhesion improving resin different from the copolymer (a) may be contained as an adhesion improving component of the optical film to the polarizer.
- the adhesion improving resin preferably has a heat-crosslinkable group, and the adhesion improving resin preferably comprises a repeating unit derived from a styrenic monomer.
- the thermally crosslinkable group is the same as that described for the above-mentioned copolymer (a).
- the copolymer (a) is immobilized on the surface of the functional film It is possible to develop higher adhesion.
- the copolymer (a) can be immobilized on the surface of the functional film by reacting the thermally crosslinkable group by heating, a compound (monomer) having a reactive group in the molecule is contained.
- the process of fixing the copolymer (a) to the surface of the functional film becomes unnecessary by curing the monomer by irradiation of ionizing radiation such as ultraviolet rays, it is preferable.
- the adhesion-improving resin may be used alone or in combination of two or more kinds having different repeating unit compositions, molecular weights and the like as the adhesion-improving resin.
- the adhesion improving resin can be obtained by known anionic, bulk, suspension, emulsion or solution polymerization methods.
- the unsaturated double bond of the benzene ring of a conjugated diene or a styrenic monomer may be hydrogenated.
- the hydrogenation rate can be measured by nuclear magnetic resonance (NMR).
- NMR nuclear magnetic resonance
- a commercial item can also be used as the adhesion improving resin, and examples thereof include Epocross RPS-1005: styrene-oxazoline copolymer (manufactured by Nippon Shokubai).
- the optical film of the present invention may or may not contain the adhesion improving resin, but when it is contained, the adhesion improving resin is relative to the total solid content of the optical film of the present invention.
- the content is preferably 0.0001 to 60% by mass, more preferably 0.001 to 55% by mass, and still more preferably 0.005 to 50% by mass.
- the optical film of the present invention may be a single film or have a laminated structure of two or more layers.
- the film thickness of the optical film preferable in the present invention is 3 to 20 ⁇ m, more preferably 3 to 15 ⁇ m, still more preferably 4 to 10 ⁇ m, particularly preferably 4 to 7 ⁇ m, and most preferably 4 to 6 ⁇ m.
- the film thickness is 3 to 20 ⁇ m, more preferably 3 to 15 ⁇ m, still more preferably 4 to 10 ⁇ m, particularly preferably 4 to 7 ⁇ m, and most preferably 4 to 6 ⁇ m.
- the optical film of the present invention can be produced using a known solution film forming method or melt extrusion method. Moreover, when laminating
- the optical film can be formed on the temporary support by the following coating method. Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, slide coating method, extrusion coating method (die coating method) (refer to JP-A-2003-164788), A known method such as a microgravure coating method is used, and among them, the microgravure coating method and the die coating method are preferable.
- crosslinks a thermally crosslinkable group can be used suitably.
- ⁇ Material of temporary support> As a material for forming a temporary support used in the transfer film of the present invention, in addition to the viewpoints of mechanical strength, surface roughness, thermal stability, etc., it may be selected by adhesion (adhesive force) with the optical film. it can.
- a well-known raw material and film can be used suitably as such a temporary support body.
- the material include polyester polymers, olefin polymers, cycloolefin polymers, (meth) acrylic polymers, cellulose polymers, and polyamide polymers.
- polyester-based polymers and olefin-based polymers are preferable as the material of the base film, polyester-based polymers are more preferable, and among polyester-based polymers, polyethylene terephthalate (PET) is particularly preferable.
- the surface energy of the temporary support is not particularly limited, the relationship between the surface energy of the material of the optical film and the coating solution and the surface energy of the surface of the temporary support on which the optical film is formed is adjusted. By doing this, the adhesion between the optical film and the temporary support can be adjusted. If the surface energy difference is reduced, the adhesive force tends to increase, and if the surface energy difference is increased, the adhesive force tends to decrease and can be set appropriately.
- the surface energy of the temporary support can be calculated using the method of Owens.
- DM 901 a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
- the surface energy of the temporary support on the side of forming the optical film is preferably 41.0 to 48.0 mN / m, and more preferably 42.0 to 48.0 mN / m. It is preferable that the surface energy is 41.0 mN / m or more, because the uniformity of the thickness of the optical film can be enhanced, and the peeling force of the optical film to the temporary support is suitably within the range of 48.0 mN / m or less. Because it is easy to control
- a release agent may be applied in advance.
- the optical film can be used after peeling off the temporary support after being bonded to the polarizer through an adhesive or a pressure-sensitive adhesive in a later step.
- the optical properties and mechanical properties can be adjusted by appropriately stretching the temporary support together with the optical film laminated on the temporary support.
- the surface of the temporary support on which the optical film is to be formed preferably has an arithmetic average roughness (Ra) of 40 nm or less, more preferably 0.1 to 38 nm, and 1 to 36 nm. It is further preferred that Arithmetic mean roughness (Ra) in the present invention is based on Japanese Industrial Standard (JIS) B0601: 2013. By setting Ra to 40 nm or less, the recess depth on the optical film side becomes small, and it is possible to suppress the breakage of the polarizing plate due to the extension of the polarizer under high temperature and high humidity.
- JIS Japanese Industrial Standard
- Ra 0.1 nm or more.
- the Ra of the present invention can be obtained, for example, by measuring 465.48 ⁇ m long and 620.64 ⁇ m wide using a non-contact surface / layer cross-sectional shape measurement system VertScan 2.0 (manufactured by Ryoka Systems Co., Ltd.) Can. Further, as another index, the height of the surface convex portion on the optical film side of the temporary support is preferably 0.1 to 10.0 ⁇ m.
- the height of the surface convex portion of the temporary support can be measured, for example, by observing the cross-sectional image of the temporary support with an optical microscope and observing the height of the convex portion protruding from the flat portion. .
- the surface convex portion By setting the surface convex portion to 10.0 ⁇ m or less, the depth of the concave portion on the optical film side can be reduced, and the breakage due to the extension of the polarizer under high temperature and high humidity can be suppressed.
- the thickness of the temporary support used to form the optical film by the coating method is preferably 5 to 100 ⁇ m, more preferably 10 to 75 ⁇ m, and still more preferably 15 to 55 ⁇ m.
- the film thickness is 5 ⁇ m or more, sufficient mechanical strength is easily secured, and a failure such as curl, wrinkle, or buckling does not easily occur, which is preferable.
- the transfer film of the optical film of the present invention and the temporary support is stored, for example, in the form of a long roll, the surface pressure applied to the transfer film is adjusted to an appropriate range as the film thickness is 100 ⁇ m or less. It is preferable because it is easy to cause and adhesion failure does not easily occur. Thicknessing processing can also be given to both ends as appropriate.
- the temporary support used in the transfer film of the present invention is provided with a thickening process at both ends.
- Thickening also referred to as knurling
- the height of the thickness setting processing to be applied can be appropriately adjusted according to the thickness of the optical film, and is, for example, 0.2 to 5.5 ⁇ m, and preferably 0.5 to 5.0 ⁇ m. 0 to 4.5 ⁇ m is more preferable, and 1.5 to 4.0 ⁇ m is more preferable.
- the height of the thickness forming process is obtained by cutting out the thickness forming part of the most pressed part and measuring the height of unevenness with a thickness meter.
- the position of thickness processing is preferably 0 to 10% relative to the substrate from both ends of the substrate, more preferably 0.1 to 7%, and still more preferably 0.3 to 5%.
- the width of the thickness forming process is preferably 3 to 40 mm, more preferably 5 to 30 mm, and still more preferably 10 to 25 mm.
- the transfer film on which the optical film is coated is composed of at least a temporary support and an optical film, and is referred to as a transfer film as one integrated.
- the transfer film can adhere the optical film to other layers, films, films or other articles, and in particular can bond the optical film to the polarizer through the adhesive layer, and the obtained polarizing plate
- the temporary support can be peeled off from the optical film or can be used as it is as a part of the polarizing plate without peeling off, the temporary support can be peeled off from the optical film from the viewpoint of thinning the polarizing plate. It is preferable to use it.
- the peeling force between the optical film and the temporary support is determined by the material of the optical film, the material of the temporary support, and the internal strain of the optical film. Etc. can be adjusted and controlled.
- the peeling force can be measured, for example, by a test in which the temporary support is peeled in the direction of 90 ° with respect to the surface of the optical film, and the peeling force when measured at a speed of 300 mm / min is 0.001 to 5N.
- / 25 mm is preferable, 0.01 to 3 N / 25 mm is more preferable, and 0.05 to 1 N / 25 mm is more preferable. If it is 0.001 N / 25 mm or more, peeling of the temporary support in the peeling step can be prevented, and if it is 5 N / 25 mm or less, peeling failure in the peeling step (eg, dipping or cracking of the optical film) You can prevent.
- the polarizing plate in the present invention includes at least a polarizer and the optical film of the present invention.
- the polarizer and the optical film of the present invention may be bonded via an adhesive layer.
- the polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers.
- the iodine based polarizer and the dye based polarizer are generally produced using a polyvinyl alcohol based film.
- Any polarizer may be used in the present invention.
- the polarizer is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule.
- PVA polyvinyl alcohol
- dichroic molecule the description in JP-A-2009-237376 can be referred to, for example.
- the film thickness of the polarizer is usually 1 to 50 ⁇ m, preferably 2 to 30 ⁇ m, and more preferably 3 to 20 ⁇ m.
- the optical film of the present invention may be further bonded to the opposite surface of the surface to which the optical film of the present invention is bonded to the polarizer, or even if a polarizing plate protective film known in the prior art is bonded.
- the conventionally known polarizing plate protective film is not particularly limited with respect to any of the optical properties and materials, but includes a cellulose ester resin, an acrylic resin, and / or a cyclic olefin resin, a polyester resin (or a main component Film) can be preferably used, and an optically isotropic film or an optically anisotropic retardation film may be used.
- a polarizing plate protective film As a polarizing plate protective film conventionally known, as a thing containing cellulose ester resin, Fujitac TD40UC (made by Fujifilm Co., Ltd.) etc. can be utilized, for example.
- the polarizing plate protective film conventionally known includes, as a film containing an acrylic resin, a polarizing plate protective film containing a (meth) acrylic resin containing a styrene resin described in Japanese Patent No. 4570042, Japanese Patent No.
- a polarizing plate protective film containing a (meth) acrylic resin having a glutarimide ring structure described in claim 1 in the main chain, a polarizing plate containing a (meth) acrylic resin having a lactone ring structure described in JP2009-122664A A film, a polarizing plate protective film containing a (meth) acrylic resin having a glutaric anhydride unit described in JP-A-2009-139754 can be used.
- polarizing plate protective film As the polarizing plate protective film conventionally known, as a film containing cyclic olefin resin, cyclic olefin resin film described in paragraph [0029] or later of JP 2009-237376 A, JP 4881827 A, JP JP The cyclic olefin resin film containing the additive which reduces Rth of the 2008-063536 gazette can be utilized. As a film containing a polyester resin, a conventionally known polarizing plate protective film can be exemplified by Cosmo Shine SRF (Toyobo Co., Ltd.) made of polyethylene terephthalate.
- Cosmo Shine SRF Toyobo Co., Ltd.
- the polarizing plate can be produced by a known method, and is preferably produced by bonding so that the transport direction of the polarizer and the transport direction of the transfer film are parallel.
- the optical film may be subjected to surface treatment (described in JP-A-6-94915 and JP-A-6-118232) to make it hydrophilic, and for example, glow discharge treatment, corona discharge treatment, or alkali It is preferable to carry out saponification treatment and the like. Corona discharge treatment is most preferably used as the surface treatment.
- the transfer film in the present invention can be used by laminating the polarizer with a polarizer in the polarizing plate processing step via an adhesive or a pressure-sensitive adhesive, peeling off the temporary support, leaving only the optical film on the polarizing plate.
- the adhesive layer may be formed of an adhesive.
- an adhesive containing a resin having a hydroxyl group is preferable, and in addition to a polyvinyl alcohol-based adhesive, an epoxy-based active energy ray-curable adhesive, for example, a molecule as shown in JP-A 2004-245925
- An adhesive containing an epoxy compound which does not contain an aromatic ring and curing by heating or irradiation of active energy rays, the total amount of (meth) acrylic compounds described in JP-A-2008-174667 is 100 parts by mass ( a1) A (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule, and (b) a (meth) acrylic compound having a hydroxyl group in the molecule and having only one polymerizable double bond , (C1) containing phenol ethylene oxide modified acrylate or nonyl phenol ethylene oxide modified acrylate Such as sexual energy ray-curable adhesive.
- the polyvinyl alcohol-based adhesive is an adhesive containing modified or non-modified polyvinyl alcohol.
- the polyvinyl alcohol-based adhesive may contain a crosslinking agent in addition to the modified or unmodified polyvinyl alcohol.
- Specific examples of the adhesive include aqueous solutions of polyvinyl alcohol or polyvinyl acetal (eg, polyvinyl butyral), and latexes of vinyl polymers (eg, polyvinyl chloride, polyvinyl acetate, polybutyl acrylate).
- a particularly preferred adhesive is an aqueous solution of polyvinyl alcohol.
- polyvinyl alcohol is preferably completely saponified.
- the epoxy-based active energy ray-curable adhesive can be crosslinked with the copolymer (a) because the epoxy group is opened by irradiation of active energy rays to form a hydroxyl group. Therefore, in the present invention, an epoxy-type active energy ray-curable adhesive is also included as a hydroxyl group-containing adhesive and can be used appropriately.
- epoxy-based active energy ray-curable adhesives are disclosed in JP-A-2012-140610, JP-A-2012-140610, JP-A-2013-213214, JP-A-2015-40283, and JP-A-2015-. Those described in JP-A-143,352 and JP-A-2015-187744 can be used as appropriate.
- the heat treatment for polymerization of the thermally crosslinkable group of the optical film of the present invention described above can be carried out in the step of bonding a polarizer to the air interface side surface of the optical film in the transfer film. Moreover, after laminating
- the thermal crosslinking step is a heating step to accelerate the reaction of the thermal crosslinking group, and is not particularly limited as long as it does not impair the properties of the optical film, but preferably 40 to 200 ° C., more preferably 50. ⁇ 130 ° C.
- the temperature is preferably 50 ° C. or more from the viewpoint of facilitating the progress of the reaction, and is preferably 130 ° C. or less from the viewpoint of suppressing the deformation of the resin used for the substrate.
- the time required for heating varies depending on the type and amount of the thermally crosslinkable site group used, but is preferably 5 seconds to 1 hour, more preferably 10 seconds to 30 minutes, still more preferably 15 seconds to 5 minutes. 15 seconds or more are preferable in the viewpoint which makes reaction advance more easily, and 5 minutes or less are preferable in the viewpoint which heightens productivity.
- the manufacturing method of the polarizing plate of the present invention is A step of forming a coating layer on a temporary support and drying to form a transfer film having an optical film formed on the temporary support, Attaching a polarizer to the air interface side surface of the optical film in the transfer film; It is a manufacturing method of the polarizing plate which has the process of exfoliating the above-mentioned temporary support from the above-mentioned transfer film,
- the optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
- the optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film;
- the thickness of the optical film is 4 to 10 ⁇ m,
- the elongation at break of the optical film is 2.5% or more in an environment of 25 ° C.
- the temporary support and the polarizer used in the method for producing a polarizing plate of the present invention are the same as those described above.
- the coating solution for forming an optical film the component contained in the coating solution such as a copolymer containing a structural unit derived from butadiene, a polyester-based additive, other components, etc. or a component which may be included is the same as described above. It is.
- the coating method of the coating solution is also the same as described above.
- the thickness of the optical film, the breaking elongation and the like are also the same as those described above.
- the method for drying the coating layer formed on the temporary support is not particularly limited and can be carried out by a known method.
- the process of bonding a polarizer together on the optical film side surface in a transfer film can be performed by a well-known method, Preferably it is the same as that of what was mentioned above.
- the optical film side surface is usually the air interface side surface of the optical film.
- the step of peeling the temporary support from the transfer film is not particularly limited and can be performed by a known method.
- the present invention also relates to a display device including the polarizing plate of the present invention.
- the display device is not particularly limited, and may be a liquid crystal display device including a liquid crystal cell, an organic EL image display device including an organic EL layer, or a plasma image display device.
- the polarizing plate of the present invention can be disposed, for example, on the display surface side.
- any configuration of a known display device can be adopted.
- the liquid crystal display device of the present invention further has a backlight, and the polarizing plate is disposed on the backlight side or the viewing side.
- the liquid crystal display device of the present invention is preferably laminated in the order of the backlight, the backlight side polarizing plate, the liquid crystal cell, and the viewing side polarizing plate.
- any configuration of a known liquid crystal display device can be adopted.
- the mode (mode) of the liquid crystal cell there is also no particular limitation on the mode (mode) of the liquid crystal cell, and a TN (Twisted Nematic) mode liquid crystal cell, a horizontal electric field switching IPS (In-Plane Switching) mode liquid crystal cell, and an FLC (Ferroelectric Liquid Crystal) mode liquid crystal cell Liquid crystal cell of AFLC (Anti-ferroelectric Liquid Crystal) system, liquid crystal cell of OCB (Optically Compensatory Bend) system, liquid crystal cell of STN (Supper Twisted Nematic) system, liquid crystal cell of VA (Vertically Aligned) system, and HAN (Hybrid Aligned Nematic)
- the liquid crystal cell is preferably an IPS system.
- any configuration of a known liquid crystal display device can be adopted.
- the method for producing a liquid crystal display device of the present invention is a method for producing a liquid crystal display device, comprising the step of bonding the optical film side of the polarizing plate produced by the method for producing a polarizing plate of the present invention to the liquid crystal cell side. .
- Synthesis Example 1 (Synthesis example of fluorine-containing copolymer (A-19)) In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 23.3 g of cyclohexanone was charged, and the temperature was raised to 78 ° C.
- the component ratio of the fluorine-containing copolymer (A-19) was the following ratio as a result of the structure identification in the 1 H-NMR spectrum. 25 parts by weight of a repeating unit derived from 2- (perfluorohexyl) ethyl acrylate, 5 parts by weight of a repeating unit derived from 4- (4-acryloyloxybutoxy) benzoyloxyphenylboronic acid 1,3-dipropanol ester, acrylic acid 70 parts by weight of a repeating unit derived from
- Coating solutions 1-19 for forming an optical film were prepared with the compositions shown in Tables 1-2.
- “%” represents "% by mass”
- the numerical values in the solvent represent the content of each solvent in all the solvents contained in the total amount of the coating liquid
- the numerical values in the other components represent the coating It represents the content in the components (total solids) excluding the solvent in the liquid.
- the total solid concentration of the coating solutions 1 to 19 for forming an optical film was 14.3% by mass.
- F-552 Commercially available fluorine-based surface modifier (made by DIC Corporation, product name: Megafac F-552)
- SGP-10 Polystyrene (made by PS Japan)
- Epocross RPS-1005 Styrene-Oxazoline Copolymer (manufactured by Nippon Shokubai)
- Coating of Optical Film 1 Preparation of Optical Film A1 to A19 Using commercially available polyethylene terephthalate film, Emblet S38 (film thickness 38 ⁇ m, manufactured by UNITIKA CO., LTD.) As a base material and using coating liquids 1 to 19 so that the optical films A1 to A19 each have a film thickness of 30 ⁇ m It was made. Specifically, each coating solution is applied on a substrate at a transfer speed of 60 m / min by a die coating method using a slot die described in JP-A-2006-122889, Example 1; Dried for a second. Then it was rolled up. Thus, optical films A1 to A19 were produced. In addition, Ra of the surface of the side which forms the optical film of the said polyethylene terephthalate film was 34 nm.
- the film thicknesses and breaking elongations of the produced optical films A1 to A19 were evaluated by the following methods.
- the film thickness of the optical film is obtained by measuring the film thickness of a laminate (transfer film) manufactured using a contact film thickness meter KG30001 (manufactured by Anritsu Co., Ltd.), and subtracting the substrate thickness similarly measured therefrom. Calculated.
- the film thicknesses of the optical films A1 to A19 were all 30.0 ⁇ m.
- the elongation at break measurement of the optical films A1 to A19 prepared above was performed according to the following. That is, using a tensile tester Tensilon RTC-1210A (Orientech Co., Ltd.), a sample is cut out to a width of 10 mm and a length of 120 mm in a dry state (25 ° C., relative humidity 60%), and an optical film is made of polyethylene terephthalate film. Peel and prepare. The breaking elongation of this sample is measured at a tension rate of 300 mm / min and a load cell 50N setting. The measurement is made 5 times for each sample, and the results of three times excluding the maximum value and the minimum value are averaged to give a breaking elongation.
- ⁇ Coating of optical film 2 Preparation of optical films 1 to 19> A commercially available polyethylene terephthalate film, Lumirror (R) S105 (film thickness 38 ⁇ m, manufactured by Toray Industries, Inc.) is used as a substrate (temporary support), and coating liquids 1 to 19 are used to form optical films 1 to 19, respectively. It produced so that thickness might be set to 5.0 micrometers. Specifically, each coating solution is applied on a substrate at a transfer speed of 60 m / min by a die coating method using a slot die described in JP-A-2006-122889, Example 1; Dried for a second. Then it was rolled up. Thus, optical films 1 to 19 with a polyethylene terephthalate film temporary support were produced. In addition, Ra of the surface of the side which forms the optical film of the said polyethylene terephthalate film was 34 nm.
- the peeled surfaces of the optical films 1 to 19 produced above were evaluated by the following method. That is, an acrylic adhesive (20 ⁇ m in thickness) is attached to a glass substrate of 50 mm in length ⁇ 50 mm in width ⁇ 0.7 mm in thickness. Then, the optical film (thickness 5.0 ⁇ m, with a polyethylene terephthalate film temporary support) is attached such that the optical film is adjacent to the adhesive. After peeling off the temporary support, the optical film is observed with illumination at an angle of 45 to 30 °, with the vertical position being 90 °. If the peeled surface is whitish (if the peeling mark is "presence”), it is judged that there is a problem with the quality.
- Table 3 shows the evaluation results of the type of coating solution for forming an optical film, the elongation at break of optics A1 to A19, and the peeling marks of optical films 1 to 19 used in each example and comparative example.
- a polarizer was obtained using the following adhesive 1 using the thus obtained polarizer, the optical films 1 to 4, 7, 9, 12 to 19 with a temporary support, and the saponified cellulose acetate film.
- the film was laminated by roll-to-roll so that the absorption axis of the film and the longitudinal direction of each film were parallel.
- one surface of the polarizer is such that the coated surface (optical film side surface) of any one of the optical films 1 to 4, 7, 9 and 12 to 19 with a temporary support is on the polarizer side.
- the other side of the polarizer was laminated with the saponified cellulose acetate film.
- Adhesive 1 A 3% aqueous solution of polyvinyl alcohol (PVA-117H, manufactured by Kuraray Co., Ltd.) was used as an adhesive. When Adhesive 1 was used, it was cured by drying at 70 ° C. for 20 minutes after lamination.
- Adhesive 2 The ultraviolet curable adhesive of the composition shown below was produced. Celloxide 2021P 25 parts by mass Aron oxetane OXT-221 50 parts by mass Rika Resin DME-100 25 parts by mass Photoacid generator 1 5 parts by mass
- Adhesive 2 When Adhesive 2 is used, an ultraviolet ray with an illuminance of 200 mW / cm 2 and an irradiation amount of 160 mJ / cm 2 is irradiated at a temperature of 30 ° C. using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) And allowed to cure.
- the polyethylene terephthalate film as a substrate was continuously peeled off using the same apparatus as the separator peeling apparatus to produce a polarizing plate.
- ⁇ Mounting evaluation 1 for liquid crystal display> The above-prepared polarizing plate was used as a front side polarizing plate and rear side polarizing plate of an IPS mode liquid crystal television (slim type 55 type liquid crystal television, backlight and cell clearance 0.5 mm) It was bonded to the liquid crystal cell via an adhesive so as to be disposed on the cell side.
- the obtained liquid crystal television is kept in an environment of 60 ° C. and relative humidity 90% for 3 days, then transferred to an environment of 25 ° C. and relative humidity 60% and lighted in a black display state to cause light leakage defects due to the polarization plate breakage. evaluated.
- Table 4 shows the results of evaluation of light leakage due to breakage of the polarizing plate.
- the light leakage defect (in other words, the crack of the polarizing plate) at the time of black display when observed from the front of the device was observed and evaluated according to the following criteria.
- Example 1 to 12 the elongation at break was 4.1% or more, and there was no light leakage defect of the polarizing plate.
- Comparative Examples 1 to 5 peeling marks were observed, and the optical film used for the polarizing plate was at a level to be discarded.
- Examples 101 to 112 were of satisfactory quality in which light leakage defects were not confirmed by lighting in a black display state. The light leakage defect was confirmed in Comparative Examples 106 and 107. It is considered that this is because the optical film is broken (i.e., the polarizing plate is broken) by the extension of the polarizer under high temperature and high humidity.
- Examples 201 to 203, Comparative Examples 201 and 202 The optical films of Examples 201 to 203 and Comparative Examples 201 to 202 were obtained in the same manner as the optical film 1 except that the film thickness and the temporary support used were changed.
- the film thickness was produced with the film thickness described in Table 5.
- the temporary support was Emblet S38, and the surface asperity (Ra (nm)) was 34 nm as described in the table.
- a polarizing plate was produced in the same manner as in Example 101 except that the above-mentioned optical film was used. Using the produced polarizing plate, evaluation 1 for mounting on the liquid crystal display device and evaluation 2 for mounting on the following liquid crystal display device were performed.
- ⁇ Mounting evaluation 2 for liquid crystal display> The optical film produced as described above for the polarizing plate produced as the front side polarizing plate and rear side polarizing plate of an IPS mode liquid crystal television (slim type 55 type liquid crystal television, the clearance between the backlight and the cell is 0.5 mm) It was bonded to the liquid crystal cell via an adhesive so as to be disposed on the cell side.
- the obtained liquid crystal television is kept in an environment of 60 ° C. and relative humidity 90% for 3 days, then transferred to an environment of 25 ° C. and relative humidity 60% and kept on in a black state, and visually observed 24 hours later
- the light unevenness (brightness unevenness) caused by the panel warpage was evaluated.
- Examples 201 to 203 were of satisfactory quality with no light leakage defect and no luminance unevenness.
- Comparative Example 201 it is considered that the film thickness of the optical film is thin, and a portion where the film thickness is particularly thin due to the surface unevenness of the temporary support is cracked and thus a light leakage defect is generated.
- Comparative Example 202 it is considered that uneven brightness was generated because the film thickness of the optical film was increased.
- Example 204 Comparative Example 203
- the same procedure as in Example 101 was repeated except that the temporary support was changed to Theonex Q51 (Ra 9 nm, film thickness 38 ⁇ m, Teijin DuPont Film Co., Ltd.), to obtain an optical film 20 (film thickness 5.0 ⁇ m) .
- the same operation as in Example 101 was conducted except that the temporary support was changed to OPU-1 (Ra 76 nm, film thickness 38 ⁇ m, Mitsui Chemicals Tosoh Co., Ltd.), to obtain an optical film 21 (film thickness 5.0 ⁇ m) .
- Example 204 and Comparative Example 203 were produced in the same manner as in Example 101 except that the above optical film was used, and the evaluation of mounting on a liquid crystal display device 1 and the evaluation of mounting on a liquid crystal display device 2 were performed. . The results are shown below.
- Example 204 was of satisfactory quality with no light leakage defects and no luminance unevenness. Comparative Example 203 is considered to have caused a light leakage defect because the surface asperity of the temporary support was large and the portion where the film thickness of the optical film was particularly thin was broken.
- Example 205 to 209 ⁇ Production of Polarizing Plate>
- a polarizing plate 301 was obtained in the same manner as in Example 101 except that the polarizing plate protective film was replaced with a cellulose acetate film to make the above-mentioned polymethyl methacrylate film.
- a polarizing plate 302 was obtained in the same manner as in Example 101 except that the polarizing plate protective film was replaced with a cellulose acetate film to make the above-mentioned polyethylene terephthalate film.
- the adhesive was changed to the adhesive 2 instead of the adhesive 1, and the same operation was performed except that the ultraviolet ray was irradiated and cured to obtain a polarizing plate 303.
- Example 101 the polarizing plate protective film is replaced with a cellulose acetate film to make the above-mentioned polymethyl methacrylate film, and the adhesive is replaced with the adhesive 1 to make the adhesive 2, and the same procedure is followed except that curing is performed by irradiating ultraviolet light.
- the following operation was performed to obtain a polarizing plate 304.
- Example 101 is the same as Example 101 except that the polarizing plate protective film is replaced with a cellulose acetate film to form the above-mentioned polyethylene terephthalate film, and the adhesive is replaced by the adhesive 1 to form the adhesive 2 and irradiated with ultraviolet light to cure.
- the work was performed to obtain a polarizing plate 305.
- the evaluations 1 and 2 of mounting to the liquid crystal display devices of Examples 205 to 209 were performed using the above polarizing plates. The results are shown below.
- Examples 205 to 209 had satisfactory quality with no light leakage defect and no luminance unevenness.
- the optical film of the present invention is highly effective in suppressing the breakage of the polarizing plate under high temperature and high humidity. Moreover, it turned out that the liquid crystal display which comprises the polarizing plate which has an optical film of this invention can suppress a brightness nonuniformity.
- a method of manufacturing a polarizing plate capable of suppressing breakage failure under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device a method of manufacturing a liquid crystal display device having the above polarizing plate, and The optical film which can suppress the destructive failure of a polarizing plate under high humidity, and can suppress a brightness nonuniformity when it applies to an image display can be provided.
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本発明は、偏光板の製造方法及び液晶表示装置の製造方法、並びに光学フィルムに関する。 The present invention relates to a method of manufacturing a polarizing plate, a method of manufacturing a liquid crystal display, and an optical film.
光学フィルムは種々の用途に用いられており、例えば偏光板に用いられている。
偏光板は液晶表示装置(LCD)や有機エレクトロルミネッセンス(有機EL)ディスプレイ(OLED)などの部材として用いられ、その表示性能において重要な役割を果たす。一般的な偏光板は、ポリビニルアルコール(PVA)系樹脂にヨウ素錯体などの二色性色素を吸着配向させた偏光子の片面、もしくは両面に光学フィルムを貼合させた構成を有する。
近年、表示装置の大型化、薄型化、フレキシブル化が進んでおり、これに伴って偏光板もこれまでと異なる機能や、薄型化が求められる。
Optical films are used for various applications, for example, for polarizing plates.
A polarizing plate is used as a member such as a liquid crystal display (LCD) or an organic electroluminescence (organic EL) display (OLED), and plays an important role in the display performance. A general polarizing plate has a configuration in which an optical film is bonded to one side or both sides of a polarizer in which a dichroic dye such as iodine complex is adsorbed and oriented to a polyvinyl alcohol (PVA) resin.
In recent years, display devices have been increased in size, thickness, and flexibility, and accordingly, polarizing plates have been required to have different functions and thicknesses.
偏光板を薄型化するためには偏光板を構成する光学フィルムの薄型化が必要である。例えば特許文献1には、仮支持体上に塗布膜を設け、その塗布膜に偏光子を貼合した後、塗布膜から仮支持体を剥離することにより膜厚10μm未満の塗布膜フィルムが貼合された偏光板を作製する方法が記載されている。 In order to reduce the thickness of the polarizing plate, it is necessary to reduce the thickness of the optical film constituting the polarizing plate. For example, in Patent Document 1, a coating film is provided on a temporary support, and a polarizer is attached to the coating film, and then the coating film having a thickness of less than 10 μm is attached by peeling the temporary support from the coating film. A method of making combined polarizers is described.
特許文献1には主としてシクロオレフィンポリマーからなる塗布膜フィルムが記載されており、本発明者らの検討によると、仮支持体との剥離性に優れ、かつ低い複屈折性を有する塗布膜フィルムではあるが、一方で、偏光板形態とした後、大型表示装置に組み立て、高温高湿下に置くと、偏光子を形成するPVA系樹脂の吸湿等に起因する伸長に塗布膜フィルムが追従できず、偏光板が破壊する事象があることが分かった。
フィルムの特長となる機能は一般にフィルムの主材料によるところが大きいが、その主材料は必ずしも高温高湿下でのPVA系樹脂の変形に対応出来るわけではなく、むしろ不利である場合が多い。また、光学フィルムやそれを含む偏光板を画像表示装置に適用した際に、輝度ムラが抑制されることも望ましい。
Patent Document 1 describes a coated film mainly composed of a cycloolefin polymer, and according to the study of the present inventors, a coated film having excellent releasability from a temporary support and having low birefringence is disclosed. On the other hand, after being made into a polarizing plate form and then assembled into a large display device and placed under high temperature and high humidity, the coating film can not follow the elongation due to the moisture absorption of the PVA-based resin forming the polarizer. , It was found that there is an event that the polarizing plate breaks down.
In general, the characteristic function of the film largely depends on the main material of the film, but the main material is not necessarily able to cope with the deformation of the PVA-based resin under high temperature and high humidity, and is rather disadvantageous in many cases. In addition, it is also desirable that unevenness in luminance be suppressed when an optical film or a polarizing plate including the same is applied to an image display device.
上記問題に鑑み、本発明の解決しようとする課題は、高温高湿下における破壊故障が抑制され、かつ画像表示装置に適用した際に輝度ムラを抑制できる偏光板の製造方法及び上記偏光板を有する液晶表示装置の製造方法、並びに、高温高湿下において偏光板の破壊故障を抑制でき、かつ画像表示装置に適用した際に輝度ムラを抑制できる光学フィルムを提供することにある。 In view of the above problems, the problem to be solved by the present invention is a method of manufacturing a polarizing plate capable of suppressing breakage failure under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device. It is an object of the present invention to provide a method of manufacturing a liquid crystal display device, and an optical film capable of suppressing a breakdown failure of a polarizing plate under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device.
本発明者らは、本発明にかかる光学フィルム(機能性膜)の下記作用により前述の課題を解決できることを見出した。
すなわち、本発明の光学フィルムは、伸長性を有する成分を含有しており、本発明の光学フィルムを偏光板に用いた場合、高温高湿下での偏光子の伸長に追従して本発明の光学フィルムが伸長することで、偏光板の破壊故障を抑制できると考えられる。
The present inventors have found that the above-mentioned problems can be solved by the following action of the optical film (functional film) according to the present invention.
That is, the optical film of the present invention contains a component having extensibility, and when the optical film of the present invention is used for a polarizing plate, the optical film of the present invention follows the elongation of the polarizer under high temperature and high humidity. It is thought that the failure of the polarizing plate can be suppressed by the extension of the optical film.
したがって、上記課題を解決するための具体的手段である本発明は、以下の通りである。 Therefore, the present invention which is a specific means for solving the above-mentioned subject is as follows.
<1>
仮支持体上に塗布層を形成し、乾燥することにより、上記仮支持体上に光学フィルムを形成した転写フィルムを作成する工程、
上記転写フィルムにおける上記光学フィルムの空気界面側表面に偏光子を貼り合わせる工程、
上記転写フィルムから上記仮支持体を剥離する工程を有する偏光板の製造方法であって、
上記光学フィルムが、ブタジエンに由来する構成単位を含む共重合体を上記光学フィルムの全固形分に対して25~45質量%含み、
上記光学フィルムが、ポリエステル系添加剤を上記光学フィルムの全固形分に対して0.1~10質量%含み、
上記光学フィルムの厚さが、4~10μmであり、
上記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上であり、
上記仮支持体の上記光学フィルムを形成する側の表面の算術平均粗さが、40nm以下である、偏光板の製造方法。
<2>
上記光学フィルムが、スチレン系樹脂を含む<1>に記載の偏光板の製造方法。
<3>
<1>又は<2>に記載の製造方法により製造された偏光板の上記光学フィルム側を液晶セル側に貼り合わせる工程を有する、液晶表示装置の製造方法。
<4>
ブタジエンに由来する構成単位を含む共重合体と、ポリエステル系添加剤とを含む光学フィルムであって、
上記ブタジエンに由来する構成単位を含む共重合体の含有量が、上記光学フィルムの全固形分に対して25~45質量%であり、
上記ポリエステル系添加剤の含有量が、上記光学フィルムの全固形分に対して0.1~10質量%であり、
上記光学フィルムの厚さが、4~10μmであり、
上記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上である、光学フィルム。
<5>
スチレン系樹脂を含む、<4>に記載の光学フィルム。
<1>
A step of forming a coating layer on a temporary support and drying to form a transfer film having an optical film formed on the temporary support,
Attaching a polarizer to the air interface side surface of the optical film in the transfer film;
It is a manufacturing method of the polarizing plate which has the process of exfoliating the above-mentioned temporary support from the above-mentioned transfer film,
The optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
The optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film;
The thickness of the optical film is 4 to 10 μm,
The elongation at break of the optical film is 2.5% or more in an environment of 25 ° C. in a sample with a thickness of 30 μm and a width of 10 mm,
The manufacturing method of the polarizing plate whose arithmetic mean roughness of the surface of the side which forms the said optical film of the said temporary support body is 40 nm or less.
<2>
The manufacturing method of the polarizing plate as described in <1> in which the said optical film contains styrene resin.
<3>
The manufacturing method of the liquid crystal display device which has the process of bonding together the said optical film side of the polarizing plate manufactured by the manufacturing method as described in <1> or <2> on the liquid crystal cell side.
<4>
An optical film comprising a copolymer containing a structural unit derived from butadiene, and a polyester-based additive,
The content of the copolymer containing a structural unit derived from butadiene is 25 to 45% by mass with respect to the total solid content of the optical film,
The content of the polyester-based additive is 0.1 to 10% by mass with respect to the total solid content of the optical film,
The thickness of the optical film is 4 to 10 μm,
The optical film whose breaking elongation of the said optical film is 2.5% or more in a 25 degreeC environment in the sample of thickness 30 micrometers and width 10 mm.
<5>
The optical film as described in <4> containing styrene resin.
本発明により、高温高湿下における破壊故障が抑制され、かつ画像表示装置に適用した際に輝度ムラを抑制できる偏光板の製造方法及び上記偏光板を有する液晶表示装置の製造方法、並びに、高温高湿下において偏光板の破壊故障を抑制でき、かつ画像表示装置に適用した際に輝度ムラを抑制できる光学フィルムを提供することができる。 According to the present invention, a method of manufacturing a polarizing plate capable of suppressing breakage failure under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device, a method of manufacturing a liquid crystal display device having the above polarizing plate, and The optical film which can suppress the destructive failure of a polarizing plate under high humidity, and can suppress a brightness nonuniformity when it applies to an image display can be provided.
本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。尚、本願明細書において「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
また、本発明において、「(メタ)アクリル基」は、「アクリル基およびメタアクリル基のいずれか一方または双方」の意味で使用される。「(メタ)アクリル酸」、「(メタ)アクリルアミド」、「(メタ)アクリロイル基」なども同様である。
The contents of the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
In the present invention, "(meth) acrylic group" is used in the meaning of "either or both of an acrylic group and a methacrylic group". The same applies to “(meth) acrylic acid”, “(meth) acrylamide”, “(meth) acryloyl group” and the like.
本発明の偏光板の製造方法は、
仮支持体上に塗布層を形成し、乾燥することにより、上記仮支持体上に光学フィルムを形成した転写フィルムを作成する工程、
上記転写フィルムにおける上記光学フィルムの空気界面側表面に偏光子を貼り合わせる工程、
上記転写フィルムから上記仮支持体を剥離する工程を有する偏光板の製造方法であって、
上記光学フィルムが、ブタジエンに由来する構成単位を含む共重合体を上記光学フィルムの全固形分に対して25~45質量%含み、
上記光学フィルムが、ポリエステル系添加剤を上記光学フィルムの全固形分に対して0.1~10質量%含み、
上記光学フィルムの厚さが、4~10μmであり、
上記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上であり、
上記仮支持体の上記光学フィルムを形成する側の表面の算術平均粗さが、40nm以下である、偏光板の製造方法である。
また、本発明の光学フィルムは、
ブタジエンに由来する構成単位を含む共重合体と、ポリエステル系添加剤とを含む光学フィルムであって、
上記ブタジエンに由来する構成単位を含む共重合体の含有量が、上記光学フィルムの全固形分に対して25~45質量%であり、
上記ポリエステル系添加剤の含有量が、上記光学フィルムの全固形分に対して0.1~10質量%であり、
上記光学フィルムの厚さが、4~10μmであり、
上記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上である、光学フィルムである。
The manufacturing method of the polarizing plate of the present invention is
A step of forming a coating layer on a temporary support and drying to form a transfer film having an optical film formed on the temporary support,
Attaching a polarizer to the air interface side surface of the optical film in the transfer film;
It is a manufacturing method of the polarizing plate which has the process of exfoliating the above-mentioned temporary support from the above-mentioned transfer film,
The optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
The optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film;
The thickness of the optical film is 4 to 10 μm,
The elongation at break of the optical film is 2.5% or more in an environment of 25 ° C. in a sample with a thickness of 30 μm and a width of 10 mm,
It is a manufacturing method of a polarizing plate whose arithmetic mean roughness of the surface of the side which forms the above-mentioned optical film of the above-mentioned temporary support body is 40 nm or less.
Moreover, the optical film of the present invention is
An optical film comprising a copolymer containing a structural unit derived from butadiene, and a polyester-based additive,
The content of the copolymer containing a structural unit derived from butadiene is 25 to 45% by mass with respect to the total solid content of the optical film,
The content of the polyester-based additive is 0.1 to 10% by mass with respect to the total solid content of the optical film,
The thickness of the optical film is 4 to 10 μm,
It is an optical film whose breaking elongation of the said optical film is 2.5% or more in a 25 degreeC environment in the sample of thickness 30 micrometers and width 10 mm.
<光学フィルム>
本発明の光学フィルムは種々の用途に用いることができる。本発明の光学フィルムの用途の一例として、偏光板の構成部材として用いることが挙げられる。
本発明の光学フィルムは、偏光板を構成する部材として用いる場合、偏光子を保護する膜(「偏光板保護フィルム」とも呼ぶ。)として用いることができる。特に、粘着剤を介して表示装置側に位置する側の偏光板保護フィルムとして用いることが好適である。
<Optical film>
The optical film of the present invention can be used in various applications. As an example of the use of the optical film of this invention, using as a structural member of a polarizing plate is mentioned.
When the optical film of the present invention is used as a member constituting a polarizing plate, it can be used as a film for protecting a polarizer (also referred to as "polarizing plate protective film"). It is preferable to use as a polarizing plate protective film of the side located in the display apparatus side through an adhesive especially.
本発明の光学フィルムは、偏光板保護フィルムとして偏光板に用いられた際に、高温高湿下において偏光板の破壊故障を抑制できる。
本発明の光学フィルムを用いた偏光板を、例えば高温高湿条件として、60℃、相対湿度90%の条件下に置いて、3日間経過した後に、偏光板が破壊されていないことが好ましい。
偏光板の破壊は、高温高湿下で、偏光子であるPVA系樹脂が吸湿して伸長し、同時に温度上昇により室温下より伸長することにより、偏光板保護フィルムが破壊されることが切っ掛けとなる。この破壊は、偏光板保護フィルムが薄くなる、具体的には10μm以下になると、起こることがある。
When the optical film of the present invention is used as a polarizing plate protective film in a polarizing plate, the breakage failure of the polarizing plate can be suppressed under high temperature and high humidity.
The polarizing plate using the optical film of the present invention is preferably placed under conditions of 60 ° C. and 90% relative humidity as high-temperature and high-humidity conditions, for example.
The destruction of the polarizing plate is caused by the fact that the polarizing plate protective film is destroyed by the fact that the PVA-based resin, which is a polarizer, absorbs moisture and elongates under high temperature and high humidity, and simultaneously extends from under room temperature due to temperature rise. Become. This destruction may occur when the polarizing plate protective film becomes thin, specifically 10 μm or less.
本発明の光学フィルムは、厚さ30μm、幅10mmの試料形態において、25℃での破断伸度が2.5%以上であるという特性を有する(すなわち、高い伸長性を有する)。この特性を有することにより、本発明の光学フィルムは、偏光板保護フィルムとして用いられることで、高温高湿下での偏光板の破壊を抑制する。より好ましくは上記破断伸度が3.0%以上であり、更に好ましくは3.5%以上である。なお、上記破断伸度の上限は特に限定されないが、通常25%以下であることが好ましい。 The optical film of the present invention has the property of having a breaking elongation at 25 ° C. of 2.5% or more (that is, having high extensibility) in a sample form having a thickness of 30 μm and a width of 10 mm. By having this characteristic, the optical film of the present invention is used as a polarizing plate protective film to suppress destruction of the polarizing plate under high temperature and high humidity. More preferably, the breaking elongation is 3.0% or more, and further preferably 3.5% or more. The upper limit of the elongation at break is not particularly limited, but is preferably 25% or less.
本発明において、破断伸度の測定は、乾燥状態(25℃、相対湿度60%)で、厚さ30μm、幅10mm、長さ120mmの試料を用いて行う。この試料に対して、引っ張り試験機テンシロンRTC-1210A((株)オリエンテック)を用い、引っ張り速度300mm/分、ロードセル50Nの設定で、破断伸度を測定する。上記測定を5回行い、最大値と最小値を除いた3回の結果を平均し、破断伸度とする。
なお、本発明における光学フィルムの膜厚は4~10μmであるが、破断伸度の測定において、安定的に試験が行えるように、厚さ30μmの試料で破断伸度を測定することとした。厚さ30μmの試料は、例えば、光学フィルムを製造するための塗布組成物を用い、厚さが30μmとなるように調整して製膜することや、30μm未満の光学フィルムを積層するなどして作製することができる。
In the present invention, the elongation at break is measured in a dry state (25 ° C., relative humidity 60%) using a sample having a thickness of 30 μm, a width of 10 mm, and a length of 120 mm. Using this tensile testing machine Tensilon RTC-1210A (Orientech Co., Ltd.), the breaking elongation is measured at a tension rate of 300 mm / min and a load cell 50N setting. The above measurement is carried out 5 times, and the results of 3 times excluding the maximum value and the minimum value are averaged to give a breaking elongation.
Although the film thickness of the optical film in the present invention is 4 to 10 μm, it was decided to measure the elongation at break of a 30 μm-thick sample so that the test can be stably carried out in the measurement of the elongation at break. The sample with a thickness of 30 μm can be formed, for example, by using a coating composition for producing an optical film, adjusting to a thickness of 30 μm and laminating an optical film less than 30 μm, etc. It can be made.
<伸長性を有する成分>
本発明の光学フィルムは、伸長性を有する成分を適宜選んで含むことができる。
伸長性を有する成分としては、具体的には、ABS樹脂(アクリロニトリル-ブタジエンースチレン樹脂)、SB樹脂(スチレン-ブタジエン樹脂)、イソプレン樹脂、ブタジエン樹脂や、イソブチエン-イソブテン樹脂、ポリエーテル-ウレタン樹脂、シリコーン樹脂、等を挙げることができる。また、上記樹脂は、適宜水素添加してもよい。
本発明の光学フィルムは、伸長性を有する成分として、ブタジエンに由来する構成単位を含む共重合体を含むことが好ましい。
本発明の光学フィルムは、ABS樹脂またはSB樹脂を含むことが好ましく、SB樹脂を含むことがさらに好ましい。
<Component having extensibility>
The optical film of the present invention can contain appropriately selected components having extensibility.
Specifically, the components having extensibility include ABS resin (acrylonitrile-butadiene-styrene resin), SB resin (styrene-butadiene resin), isoprene resin, butadiene resin, isobutyene-isobutene resin, polyether-urethane resin , Silicone resins, and the like. In addition, the above resin may be appropriately hydrogenated.
The optical film of the present invention preferably contains, as a component having extensibility, a copolymer including a structural unit derived from butadiene.
The optical film of the present invention preferably contains an ABS resin or an SB resin, and more preferably contains an SB resin.
本発明の光学フィルムに用いることができるSB樹脂は、特に限定されないが、具体的には、市販されているものが使用でき、例えば、TR2000、TR2003、TR2250(以上、JSR(株)製)、クリアレン210M、220M、730V(以上、デンカ(株)製)、アサフレックス800S、805、810、825、830、840(以上、旭化成(株)製)、エポレックスSB2400、SB2610、SB2710(以上、住友化学(株))、等を挙げることができる。 The SB resin that can be used for the optical film of the present invention is not particularly limited, but specifically, commercially available ones can be used. For example, TR2000, TR2003, TR2250 (all manufactured by JSR Corporation), Clearene 210M, 220M, 730V (above, Denka Co., Ltd. product), Asaflex 800S, 805, 810, 825, 830, 840 (above, Asahi Kasei Co., Ltd. product), Eporex SB2400, SB2610, SB2710 (above, Sumitomo Chemical Co., Ltd.) Inc.), etc. can be mentioned.
本発明の光学フィルムは、伸長性を有する成分を、光学フィルムの全固形分中15~95質量%含むことが好ましく、より好ましくは、20~50質量%含むことであり、更に好ましくは、25~45質量%含むことである。
なお、光学フィルムの全固形分とは、光学フィルムに含まれる成分のうち、溶剤を除いた全成分をいう。
本発明の光学フィルムは、ブタジエンに由来する構成単位を含む共重合体を光学フィルムの全固形分に対して25~45質量%含むことが好ましく、25~40質量%含むことがより好ましく、25~30質量%含むことが更に好ましい。
The optical film of the present invention preferably contains 15 to 95% by mass, more preferably 20 to 50% by mass of the component having extensibility in the total solid content of the optical film, and still more preferably 25 It is to contain up to 45% by mass.
In addition, the total solid of an optical film means all the components except a solvent among the components contained in an optical film.
The optical film of the present invention preferably comprises 25 to 45% by mass, more preferably 25 to 40% by mass, of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film. It is further more preferable that the content be 30% by mass.
伸長性を有する成分は、それ自身で、すなわち伸長性を有する成分100質量%からなる、厚さ30μm、幅10mmの試料形態において、25℃での破断伸度が10%以上であることが好ましく、20%以上であることがより好ましい。 The component having extensibility itself preferably has an elongation at break of 10% or more at 25 ° C. in a sample form having a thickness of 30 μm and a width of 10 mm consisting of 100 wt% of the component having extensibility by itself And 20% or more is more preferable.
<基材からの剥離性を制御する成分>
本発明の光学フィルムは、本発明の偏光板の製造方法において、仮支持体からの剥離を行う工程における剥離性を制御する成分を含むことができる。仮支持体(基材)からの光学フィルムの剥離性を制御することで、剥離後の光学フィルムに剥離跡が付くことを防いだり、剥離工程の加工速度に適宜対応することができ、偏光板の品質や、生産性向上に好ましい効果を得ることができる。
<Component to control the removability from the substrate>
The optical film of the present invention can include, in the method of producing a polarizing plate of the present invention, a component for controlling the releasability in the step of peeling from the temporary support. By controlling the releasability of the optical film from the temporary support (base material), it is possible to prevent the formation of a peeling mark on the optical film after peeling, and to appropriately cope with the processing speed of the peeling step. It is possible to obtain favorable effects on the quality and productivity improvement of the
本発明の光学フィルムは、剥離性を制御する成分を適宜選ぶことができる。本発明の光学フィルムは、後述するように仮支持体としてポリエステル系高分子フィルムを用いることが好ましいことから、ポリエステル系高分子フィルムとの剥離性を制御する成分を有することが好ましい。剥離性を制御する成分としては、ポリエステル系添加剤を用いることが好ましい。 In the optical film of the present invention, a component for controlling the releasability can be appropriately selected. The optical film of the present invention preferably has a component for controlling the releasability from the polyester-based polymer film, as it is preferable to use a polyester-based polymer film as a temporary support as described later. As a component for controlling the releasability, it is preferable to use a polyester-based additive.
ポリエステル系添加剤は、多価塩基酸と多価アルコールとの脱水縮合反応、又は、多価アルコールへの無水二塩基酸の付加及び脱水縮合反応などの公知の方法で得ることができ、好ましくは二塩基酸とジオールとから形成される重縮合エステルである。 The polyester-based additive can be obtained by a known method such as dehydration condensation reaction of polybasic acid and polyhydric alcohol, or addition of dibasic acid anhydride to polyhydric alcohol and dehydration condensation reaction, and preferably It is a polycondensed ester formed from a dibasic acid and a diol.
ポリエステル系添加剤の重量平均分子量(Mw)は500~50000であることが好ましく、750~40000であることがより好ましく、2000~30000であることが更に好ましい。
ポリエステル系添加剤の重量平均分子量が500以上であると、脆性、湿熱耐久性の観点で好ましく、50000以下であると、樹脂との相溶性の観点で好ましい。
ポリエステル系添加剤の重量平均分子量は、以下の条件で標準ポリスチレン換算の重量平均分子量(Mw)および分子量分布(Mw/Mn)を測定した。なお、Mnは標準ポリスチレン換算の数平均分子量である。
GPC:ゲル浸透クロマトグラフ装置(東ソー(株)製HLC-8220GPC、カラム;東ソー(株)製ガードカラムHXL-H、TSK gel G7000HXL、TSK gel GMHXL2本、TSK gel G2000HXLを順次連結、溶離液;テトラヒドロフラン、流速;1mL/min、サンプル濃度;0.7~0.8質量%、サンプル注入量;70μL、測定温度;40℃、検出器;示差屈折(RI)計(40℃)、標準物質;東ソー(株)製TSKスタンダードポリスチレン)
The weight average molecular weight (Mw) of the polyester-based additive is preferably 500 to 50000, more preferably 750 to 40000, and still more preferably 2000 to 30000.
The weight average molecular weight of the polyester-based additive is preferably 500 or more in view of brittleness and wet heat durability, and is preferably 50000 or less in view of compatibility with the resin.
The weight average molecular weight of polyester type additive measured the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of standard polystyrene conversion on condition of the following. In addition, Mn is a number average molecular weight of standard polystyrene conversion.
GPC: gel permeation chromatograph (HLC-8220GPC manufactured by Tosoh Corp .; column; guard column HXL-H manufactured by Tosoh Corp.) TSK gel G7000HXL, two TSK gel GMHXL, TSK gel G2000HXL sequentially, eluent: tetrahydrofuran , Flow rate: 1 mL / min, sample concentration: 0.7 to 0.8 mass%, sample injection amount: 70 μL, measurement temperature: 40 ° C., detector; differential refraction (RI) meter (40 ° C.), standard substance; Co., Ltd. TSK standard polystyrene)
ポリエステル系添加剤を構成する二塩基酸としては、ジカルボン酸を好ましく挙げることができる。
ジカルボン酸としては、脂肪族ジカルボン酸、芳香族ジカルボン酸等が挙げられ、芳香族ジカルボン酸、又は芳香族ジカルボン酸と脂肪族ジカルボン酸の混合物を好ましく用いることができる。
As a dibasic acid which comprises a polyester type additive, dicarboxylic acid can be mentioned preferably.
Examples of dicarboxylic acids include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and aromatic dicarboxylic acids or a mixture of aromatic dicarboxylic acids and aliphatic dicarboxylic acids can be preferably used.
芳香族ジカルボン酸の中でも、炭素数8~20の芳香族カルボン酸が好ましく、炭素数8~14の芳香族ジカルボン酸がより好ましく、具体的には、フタル酸、イソフタル酸、及びテレフタル酸から選ばれる少なくとも1種が好ましい。 Among the aromatic dicarboxylic acids, aromatic carboxylic acids having 8 to 20 carbon atoms are preferable, and aromatic dicarboxylic acids having 8 to 14 carbon atoms are more preferable. Specifically, it is selected from phthalic acid, isophthalic acid, and terephthalic acid Preferably, at least one of them is used.
脂肪族ジカルボン酸の中でも、炭素数3~8の脂肪族ジカルボン酸が好ましく、炭素数4~6の脂肪族ジカルボン酸がより好ましく、具体的には、コハク酸、マレイン酸、アジピン酸、及びグルタル酸から選ばれる少なくとも1種が好ましく、コハク酸及びアジピン酸から選ばれる少なくとも1種がより好ましい。 Among the aliphatic dicarboxylic acids, aliphatic dicarboxylic acids having 3 to 8 carbon atoms are preferable, and aliphatic dicarboxylic acids having 4 to 6 carbon atoms are more preferable. Specifically, succinic acid, maleic acid, adipic acid, and glutar acid are preferable. At least one selected from acids is preferable, and at least one selected from succinic acid and adipic acid is more preferable.
また、ポリエステル系添加剤を構成するジオールとしては、脂肪族ジオール、芳香族ジオール等が挙げられ、特に脂肪族ジオールが好ましい。
脂肪族ジオールの中でも、炭素数2~4の脂肪族ジオールが好ましく、炭素数2~3の脂肪族ジオールがより好ましい。
脂肪族ジオールとしては、例えば、エチレングリコール、ジエチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、1,3-ブチレングリコール、1,4-ブチレングリコールなどが挙げることができ、これらを単独又は二種類以上を併用して用いることができる。
Moreover, as diol which comprises a polyester type additive, aliphatic diol, an aromatic diol, etc. are mentioned, Especially aliphatic diol is preferable.
Among the aliphatic diols, aliphatic diols having 2 to 4 carbon atoms are preferable, and aliphatic diols having 2 to 3 carbon atoms are more preferable.
Examples of aliphatic diols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol and the like, which may be used alone. Or it can use together and use two or more types.
ポリエステル系添加剤は、特に、フタル酸、イソフタル酸、及びテレフタル酸から選ばれる少なくとも1種と脂肪族ジオールとを縮合して得られる化合物であることが好ましい。 The polyester-based additive is particularly preferably a compound obtained by condensing an aliphatic diol with at least one selected from phthalic acid, isophthalic acid and terephthalic acid.
ポリエステル系添加剤の末端はモノカルボン酸と反応させて封止してもよい。封止に用いるモノカルボン酸としては脂肪族モノカルボン酸が好ましく、酢酸、プロピオン酸、ブタン酸、安息香酸及びその誘導体が好ましく、酢酸又はプロピオン酸がより好ましく、酢酸が最も好ましい。 The end of the polyester based additive may be sealed by reacting with a monocarboxylic acid. As a monocarboxylic acid used for sealing, aliphatic monocarboxylic acids are preferable, acetic acid, propionic acid, butanoic acid, benzoic acid and derivatives thereof are preferable, acetic acid or propionic acid is more preferable, and acetic acid is most preferable.
市販のポリエステル系添加剤としては、日本合成化学工業株式会社製エステル系樹脂ポリエスター(例えば、LP050、TP290、LP035、LP033、TP217、TP220)、東洋紡株式会社製エステル系樹脂バイロン(例えば、バイロン245、バイロンGK890、バイロン103、バイロン200、バイロン550、バイロンGK880、バイロンGK680)等が挙げられる。 Examples of commercially available polyester-based additives include ester-based resin polyester resin (for example, LP050, TP290, LP035, LP033, TP217, TP220) manufactured by Japan Synthetic Chemical Industry Co., Ltd., ester-based resin Byron manufactured by Toyobo Co., Ltd. (for example, Byron 245) , Byron GK 890, Byron 103, Byron 200, Byron 550, Byron GK 880, Byron GK 680), and the like.
本発明の光学フィルムは、基材からの剥離性を制御する成分(好ましくはポリエステル系添加剤)の含有量が、光学フィルムの全固形分に対して、0.1質量%以上であることが好ましく、0.15質量%以上であることがより好ましく、0.2質量%以上であることがさらに好ましい。また、基材からの剥離性を制御する成分(好ましくはポリエステル系添加剤)の含有量は、光学フィルムの全固形分に対して、10質量%以下であることが好ましく、8質量%以下であることがより好ましく、7.5質量%以下であることが更に好ましい。基材からの剥離性とともに、適度な密着性を得る観点から上記範囲が好ましい。 In the optical film of the present invention, the content of the component (preferably a polyester-based additive) for controlling the releasability from the substrate is 0.1% by mass or more based on the total solid content of the optical film Preferably, the content is 0.15% by mass or more, and more preferably 0.2% by mass or more. In addition, the content of the component (preferably a polyester-based additive) for controlling the releasability from the substrate is preferably 10% by mass or less, and 8% by mass or less, based on the total solid content of the optical film The content is more preferably 7.5% by mass or less. The above range is preferable from the viewpoint of obtaining appropriate adhesion together with the releasability from the base material.
<レベリング剤>
本発明における光学フィルムは、少なくとも1種のレベリング剤を含有することができる。
これにより、仮支持体上に塗布層を形成し、乾燥して、光学フィルムを有する転写フィルムを作製する工程において、乾燥風の局所的な分布による乾燥バラツキに起因する膜厚ムラ等を抑制したり、塗布物のハジキを改良することができる。
<Leveling agent>
The optical film in the present invention can contain at least one leveling agent.
Thereby, in the process of forming an application layer on a temporary support and drying to produce a transfer film having an optical film, film thickness unevenness and the like caused by drying variation due to local distribution of drying wind is suppressed. And improve the repelling of the coated material.
レベリング剤として、例えば、シリコーン系レベリング剤及びフッ素系レベリング剤から選択される少なくとも1種のレベリング剤を用いることができる。なお、レベリング剤は、低分子化合物よりもオリゴマー又はポリマーであることが好ましい。 As the leveling agent, for example, at least one leveling agent selected from silicone-based leveling agents and fluorine-based leveling agents can be used. The leveling agent is preferably an oligomer or a polymer rather than a low molecular weight compound.
レベリング剤を添加すると、塗布された塗膜の表面にレベリング剤が速やかに移動して偏在化し、塗膜の乾燥後もレベリング剤がそのまま表面に偏在することになるため、レベリング剤を添加した膜の表面エネルギーは、レベリング剤によって低下する。膜厚不均一性、ハジキ、及びムラを防止するという観点からは、膜の表面エネルギーが低いことが好ましい。 When the leveling agent is added, the leveling agent moves quickly on the surface of the applied coating film and becomes unevenly distributed, and the leveling agent will be unevenly distributed on the surface even after drying of the coated film, so a film to which the leveling agent is added Surface energy is reduced by the leveling agent. The surface energy of the film is preferably low from the viewpoint of preventing film thickness nonuniformity, repelling, and nonuniformity.
シリコーン系レベリング剤の好ましい例としては、ジメチルシリルオキシ単位を繰り返し単位として複数個含み、末端及び/又は側鎖に置換基を有するポリマーあるいはオリゴマーが挙げられる。ジメチルシリルオキシを繰り返し単位として含むポリマーあるいはオリゴマー中にはジメチルシリルオキシ以外の構造単位を含んでもよい。置換基は同一であっても異なっていてもよく、複数個あることが好ましい。好ましい置換基の例としてはポリエーテル基、アルキル基、アリール基、アリールオキシ基、シンナモイル基、オキセタニル基、フルオロアルキル基、ポリオキシアルキレン基、などを含む基が挙げられる。 Preferred examples of the silicone-based leveling agent include polymers or oligomers having a plurality of dimethylsilyloxy units as repeating units and having a substituent at the terminal and / or side chain. The polymer or oligomer containing dimethylsilyloxy as a repeating unit may contain structural units other than dimethylsilyloxy. The substituents may be the same or different and are preferably a plurality. Preferred examples of the substituent include groups containing a polyether group, an alkyl group, an aryl group, an aryloxy group, a cinnamoyl group, an oxetanyl group, a fluoroalkyl group, a polyoxyalkylene group, and the like.
シリコーン系レべリング剤の数平均分子量に特に制限はないが、10万以下であることが好ましく、5万以下であることがより好ましく、1000~30000であることが特に好ましく、1000~20000であることが最も好ましい。 The number average molecular weight of the silicone leveling agent is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, particularly preferably 1,000 to 30,000, and 1,000 to 20,000. Most preferably.
好ましいシリコーン系レベリング剤の例としては、電離放射線硬化基を有しない市販のシリコーン系レベリング剤として、信越化学工業(株)製のX22-3710、X22-162C、X22-3701E、X22160AS、X22170DX、X224015、X22176DX、X22-176F、X224272、KF8001、X22-2000等;チッソ(株)製のFM4421、FM0425、FMDA26、FS1265等;東レ・ダウコーニング(株)製のBY16-750、BY16880、BY16848、SF8427、SF8421、SH3746、SH8400、SF3771、SH3749、SH3748、SH8410等;モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製のTSFシリーズ(TSF4460、TSF4440、TSF4445、TSF4450、TSF4446、TSF4453、TSF4452、TSF4730、TSF4770等)、FGF502、SILWETシリーズ(SILWETL77、SILWETL2780、SILWETL7608、SILWETL7001、SILWETL7002、SILWETL7087、SILWETL7200、SILWETL7210、SILWETL7220、SILWETL7230、SILWETL7500、SILWETL7510、SILWETL7600、SILWETL7602、SILWETL7604、SILWETL7604、SILWETL7605、SILWETL7607、SILWETL7622、SILWETL7644、SILWETL7650、SILWETL7657、SILWETL8500、SILWETL8600、SILWETL8610、SILWETL8620、SILWETL720)等を挙げることができるがこれに限定されるものではない。 As an example of a preferable silicone type leveling agent, as a commercially available silicone type leveling agent which does not have an ionizing radiation curing group, Shin-Etsu Chemical Co., Ltd. X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015. X22176DX, X22-176F, X224272, KF8001, X22-2000, etc .; FM4421, FM0425, FMDA26, FS1265 etc. made by Chisso Corporation; BY16-750, BY16880, BY16848, SF8427, made by Toray Dow Corning Corporation. SF8421, SH3746, SH8400, SF3771, SH3749, SH3748, SH8410, etc .; TSF series manufactured by Momentive Performance Materials Japan Ltd. (TSF 4460, TSF 4440, TSF 4445, TSF 4446, TSF 4453, TSF 4452, TSF 4730, TSF 4770, etc.), FGF 502, SILWET series (SILWETL 77, SILWETL 2 780, SILWETL 7608, SILWETL 7001, SILWETL 7002 SILWETL7600, SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, S LWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720) is not limited thereto but can be exemplified.
電離放射線硬化基を有するものとして、信越化学工業(株)製のX22-163A、X22-173DX、X22-163C、KF101、X22164A、X24-8201、X22174DX、X22164C、X222426、X222445、X222457、X222459、X22245、X221602、X221603、X22164E、X22164B、X22164C、X22164D、TM0701等;チッソ(株)製のサイラプレーンシリーズ(FM0725、FM0721、FM7725、FM7721、FM7726、FM7727等);東レ・ダウコーニング(株)製のSF8411、SF8413、BY16-152D、BY16-152、BY16-152C、8388A等;エボニックデグサ ジャパン(株)製のTEGO Rad2010、2011、2100、2200N、2300、2500、2600,2700等;ビックケミー・ジャパン(株)製のBYK3500;信越シリコーン社製のKNS5300;モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製のUVHC1105、UVHC8550等を挙げることができるがこれに限定されるものではない。 As those having an ionizing radiation curing group, X22-163A, X22-173DX, X22-163C, KF101, X22164A, X24-8201, X22174DX, X22164C, X222426, X222445, X222457, X222245, X22245 X22-163A manufactured by Shin-Etsu Chemical Co., Ltd. , X221602, X221603, X22164E, X22164B, X22164C, X22164D, TM0701 etc .; Silyoplane series (FM0725, FM0721, FM7725, FM7721, FM7726, FM7727 etc.) manufactured by Chisso Corporation; SF8411 manufactured by Toray Dow Corning Co., Ltd. , SF 8413, BY16-152D, BY16-152, BY16-152C, 8388A, etc .; Evonik Degussa TEGO Rad 2010, 2011, 2100, 2200 N, 2300, 2500, 2600, 2700 etc. manufactured by N Inc .; BYK 3500 manufactured by Bick Chemie Japan Ltd .; KNS 5300 manufactured by Shin-Etsu Silicone Co., Ltd .; Momentive Performance Materials Japan Ltd. Although UVHC1105, UVHC8550 etc. made from can be mentioned, it is not limited to this.
フッ素系レベリング剤は、フルオロ脂肪族基と、例えばこのレべリング剤を添加剤として使用したときに、コーティング用、成形材料用等の各種組成物に対する親和性に寄与する親媒性基とを同一分子内に有する化合物であり、このような化合物は、一般に、フルオロ脂肪族基を有するモノマーと親媒性基を有するモノマーとを共重合させて得ることができる。
フルオロ脂肪族基を有するモノマーと共重合される、親媒性基を有するモノマーの代表的な例としては、ポリ(オキシアルキレン)アクリレート、ポリ(オキシアルキレン)メタクリレート等が挙げられる。
The fluorine-based leveling agent comprises a fluoroaliphatic group and a hydrophilic group which contributes to the affinity to various compositions such as coating and molding materials when, for example, this leveling agent is used as an additive. These compounds are compounds having the same molecule, and such compounds can be generally obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a hydrophilic group.
Representative examples of the monomer having a hydrophilic group, which is copolymerized with the monomer having a fluoroaliphatic group, include poly (oxyalkylene) acrylate, poly (oxyalkylene) methacrylate and the like.
好ましい市販のフッ素系レベリング剤としては、電離放射線硬化基を有しないものとしてDIC(株)製のメガファックシリーズ(MCF350-5、F472、F476、F445、F444、F443、F178、F470、F475、F479、F477、F482、F486、TF1025、F478、F178K、F-784-F、F552等);ネオス(株)製のフタ―ジェントシリーズ(FTX218、250、245M、209F、222F、245F、208G、218G、240G、206D、240D等)が挙げられ、電離放射線硬化基を有するものとして、ダイキン工業(株)製のオプツールDAC;DIC(株)製のデイフェンサシリーズ(TF3001、TF3000、TF3004、TF3028、TF3027、TF3026、TF3025等)、RSシリーズ(RS71、RS101、RS102、RS103、RS104、RS105等)が挙げられるがこれらに限定されるものではない。 As preferable commercially available fluorine-based leveling agents, Megafac series (MCF 350-5, F 472, F 476, F 445, F 444, F 443, F 178, F 470, F 475, F 479, manufactured by DIC Corporation) as having no ionizing radiation curing group. , F477, F482, F486, TF1025, F478, F178-F, F552 etc .; Neos Co., Ltd.'s lidagent series (FTX 218, 250, 245 M, 209 F, 222 F, 245 F, 208 G, 218 G, 240 G, 206 D, 240 D, etc.) and having an ionizing radiation curing group, Optool DAC manufactured by Daikin Industries, Ltd .; Defensor series manufactured by DIC (TF 3001, TF 3000, TF 3004, TF 3028, TF3). 27, TF3026, TF3025, etc.), RS series (RS71, RS101, RS102, RS103, RS104, RS105, etc.) are exemplified but not limited thereto.
また、特開2004-331812号公報、特開2004-163610号公報に記載の化合物等を用いることもできる。 In addition, compounds described in JP-A-2004-331812 and JP-A-2004-163610 can also be used.
上記レベリング剤は、光学フィルムの全固形分中に0.01~5.0質量%含有されることが好ましく、0.01~2.0質量%含有されることがより好ましく、0.01~1.0質量%含有されることが最も好ましい。 The leveling agent is preferably contained in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, in the total solid content of the optical film. It is most preferable to contain 1.0% by mass.
<溶剤>
本発明の光学フィルムは、光学フィルム形成用の組成物を塗布して形成した塗布層を乾燥して得ることができる。
光学フィルム形成用の組成物は、溶剤(溶媒)を含有することができる。溶剤(好ましくは有機溶剤)は、光学フィルムを形成するための材料を溶解または分散可能であること、塗布工程、乾燥工程において均一な面状となり易いこと、液保存性が確保できること、適度な飽和蒸気圧を有すること、等の観点で適宜選択することができる。このような有機溶剤としては、例えばジブチルエーテル、ジメトキシエタン、ジエトキシエタン、プロピレンオキシド、1,4-ジオキサン、1,3-ジオキソラン、1,3,5-トリオキサン、テトラヒドロフラン、アニソール、フェネトール、炭酸ジメチル、炭酸メチルエチル、炭酸ジエチル、アセトン、メチルエチルケトン(MEK)、ジエチルケトン、ジプロピルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、蟻酸エチル、蟻酸プロピル、蟻酸ペンチル、酢酸メチル、酢酸エチル、酢酸プロピル、プロピオン酸メチル、プロピオン酸エチル、γ-プチロラクトン、2-メトキシ酢酸メチル、2-エトキシ酢酸メチル、2-エトキシ酢酸エチル、2-エトキシプロピオン酸エチル、2-メトキシエタノール、2-プロポキシエタノール、2-ブトキシエタノール、1,2-ジアセトキシアセトン、アセチルアセトン、ジアセトンアルコール、アセト酢酸メチル、アセト酢酸エチル、メチルアルコール、エチルアルコール、イソプロピルアルコール、n-ブチルアルコール、シクロヘキシルアルコール、酢酸イソブチル、メチルイソブチルケトン(MIBK)、2-オクタノン、2-ペンタノン、2-ヘキサノン、エチレングリコールエチルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールブチルエーテル、プロピレングリコールメチルエーテル、エチルカルビトール、ブチルカルビトール、ヘキサン、ヘプタン、オクタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ベンゼン、トルエン、キシレン等が挙げられ、1種単独であるいは2種以上を組み合わせて用いることができる。
<Solvent>
The optical film of the present invention can be obtained by drying a coated layer formed by applying a composition for forming an optical film.
The composition for optical film formation can contain a solvent (solvent). The solvent (preferably, an organic solvent) can dissolve or disperse the material for forming the optical film, can easily form a uniform surface state in the coating step and the drying step, can ensure the liquid storage property, and is moderately saturated It can select suitably from a viewpoint of having steam pressure etc. Examples of such an organic solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate Methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, acetic acid Propyl, methyl propionate, ethyl propionate, γ-butyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2 Methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl Alcohol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol , Hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene And toluene, xylene and the like, and can be used singly or in combination of two or more.
上記の溶剤のうち、炭酸ジメチル、酢酸メチル、酢酸エチル、メチルエチルケトン、アセチルアセトン、アセトン、トルエン、キシレンのうち少なくとも1種類を用いることが好ましく、炭酸ジメチル、酢酸エチル、トルエンの何れかを用いることがより好ましく、酢酸エチルを用いることが特に好ましい。 Among the above solvents, it is preferable to use at least one selected from dimethyl carbonate, methyl acetate, ethyl acetate, methyl ethyl ketone, acetyl acetone, acetone, toluene and xylene, and it is more preferable to use any of dimethyl carbonate, ethyl acetate and toluene Preferably, it is particularly preferred to use ethyl acetate.
光学フィルム形成用の組成物の固形分の濃度は5~80質量%の範囲となるように溶剤を用いるのが好ましく、より好ましくは6~75質量%であり、更に好ましくは7~70質量%である。 It is preferable to use a solvent so that the solid concentration of the composition for forming an optical film is in the range of 5 to 80% by mass, more preferably 6 to 75% by mass, and still more preferably 7 to 70% by mass It is.
<その他の成分>
本発明の光学フィルムは、他の性能を向上する観点から、その他の成分を含むことができる。
<Other ingredients>
The optical film of the present invention can contain other components from the viewpoint of improving other performances.
本発明の光学フィルムにおいて、上述以外の特性値は、特に限定されることはなく、一般的な公知の偏光板保護フィルムと同等性能を適宜実装することができ、偏光板加工した場合に偏光層と液晶パネルとの間に配置される所謂インナーフィルムに要求される性能を適宜有していることが好ましい。具体的な特性値としては、表示特性に関連するヘイズ、光線透過率、分光特性、レタデーションの湿熱耐久性等を挙げることができ、力学特性や偏光板加工適性に関連する湿熱サーモに伴う寸法変化率、ガラス転移温度、平衡吸湿率、透湿度、接触角等を挙げることができる。 In the optical film of the present invention, characteristic values other than those described above are not particularly limited, and performance equivalent to that of a general known polarizing plate protective film can be appropriately mounted. It is preferable to appropriately have the performance required for a so-called inner film disposed between the liquid crystal panel and the liquid crystal panel. Specific property values can include haze related to display characteristics, light transmittance, spectral characteristics, wet heat durability of retardation, etc., and dimensional changes associated with wet heat thermos related to mechanical characteristics and polarizing plate processing suitability Rate, glass transition temperature, equilibrium moisture absorption rate, moisture permeability, contact angle, etc. can be mentioned.
本発明の光学フィルムにおいて、上述の所謂インナーフィルムに要求される性能を適宜付与するためには、以下に記述のポリマー樹脂を含むことが好ましい。 In the optical film of the present invention, in order to appropriately impart the required performance to the above-mentioned so-called inner film, it is preferable to include the polymer resin described below.
<ポリマー樹脂>
ポリマー樹脂は、特に限定されない。具体的な例として、環状オレフィン系樹脂、スチレン系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ビニル系樹脂、ポリイミド系樹脂、ポリアリレート系樹脂等を挙げることができ、環状ポリオレフィン樹脂、スチレン系樹脂が、インナーフィルムに要求される性能を適宜付与する観点から好ましい。
<Polymer resin>
The polymer resin is not particularly limited. Specific examples include cyclic olefin resins, styrene resins, polyester resins, polycarbonate resins, vinyl resins, polyimide resins, polyarylate resins, etc., and cyclic polyolefin resins and styrene resins And from the viewpoint of appropriately imparting the performance required for the inner film.
環状オレフィン系樹脂の例としては、例えば、ノルボルネンや多環ノルボルネン系モノマーのような環状オレフィンからなるモノマーのユニットを有する熱可塑性の樹脂であり、熱可塑性環状オレフィン系樹脂とも呼ばれる。この環状オレフィン系樹脂は、上記環状オレフィンの開環重合体や2種以上の環状オレフィンを用いた開環共重合体の水素添加物であってもよく、環状オレフィンと、鎖状オレフィンや、ビニル基の如き重合性二重結合を有する芳香族化合物などとの付加重合体であってもよい。環状オレフィン系樹脂には、極性基が導入されていてもよい。 As an example of cyclic olefin resin, it is a thermoplastic resin which has a unit of a monomer which consists of cyclic olefins, such as norbornene and a polycyclic norbornene monomer, for example, and is also called thermoplastic cyclic olefin resin. The cyclic olefin resin may be a hydrogenated product of the above ring-opening polymer of cyclic olefin or ring-opening copolymer using two or more cyclic olefins, cyclic olefin, chain olefin, vinyl It may be an addition polymer with an aromatic compound having a polymerizable double bond such as a group. A polar group may be introduced into the cyclic olefin resin.
環状オレフィンと、鎖状オレフィン及び/又はビニル基を有する芳香族化合物との共重合体で保護フィルムを構成する場合、鎖状オレフィンとしては、エチレンやプロピレンなどが用いられ、またビニル基を有する芳香族化合物としては、スチレン、α-メチルスチレン、核アルキル置換スチレンなどが用いられる。このような共重合体においては、環状オレフィンからなるモノマーのユニットが50モル%以下であってもよいが、好ましくは15~50モル%程度とされる。特に、環状オレフィンと鎖状オレフィンとビニル基を有する芳香族化合物との三元共重合体を保護フィルムとする場合、環状オレフィンからなるモノマーのユニットは、上述のとおり比較的少ない量とすることができる。かかる三元共重合体において、鎖状オレフィンからなるモノマーのユニットは、通常5~80モル%、ビニル基を有する芳香族化合物からなるモノマーのユニットは、通常5~80モル%である。 When the protective film is made of a copolymer of a cyclic olefin and an aromatic compound having a chain olefin and / or a vinyl group, ethylene, propylene and the like are used as the chain olefin, and an aromatic having a vinyl group As the group compound, styrene, α-methylstyrene, nuclear alkyl substituted styrene and the like are used. In such a copolymer, the unit of the cyclic olefin monomer may be 50 mol% or less, preferably about 15 to 50 mol%. In particular, when a terpolymer of a cyclic olefin, a chain olefin and an aromatic compound having a vinyl group is used as a protective film, the unit of the monomer comprising the cyclic olefin may be relatively small as described above. it can. In such a ternary copolymer, the unit of monomers consisting of chain olefins is usually 5 to 80 mol%, and the unit of monomers consisting of aromatic compounds having a vinyl group is usually 5 to 80 mol%.
環状オレフィン系樹脂は、適宜の市販品を用いることができ、例えば、ドイツのTOPAS ADVANCED POLYMERS GmbH にて生産され、日本ではポリプラスチック(株)から販売されている“TOPAS”、JSR(株)から販売されている“アートン”、日本ゼオン(株)から販売されている“ゼオノア”(ZEONOR)及び“ゼオネックス”(ZEONEX)、三井化学(株)から販売されている“アペル”(以上、いずれも商品名)などを挙げることができる。 As the cyclic olefin-based resin, any commercially available product can be used. For example, “TOPAS” manufactured by TOPAS ADVANCED POLYMERS GmbH, Germany, and sold by Polyplastics Co., Ltd. in Japan, from JSR Co., Ltd. "Arton" sold, "ZEONOR" (ZEONOR) sold by Nippon Zeon Co., Ltd., and "Apel" sold by Mitsui Chemical Co., Ltd. (all of which are listed above) Trade name) etc. can be mentioned.
スチレン系樹脂の例としては、スチレン系単量体を50質量%以上含む樹脂をいう。ここで、スチレン系単量体とは、その構造中にスチレン骨格を有する単量体をいう。 As an example of a styrene resin, the resin containing 50 mass% or more of styrene monomers is said. Here, the styrenic monomer refers to a monomer having a styrene skeleton in its structure.
スチレン系樹脂の具体例としては、スチレンまたはその誘導体の単独重合体であってもよく、スチレンもしくはその誘導体と他の共重合性モノマーとの、二元またはそれ以上の共重合体であってもよい。ここで、スチレン誘導体とは、スチレンに他の基が結合した化合物であって、例えば、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、2,4-ジメチルスチレン、o-エチルスチレン、p-エチルスチレンのようなアルキルスチレンや、ヒドロキシスチレン、tert-ブトキシスチレン、ビニル安息香酸、o-クロロスチレン、p-クロロスチレンのような、スチレンのベンゼン核に水酸基、アルコキシ基、カルボキシル基、ハロゲンなどが導入された置換スチレンなどが挙げられる。
スチレン系樹脂は、スチレンの単独重合体(すなわちポリスチレン)であることが好ましい。また、他の共重合性モノマーとの共重合体である場合、スチレン系樹脂は、スチレンまたはスチレン誘導体と、アクリロニトリル、無水マレイン酸、メチルメタクリレートおよびブタジエンから選ばれる少なくとも1種のモノマーとの共重合体であることが好ましい。
Specific examples of styrenic resins may be homopolymers of styrene or derivatives thereof, and binary or higher copolymers of styrene or derivatives thereof with other copolymerizable monomers. Good. Here, a styrene derivative is a compound in which another group is bound to styrene, and examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, Alkylstyrene such as p-ethylstyrene, hydroxystyrene, hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, styrene such as p-chlorostyrene, hydroxyl group, alkoxy group, carboxyl group, halogen at benzene nucleus And substituted styrene etc. into which
The styrenic resin is preferably a homopolymer of styrene (that is, polystyrene). When the copolymer is a copolymer with another copolymerizable monomer, the styrenic resin is a copolymer of styrene or a styrene derivative and at least one monomer selected from acrylonitrile, maleic anhydride, methyl methacrylate and butadiene. It is preferable to be combined.
ポリスチレンとしては、様々なものを用いることができるが、GPPSグレードであることが好ましい。一般的に、GPPSグレードのポリスチレンは、透明度が高いことによる。ポリスチレンの重合度を表す指標としては、メルトフローで測定するメルトマスフローレートやメルトボリュームフローレート、ゲルパーミエーションンクロマトグラフィーで測定する重量平均分子量(Mw)が挙げられる。 Although various things can be used as a polystyrene, It is preferable that it is GPPS grade. In general, GPPS grade polystyrene is due to its high transparency. Examples of the index indicating the degree of polymerization of polystyrene include a melt mass flow rate measured by melt flow, a melt volume flow rate, and a weight average molecular weight (Mw) measured by gel permeation chromatography.
本発明に用いるポリスチレンは、メルトマスフローレートが、18g/10分以下(200℃、5kgf加圧時、1kgf=9.807N)であることが好ましい。より好ましくは、7.5g/10分以下であり、更に好ましくは、1.9g/10分以下である。メルトマスフローレートが18g/10分以下であれば、ポリスチレンの重合度が高く、偏光板の破壊故障の抑制に有利になる。 The polystyrene used in the present invention preferably has a melt mass flow rate of 18 g / 10 min or less (200 ° C., 5 kgf under pressure, 1 kgf = 9.807 N). More preferably, it is 7.5 g / 10 min or less, still more preferably 1.9 g / 10 min or less. When the melt mass flow rate is 18 g / 10 min or less, the degree of polymerization of polystyrene is high, which is advantageous for suppressing the breakage failure of the polarizing plate.
また、本発明に用いるポリスチレンは、Mwが、180000以上であることが好ましい。更に好ましくは、350000以上である。Mwが、180000以上である場合は、ポリスチレンの重合度が高く、偏光板の破壊故障の抑制に有利になる。
好ましいポリスチレンとしては、DIC株式会社製 CR-3500、CR-4500、CR-2600、XC-315、XC-515、PSジャパン株式会社製 HF77、679、SGP-10、東洋スチレン株式会社製 G200C、G210C、G320C、HRM12、HRM26、HRM48N、等を挙げることが出来るがこれに限定されるものではない。
The polystyrene used in the present invention preferably has a Mw of 180000 or more. More preferably, it is 350000 or more. When Mw is 180,000 or more, the degree of polymerization of polystyrene is high, which is advantageous for suppressing the breakage failure of the polarizing plate.
Preferred polystyrenes include CR-3500, CR-4500, CR-2600, XC-315, XC-515 manufactured by DIC Corporation, HF77, 679, SGP-10 manufactured by PS Japan Co., Ltd., G200C, G210C manufactured by Toyo Styrene Co., Ltd. , G320C, HRM12, HRM26, HRM48N, and the like, but it is not limited thereto.
また、スチレン系樹脂にはスチレン系単量体成分に他の単量体成分を共重合したものも含まれる。共重合可能な単量体としては、メチルメタクリレ-ト、シクロヘキシルメタクリレ-ト、メチルフェニルメタクリレ-ト、イソプロピルメタクリレ-ト等のアルキルメタクリレ-ト;メチルアクリレ-ト、エチルアクリレ-ト、ブチルアクリレ-ト、2-エチルヘキシルアクリレ-ト、シクロヘキシルアクリレ-ト等のアルキルアクリレ-ト等の不飽和カルボン酸アルキルエステル単量体;メタクリル酸、アクリル酸、イタコン酸、マレイン酸、フマル酸、桂皮酸等の不飽和カルボン酸単量体;無水マレイン酸、イタコン酸、エチルマレイン酸、メチルイタコン酸、クロルマレイン酸等の無水物である不飽和ジカルボン酸無水物単量体;アクリロニトリル、メタクリロニトリル等の不飽和ニトリル単量体;1,3-ブタジエン、2-メチル-1,3-ブタジエン(イソプレン)、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエン等の共役ジエン等が挙げられ、これらの2種以上を共重合することも可能である。 Further, styrene resins include those obtained by copolymerizing styrene monomer components with other monomer components. As copolymerizable monomers, alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methyl phenyl methacrylate, isopropyl methacrylate, etc .; methyl acrylate, ethyl acrylate, Unsaturated carboxylic acid alkyl ester monomers such as alkyl acrylates such as butyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate; methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid Unsaturated carboxylic acid monomers such as cinnamic acid; unsaturated dicarboxylic acid anhydride monomers which are anhydrides such as maleic anhydride, itaconic acid, ethyl maleic acid, methyl itaconic acid, chlormaleic acid; acrylonitrile, methacryl acid Unsaturated nitrile monomers such as ronitrile; 1,3-butadiene, 2-methyl- 2,3-Butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, conjugated dienes such as 1,3-hexadiene, and the like, and copolymerization of two or more of them. Is also possible.
本発明で好適に用いることができるスチレン系樹脂は、耐熱性が高いという理由から、スチレン/アクリロニトリル共重合体、スチレン/メタクリル酸共重合体、スチレン/無水マレイン酸共重合体であってもよい。
また、スチレン/アクリロニトリル共重合体、スチレン/メタクリル酸共重合体、スチレン/無水マレイン酸共重合体は、アクリル系樹脂との相溶性が高いため、本発明の光学フィルムがアクリル系樹脂を含む場合などは、透明性が高く、使用中に相分離を起こして透明性が低下することがない光学フィルムを得られることからも好ましい。このような観点からは、特に、アクリル系樹脂としてメタクリル酸メチルを単量体成分として含む重合体を用いる場合に好ましい。
The styrene-based resin that can be suitably used in the present invention may be a styrene / acrylonitrile copolymer, a styrene / methacrylic acid copolymer, or a styrene / maleic anhydride copolymer because the heat resistance is high. .
In addition, since the styrene / acrylonitrile copolymer, styrene / methacrylic acid copolymer, and styrene / maleic anhydride copolymer have high compatibility with the acrylic resin, the optical film of the present invention contains the acrylic resin. And the like are also preferable from the viewpoint of obtaining an optical film which has high transparency and causes phase separation during use to reduce the transparency. From such a point of view, it is particularly preferable to use a polymer containing methyl methacrylate as a monomer component as the acrylic resin.
スチレン-アクリロニトリル共重合体の場合、共重合体中のアクリロニトリルの共重合体割合は1~40質量%であることが好ましい。さらに好ましい範囲は1~30質量%であり、とりわけ好ましい範囲は1~25質量%である。共重合体中のアクリロニトリルの共重合体割合が1~40質量%の場合、透明性に優れるため好ましい。
スチレン-メタクリル酸共重合体の場合、共重合体中のメタクリル酸の共重合体割合は0.1~50質量%であることが好ましい。より好ましい範囲は0.1~40質量%であり、さらに好ましい範囲は0.1~30質量%である。共重合体中のメタクリル酸の共重合体割合が0.1質量%以上であると耐熱性に優れ、50質量%以下の範囲であれば透明性に優れるので好ましい。
スチレン-無水マレイン酸共重合体の場合、共重合体中の無水マレイン酸の共重合体割合は0.1~50質量%であることが好ましい。より好ましい範囲は0.1~40質量%であり、さらに好ましい範囲は0.1質量%~30質量%である。共重合体中の無水マレイン酸含量が0.1質量%以上であると耐熱性に優れ、50質量%以下の範囲であれば透明性に優れるので好ましい。
In the case of a styrene-acrylonitrile copolymer, the copolymer proportion of acrylonitrile in the copolymer is preferably 1 to 40% by mass. A further preferred range is 1 to 30% by mass, and a particularly preferred range is 1 to 25% by mass. When the proportion of the acrylonitrile copolymer in the copolymer is 1 to 40% by mass, it is preferable because the transparency is excellent.
In the case of a styrene-methacrylic acid copolymer, the copolymer proportion of methacrylic acid in the copolymer is preferably 0.1 to 50% by mass. A more preferable range is 0.1 to 40% by mass, and a further preferable range is 0.1 to 30% by mass. It is excellent in heat resistance that the copolymer ratio of methacrylic acid in a copolymer is 0.1 mass% or more, and excellent in transparency if it is 50 mass% or less, it is preferable.
In the case of a styrene-maleic anhydride copolymer, the proportion of maleic anhydride copolymer in the copolymer is preferably 0.1 to 50% by mass. A more preferable range is 0.1 to 40% by mass, and a further preferable range is 0.1% to 30% by mass. It is excellent in heat resistance that the maleic anhydride content in a copolymer is 0.1 mass% or more, and since it is excellent in transparency if it is 50 mass% or less, it is preferable.
スチレン系樹脂として、組成、分子量等が異なる複数種類のものを併用することができる。
スチレン系樹脂は、公知のアニオン、塊状、懸濁、乳化または溶液重合方法により得ることができる。また、スチレン系樹脂においては、共役ジエンやスチレン系単量体のベンゼン環の不飽和二重結合が水素添加されていてもよい。水素添加率は核磁気共鳴装置(NMR)によって測定できる。
As the styrene resin, plural kinds of resins having different compositions, molecular weights and the like can be used in combination.
The styrenic resin can be obtained by a known anionic, bulk, suspension, emulsification or solution polymerization method. Further, in the styrene resin, the unsaturated double bond of the benzene ring of the conjugated diene or the styrene monomer may be hydrogenated. The hydrogenation rate can be measured by nuclear magnetic resonance (NMR).
ポリカーボネート樹脂の例としては、ポリカーボネート、ビスフェノールAがフルオレン変性された構造単位を含むポリカーボネート、ビスフェノールAが1,3-シクロヘキシリデン変性された構造単位を含むポリカーボネート等が挙げられる。
ビニル系樹脂の例としては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニリデン、ポリビニルアルコール、等が挙げられる。
Examples of the polycarbonate resin include polycarbonate, a polycarbonate containing a structural unit in which bisphenol A is fluorene-modified, and a polycarbonate containing a structural unit in which bisphenol A is 1,3-cyclohexylidene-modified.
Examples of vinyl resins include polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polyvinyl alcohol and the like.
本発明の光学フィルム中、上記ポリマー樹脂の含有量が、光学フィルムの全固形分に対して、5~55質量%であることが好ましく、5~45質量%であることがより好ましく、5~35質量%であることがさらに好ましく、7~30質量%であることが特に好ましく、10~25質量%であることが最も好ましい。 In the optical film of the present invention, the content of the polymer resin is preferably 5 to 55% by mass, more preferably 5 to 45% by mass, with respect to the total solid content of the optical film. The content is further preferably 35% by mass, particularly preferably 7 to 30% by mass, and most preferably 10 to 25% by mass.
<偏光子に対する光学フィルムの接着性改良成分>
その他の成分として、偏光子に対する光学フィルムの接着性改良成分を含むことで、本発明の光学フィルムを有する偏光板において、光学フィルムの偏光子に対する接着性を良化することができる。
<Adhesive improvement component of optical film to polarizer>
By including an adhesive property improvement component of the optical film to the polarizer as another component, in the polarizing plate having the optical film of the present invention, the adhesion of the optical film to the polarizer can be improved.
本発明の光学フィルムは、偏光子に対する光学フィルムの接着性改良成分として、下記一般式(I)で表される繰り返し単位と、下記一般式(II)で表される繰り返し単位とを含む共重合体(以下、「共重合体(a)」とも呼ぶ。)、及び/又は共重合体(a)に由来する架橋反応物を含有してもよい。
なお、本発明の光学フィルムは、共重合体(a)及び共重合体(a)に由来する架橋反応物のどちらか1種のみを含有していてもよいし、両方を含有していてもよい。
The optical film of the present invention is a copolymer comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) as an adhesive property improving component of the optical film to a polarizer. It may contain a crosslinking reaction product derived from coalescence (hereinafter also referred to as “copolymer (a)”) and / or copolymer (a).
The optical film of the present invention may contain only one of either the copolymer (a) or the crosslinking product derived from the copolymer (a), or may contain both of them. Good.
一般式(I)中、R1は水素原子又は炭素数1~20のアルキル基を表し、R2は少なくともひとつのフッ素原子を置換基として有するアルキル基、または-Si(Ra3)(Ra4)O-を含む基を表し、Lは-O-、-(C=O)O-、-O(C=O)-、2価の脂肪族鎖状基、及び2価の脂肪族環状基からなる群より選択される少なくとも1つから構成される2価の連結基を表す。Ra3およびRa4はそれぞれ独立に置換基を有していてもよいアルキル基又は置換基を有してもよいアリール基を表す。 In formula (I), R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 2 represents an alkyl group having at least one fluorine atom as a substituent, or —Si (R a3 ) (R a4 L represents a group containing O-, L represents -O-,-(C = O) O-, -O (C = O)-, a divalent aliphatic chain group, and a divalent aliphatic cyclic group And at least one divalent linking group selected from the group consisting of R a3 and R a4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
一般式(II)中、R10は水素原子又は炭素数1~20のアルキル基を表し、R11及びR12はそれぞれ独立に、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基、又は置換もしくは無置換のヘテロアリール基を表し、R11とR12とは連結していてもよい。X1は、2価の連結基を表す。 In formula (II), R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R 11 and R 12 may be linked. X 1 represents a divalent linking group.
<共重合体(a)、または共重合体(a)に由来する架橋反応物>
以下、光学フィルムに含有される共重合体(a)、または共重合体(a)に由来する架橋反応物について説明する。
<Cross-linked product derived from copolymer (a) or copolymer (a)>
Hereinafter, the crosslinking reaction product derived from the copolymer (a) contained in the optical film or the copolymer (a) will be described.
一般式(I)中のR1は水素原子又は炭素数1~20のアルキル基を表し、水素原子又は炭素数1~10のアルキル基が好ましく、水素原子又は炭素数1~4のアルキル基がより好ましく、水素原子又はメチル基が更に好ましい。 R 1 in the general formula (I) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms More preferred is a hydrogen atom or a methyl group.
一般式(I)中のR2は少なくともひとつのフッ素原子を置換基として有するアルキル基(フルオロアルキル基)が好ましく、炭素数1~20のフルオロアルキル基であることが好ましく、炭素数1~18のフルオロアルキル基であることがより好ましく、炭素数2~15のフルオロアルキル基であることが更に好ましい。また、フルオロアルキル基中のフッ素原子数は、1~25であることが好ましく、3~21であることがより好ましく、5~21であることが最も好ましい。 R 2 in the general formula (I) is preferably an alkyl group (fluoroalkyl group) having at least one fluorine atom as a substituent, and is preferably a fluoroalkyl group having 1 to 20 carbon atoms, and 1 to 18 carbon atoms Is more preferably a fluoroalkyl group, and more preferably a fluoroalkyl group having 2 to 15 carbon atoms. The number of fluorine atoms in the fluoroalkyl group is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.
一般式(I)中のLは-O-、-(C=O)O-、-O(C=O)-、2価の脂肪族鎖状基、及び2価の脂肪族環状基からなる群より選択される少なくとも1つから構成される2価の連結基を表す。なお、-(C=O)O-は、R1側の炭素原子とC=Oが結合し、R2とOが結合することを表し、-O(C=O)-は、R1側の炭素原子とOが結合し、R2とC=Oが結合することを表す。
Lが表す2価の脂肪族鎖状基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましい。
Lが表す2価の脂肪族環状基としては、炭素数3~20のシクロアルキレン基が好ましく、炭素数3~15のシクロアルキレン基がより好ましい。
Lとしては、-(C=O)O-、または-O(C=O)-が好ましく、-(C=O)O-がより好ましい。
L in the general formula (I) consists of -O-,-(C = O) O-, -O (C = O)-, a divalent aliphatic chain group, and a divalent aliphatic cyclic group Represents a divalent linking group composed of at least one selected from the group consisting of In addition,-(C = O) O- represents that a carbon atom on R 1 side and C = O are bonded and R 2 and O are bonded, and -O (C = O)-is a group on R 1 side And a carbon atom of the formula (I) bond to O, and R 2 and a C = O bond.
As the divalent aliphatic chain group represented by L, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
The divalent aliphatic cyclic group represented by L is preferably a cycloalkylene group having 3 to 20 carbon atoms, and more preferably a cycloalkylene group having 3 to 15 carbon atoms.
As L,-(C = O) O- or -O (C = O)-is preferable, and-(C = O) O- is more preferable.
接着性に有利な表面偏在性の観点及びラジカル重合性の観点から、一般式(I)で表される繰り返し単位は、下記一般式(III)で表される繰り返し単位であることが特に好ましい。 The repeating unit represented by the general formula (I) is particularly preferably a repeating unit represented by the following general formula (III), from the viewpoint of the surface uneven distribution advantageous to the adhesion and the radical polymerization property.
一般式(III)中、R1は水素原子又は炭素数1~20のアルキル基を表し、maおよびnaは各々独立に1~20の整数を表し、Xは水素原子またはフッ素原子を表す。 In formula (III), R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represent an integer of 1 to 20, and X represents a hydrogen atom or a fluorine atom.
一般式(III)中のR1は一般式(I)中のR1と同義であり、好ましい範囲も同様である。 R 1 in the general formula (III) is the general formula (I) in the same meaning as R 1, and preferred ranges are also the same.
一般式(III)中のmaおよびnaは各々独立に1~20の整数を表す。
接着性に有利な表面偏在の観点ならびに原料入手及び製造の容易さの観点から、一般式(III)中のmaは1~8の整数であることが好ましく、1~5の整数であることがより好ましい。また、naは1~15の整数であることが好ましく、1~12の整数であることがより好ましく、2~10の整数であることがさらに好ましく、5~7の整数が最も好ましい。
Ma and na in the general formula (III) each independently represent an integer of 1 to 20.
From the viewpoint of surface uneven distribution advantageous for adhesion and easiness of raw material acquisition and production, ma in general formula (III) is preferably an integer of 1 to 8, and an integer of 1 to 5 More preferable. Also, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, still more preferably an integer of 2 to 10, and most preferably an integer of 5 to 7.
一般式(III)中のXは水素原子またはフッ素原子を表し、フッ素原子を表すことが好ましい。 X in the general formula (III) represents a hydrogen atom or a fluorine atom, preferably a fluorine atom.
一般式(I)又は(III)で表される繰り返し単位は、単量体の重合により得ることができ、好ましい単量体としては、例えば2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,3,3,3-ペンタフルオロプロピル(メタ)アクリレート、2-(パーフルオロブチル)エチル(メタ)アクリレート、2-(パーフルオロヘキシル)エチル(メタ)アクリレート、2-(パーフルオロオクチル)エチル(メタ)アクリレート、2-(パーフルオロデシル)エチル(メタ)アクリレート、2-(パーフルオロ-3-メチルブチル)エチル(メタ)アクリレート、2-(パーフルオロ-5-メチルヘキシル)エチル(メタ)アクリレート、2-(パーフルオロ-7-メチルオクチル)エチル(メタ)アクリレート、1H,1H,3H-テトラフルオロプロピル(メタ)アクリレート、1H,1H,5H-オクタフルオロペンチル(メタ)アクリレート、1H,1H,7H-ドデカフルオロヘプチル(メタ)アクリレート、1H,1H,9H-ヘキサデカフルオロノニル(メタ)アクリレート、1H-1-(トリフオロメチル)トリフルオロエチル(メタ)アクリレート、1H,1H,3H-ヘキサフルオロブチル(メタ)アクリレート、3-パーフルオロブチル-2-ヒドロキシプロピル(メタ)アクリレート、3-パーフルオロヘキシル-2-ヒドロキシプロピル(メタ)アクリレート、3-パーフルオロオクチル-2-ヒドロキシプロピル(メタ)アクリレート、3-(パーフルオロ-3-メチルブチル)-2-ヒドロキシプロピル(メタ)アクリレート、3-(パーフルオロ-5-メチルヘキシル)-2-ヒドロキシプロピル(メタ)アクリレート、3-(パーフルオロ-7-メチルオクチル)-2-ヒドロキシプロピル(メタ)アクリレート等が挙げられる。 The repeating unit represented by the general formula (I) or (III) can be obtained by polymerization of a monomer, and preferred monomers include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-Pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ) Ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate ) Acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth ) Acrylate, 1H-1- (Trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3 -Perfluorohexyl 2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl 2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3 - Perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.
一般式(I)中のR2は、-Si(Ra3)(Ra4)O-で表されるシロキサン結合を含む繰り返し単位(ポリシロキサン構造)を有することも別の態様として好ましい。Ra3およびRa4はそれぞれ独立に置換基を有していてもよいアルキル基(好ましくは置換基を有していてもよい炭素数1~12のアルキル基)又は置換基を有してもよいアリール基を表す。この場合、共重合体(a)としては、ポリシロキサン構造が側鎖に導入されたグラフト共重合体であることが好ましい。このグラフト共重合体を得るためのシロキサン結合を有する化合物は、下記一般式(IV)で表される化合物であることがより好ましい。 It is also preferable as another aspect that R 2 in the general formula (I) has a repeating unit (polysiloxane structure) containing a siloxane bond represented by —Si (R a3 ) (R a4 ) O—. R a3 and R a4 may each independently have an alkyl group which may have a substituent (preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent) or a substituent Represents an aryl group. In this case, the copolymer (a) is preferably a graft copolymer in which a polysiloxane structure is introduced into the side chain. The compound having a siloxane bond for obtaining the graft copolymer is more preferably a compound represented by the following general formula (IV).
Ra3およびRa4は、それぞれ独立にアルキル基、ハロアルキル基、またはアリール基を表す。アルキル基としては、炭素数1~10のアルキル基が好ましい。例えば、メチル基、エチル基、ヘキシル基を挙げることができる。ハロアルキル基としては、炭素数1~10のフッ素化アルキル基が好ましい。例えば、トリフルオロメチル基、ペンタフルオロエチル基を挙げることができる。アリール基としては、炭素数6~20のアリール基が好ましい。例えばフェニル基、ナフチル基を挙げることができる。なかでも、Ra3およびRa4は、メチル基、トリフルオロメチル基、またはフェニル基が好ましく、メチル基が特に好ましい。
Ra1は水素原子または炭素数1~20のアルキル基を表す。Ra5は、炭素数1~12のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましい。
nnは、10~1000が好ましく、20~500がより好ましく、30~200がさらに好ましい。
一般式(IV)中のnn個のRa3は同じでも異なっていてもよく、nn個のRa4は同じでも異なっていてもよい。
R a3 and R a4 each independently represent an alkyl group, a haloalkyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group and a hexyl group can be mentioned. The haloalkyl group is preferably a fluorinated alkyl group having 1 to 10 carbon atoms. For example, trifluoromethyl group and pentafluoroethyl group can be mentioned. The aryl group is preferably an aryl group having 6 to 20 carbon atoms. For example, a phenyl group and a naphthyl group can be mentioned. Among them, R a3 and R a4 are preferably a methyl group, a trifluoromethyl group or a phenyl group, and a methyl group is particularly preferable.
R a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R a5 is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
nn is preferably 10 to 1000, more preferably 20 to 500, and still more preferably 30 to 200.
The nn R a3 's in the general formula (IV) may be the same or different, and the nn R a4' s may be the same or different.
グラフト共重合用のシロキサン結合を有する化合物としては、片末端(メタ)アクリロイル基含有ポリシロキサンマクロマー(例えば、サイラプレーン0721、同0725(以上、商品名、JNC(株)製)、AK-5、AK-30、AK-32(以上、商品名、東亜合成(株)社製)、KF-100T、X-22-169AS、KF-102、X-22-3701IE、X-22-164B、X-22-164C、X-22―5002、X-22-173B、X-22-174D、X-22-167B、X-22-161AS(以上、商品名、信越化学工業(株)製)等を挙げることができる。 As a compound having a siloxane bond for graft copolymerization, one end (meth) acryloyl group-containing polysiloxane macromer (for example, Silaprene 0721, 0725 (all trade names, manufactured by JNC Co., Ltd.), AK-5, AK-30, AK-32 (all trade names, manufactured by Toa Gosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701 IE, X-22-164B, X- 22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. be able to.
次に、下記一般式(II)について説明する。
共重合体(a)は、上記一般式(I)で表される繰り返し単位の他に、一般式(II)で表される繰り返し単位も有する。一般式(II)で表される繰り返し単位は、水酸基に対して強い相互作用を持つ。即ち、基材上に光学フィルム形成用の組成物の塗布液を塗布した後に、塗布液表面に水酸基を有する接着剤層を設けると、一般式(II)で表される繰り返し単位の一部又は全部が水酸基と相互作用することにより、共重合体(a)は水酸基を有する接着剤層界面及び接着剤層の内部に拡散して吸着される。
従って、光学フィルムと接着剤層が接した後では、塗布液中に添加された一般式(II)で表される繰り返し単位を有する共重合体(a)は、光学フィルム、接着剤層、及び、両者の界面で、一般式(II)そのままの化学構造を有する共重合体、もしくは、一般式(II)で表される繰り返し単位が接着剤層の水酸基と反応した構造を有する誘導体(架橋反応物)として存在する。
このように、一般式(II)で表される繰り返し単位を有する共重合体が接着剤層と相互作用するため、接着剤層及び/又は光学フィルム中に存在する共重合体の比率に拘らず、共重合体(a)を含む光学フィルムと接着剤層との接着性を高めることができる。
Next, the following general formula (II) will be described.
The copolymer (a) has a repeating unit represented by the general formula (II) in addition to the repeating unit represented by the above general formula (I). The repeating unit represented by the general formula (II) has a strong interaction with a hydroxyl group. That is, when an adhesive layer having a hydroxyl group is provided on the surface of the coating solution after applying the coating solution of the composition for forming an optical film on the substrate, part of the repeating unit represented by the general formula (II) or The entire interaction with the hydroxyl group causes the copolymer (a) to diffuse and be adsorbed to the adhesive layer interface having the hydroxyl group and the inside of the adhesive layer.
Therefore, after the optical film and the adhesive layer are in contact with each other, the copolymer (a) having the repeating unit represented by the general formula (II) added to the coating solution is an optical film, an adhesive layer, and A copolymer having the same chemical structure as that of the general formula (II) or a derivative having a structure in which the repeating unit represented by the general formula (II) is reacted with the hydroxyl group of the adhesive layer (crosslinking reaction Exist as
As such, since the copolymer having the repeating unit represented by the general formula (II) interacts with the adhesive layer, regardless of the ratio of the copolymer present in the adhesive layer and / or the optical film. The adhesion between the optical film containing the copolymer (a) and the adhesive layer can be enhanced.
一般式(II)中、R10は水素原子又は炭素数1~20のアルキル基を表し、R11及びR12はそれぞれ独立に、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基、又は置換もしくは無置換のヘテロアリール基を表し、R11とR12とは連結していてもよい。X1は、2価の連結基を表す。 In formula (II), R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R 11 and R 12 may be linked. X 1 represents a divalent linking group.
一般式(II)中、R10は水素原子又は炭素数1~20のアルキル基を表し、水素原子又は炭素数1~10のアルキル基が好ましく、水素原子又は炭素数1~4のアルキル基がより好ましく、水素原子又はメチル基が最も好ましい。 In formula (II), R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms More preferred is a hydrogen atom or a methyl group.
一般式(II)中、R11及びR12でそれぞれ表される、置換もしくは無置換の、脂肪族炭化水素基としては、置換もしくは無置換の、アルキル基、アルケニル基及びアルキニル基が含まれる。上記アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、sec-ブチル基、tert-ブチル基、イソペンチル基、ネオペンチル基、1-メチルブチル基、イソヘキシル基、2-メチルヘキシル基、シクロペンチル基、シクロヘキシル基、1-アダマンチル基、2-ノルボルニル基等の直鎖状、分枝状、又は環状のアルキル基が挙げられる。
上記アルケニル基の具体例としては、ビニル基、1-プロペニル基、1-ブテニル基、1-メチル-1-プロペニル基、1-シクロペンテニル基、1-シクロヘキセニル基等の直鎖状、分枝状、又は環状のアルケニル基が挙げられる。
上記アルキニル基の具体例としては、エチニル基、1-プロピニル基、1-ブチニル基、1-オクチニル基等が挙げられる。
The substituted or unsubstituted aliphatic hydrocarbon group represented by R 11 and R 12 in the general formula (II) includes a substituted or unsubstituted alkyl group, an alkenyl group and an alkynyl group. Specific examples of the above alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group and hexadecyl group. Octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1 And-linear, branched or cyclic alkyl groups such as adamantyl group and 2-norbornyl group.
Specific examples of the above alkenyl group include linear or branched such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like And cyclic or cyclic alkenyl groups.
Specific examples of the above alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, 1-octynyl group and the like.
R11及びR12がそれぞれ表す置換もしくは無置換の、アリール基の具体例としては、フェニル基が挙げられる。また、2個から4個のベンゼン環が縮合環を形成したもの、ベンゼン環と不飽和五員環とが縮合環を形成したものを挙げることができ、具体例としてはナフチル基、アントリル基、フェナントリル基、インデニル基、アセナブテニル基、フルオレニル基、ピレニル基等が挙げられる。
また、R11及びR12がそれぞれ表す置換もしくは無置換のヘテロアリール基の例としては、窒素原子、酸素原子及び硫黄原子からなる群から選ばれるヘテロ原子を1個以上含む複素芳香環上の水素原子を1個除し、ヘテロアリール基としたものが含まれる。窒素原子、酸素原子及び硫黄原子からなる群から選ばれるヘテロ原子を1個以上含む複素芳香環の具体例としては、ピロール、フラン、チオフェン、ピラゾール、イミダゾール、トリアゾール、オキサゾール、イソオキサゾール、オキサジアゾール、チアゾール、チアジアゾール、インドール、カルバゾール、ベンゾフラン、ジベンゾフラン、チアナフテン、ジベンゾチオフェン、インダゾールベンズイミダゾール、アントラニル、ベンズイソオキサゾール、ベンズオキサゾール、ベンゾチアゾール、プリン、ピリジン、ピリダジン、ピリミジン、ピラジン、トリアジン、キノリン、アクリジン、イソキノリン、フタラジン、キナゾリン、キノキザリン、ナフチリジン、フェナントロリン、プテリジン等が挙げられる。
A substituted or unsubstituted R 11 and R 12 represent each, specific examples of the aryl group include phenyl group. Further, those in which 2 to 4 benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated 5-membered ring form a condensed ring can be mentioned, and specific examples thereof include a naphthyl group, an anthryl group, A phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group, a pyrenyl group etc. are mentioned.
Moreover, as an example of the substituted or unsubstituted heteroaryl group represented by R 11 and R 12 respectively, a hydrogen on a heteroaromatic ring containing one or more hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom Included are those in which one atom is removed to form a heteroaryl group. Specific examples of the heteroaromatic ring containing one or more hetero atoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole Thiazole, Thiadiazole, Indole, Carbazole, Benzofuran, Dibenzofuran, Thianaphtene, Dibenzothiophene, Indazole Benzimidazole, Anthranil, Benzisoxazole, Benzoxazole, Benzothiazole, Purine, Pyridine, Pyridazine, Pyrimidin, Pyrazine, Triazine, Quinoline, Acridine, Isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine and the like can be mentioned.
R11とR12とは連結していてもよく、この場合には、R11及びR12がそれぞれ独立に、アルキル基又はアリール基であって、これらが互いに連結していることが好ましく、R11及びR12がアルキル基であって、これらが互いに連結していることがより好ましい。 R 11 and R 12 may be linked, and in this case, R 11 and R 12 each independently represent an alkyl group or an aryl group, which are preferably linked to each other, R More preferably, 11 and R 12 are alkyl groups, which are linked to each other.
X1で表される二価の連結基としては、-(C=O)O-、-O(C=O)-、-(C=O)NH-、-O-、-CO-、-NH-、-O(C=O)-NH-、-O(C=O)-O-、及び-CH2-から選択される連結基を少なくとも1つ含み、かつ炭素数が7以上であることが好ましい。 Examples of the divalent linking group represented by X 1 include-(C = O) O-, -O (C = O)-,-(C = O) NH-, -O-, -CO-,- NH -, - O (C = O) -NH -, - O (C = O) -O-, and -CH 2 - comprises at least one linking group selected from, and the number of carbon atoms is 7 or more Is preferred.
R11、R12及びX1は、可能な場合は1個以上の置換基によって置換されていてもよい。置換基としては水素原子を除く1価の非金属原子団を挙げることができ、例えば、以下の置換基群Yから選ばれる。
置換基群Y:
ハロゲン原子(-F、-Br、-Cl、-I)、ヒドロキシル基、アルコキシ基、アリーロキシ基、メルカプト基、アルキルチオ基、アリールチオ基、アルキルジチオ基、アリールジチオ基、アミノ基、N-アルキルアミノ基、N,N-ジアルキルアミノ基、N-アリールアミノ基、N,N-ジアリールアミノ基、N-アルキル-N-アリールアミノ基、アシルオキシ基、カルバモイルオキシ基、N-アルキルカルバモイルオキシ基、N-アリールカルバモイルオキシ基、N,N-ジアルキルカルバモイルオキシ基、N,N-ジアリールカルバモイルオキシ基、N-アルキル-N-アリールカルバモイルオキシ基、アルキルスルホキシ基、アリールスルホキシ基、アシルチオ基、アシルアミノ基、N-アルキルアシルアミノ基、N-アリールアシルアミノ基、ウレイド基、N'-アルキルウレイド基、N',N'-ジアルキルウレイド基、N'-アリールウレイド基、N',N'-ジアリールウレイド基、N'-アルキル-N'-アリールウレイド基、N-アルキルウレイド基、N-アリールウレイド基、N'-アルキル-N-アルキルウレイド基、N'-アルキル-N-アリールウレイド基、N',N'-ジアルキル-N-アルキルウレイド基、N',N'-ジアルキル-N-アリールウレイド基、N'-アリール-N-アルキルウレイド基、N'-アリール-N-アリールウレイド基、N',N'-ジアリール-N-アルキルウレイド基、N',N'-ジアリール-N-アリールウレイド基、N'-アルキル-N'-アリール-N-アルキルウレイド基、N'-アルキル-N'-アリール-N-アリールウレイド基、アルコキシカルボニルアミノ基、アリーロキシカルボニルアミノ基、N-アルキル-N-アルコキシカルボニルアミノ基、N-アルキル-N-アリーロキシカルボニルアミノ基、N-アリール-N-アルコキシカルボニルアミノ基、N-アリール-N-アリーロキシカルボニルアミノ基、ホルミル基、アシル基、カルボキシル基及びその共役塩基基、アルコキシカルボニル基、アリーロキシカルボニル基、カルバモイル基、N-アルキルカルバモイル基、N,N-ジアルキルカルバモイル基、N-アリールカルバモイル基、N,N-ジアリールカルバモイル基、N-アルキル-N-アリールカルバモイル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、スルホ基(-SO3H)及びその共役塩基基、アルコキシスルホニル基、アリーロキシスルホニル基、スルフィナモイル基、N-アルキルスルフィナモイル基、N,N-ジアルキルスルフィナモイル基、N-アリールスルフィナモイル基、N,N-ジアリールスルフィナモイル基、N-アルキル-N-アリールスルフィナモイル基、スルファモイル基、N-アルキルスルファモイル基、N,N-ジアルキルスルファモイル基、N-アリールスルファモイル基、N,N-ジアリールスルファモイル基、N-アルキル-N-アリールスルファモイル基、N-アシルスルファモイル基及びその共役塩基基、N-アルキルスルホニルスルファモイル基(-SO2NHSO2(alkyl))及びその共役塩基基、N-アリールスルホニルスルファモイル基(-SO2NHSO2(aryl))及びその共役塩基基、N-アルキルスルホニルカルバモイル基(-CONHSO2(alkyl))及びその共役塩基基、N-アリールスルホニルカルバモイル基(-CONHSO2(aryl))及びその共役塩基基、アルコキシシリル基(-Si(Oalkyl)3)、アリーロキシシリル基(-Si(Oaryl)3)、ヒドロキシシリル基(-Si(OH)3)及びその共役塩基基、ホスホノ基(-PO3H2)及びその共役塩基基、ジアルキルホスホノ基(-PO3(alkyl)2)、ジアリールホスホノ基(-PO3(aryl)2)、アルキルアリールホスホノ基(-PO3(alkyl)(aryl))、モノアルキルホスホノ基(-PO3H(alkyl))及びその共役塩基基、モノアリールホスホノ基(-PO3H(aryl))及びその共役塩基基、ホスホノオキシ基(-OPO3H2)及びその共役塩基基、ジアルキルホスホノオキシ基(-OPO3(alkyl)2)、ジアリールホスホノオキシ基(-OPO3(aryl)2)、アルキルアリールホスホノオキシ基(-OPO3(alkyl)(aryl))、モノアルキルホスホノオキシ基(-OPO3H(alkyl))及びその共役塩基基、モノアリールホスホノオキシ基(-OPO3H(aryl))及びその共役塩基基、シアノ基、ニトロ基、アリール基、アルケニル基及びアルキニル基。
また、これらの置換基は、可能であるならば置換基同士、又は置換している炭化水素基と結合して環を形成してもよい。
R 11 , R 12 and X 1 may be optionally substituted by one or more substituents. Examples of the substituent include monovalent nonmetallic atomic groups other than hydrogen atoms, and are selected from, for example, the following Substituent Group Y.
Substituent group Y:
Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, aryldithio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ally N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N -Alkylacylamino group, N-aryl Silamino group, ureido group, N'-alkyl ureido group, N ', N'-dialkyl ureide group, N'-aryl ureido group, N', N'- diaryl ureido group, N'-alkyl-N'- aryl ureido Group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl ureido group, N ', N'-dialkyl-N-alkyl ureido group, N ', N'-dialkyl-N-aryl ureido group, N'-aryl-N-alkyl ureido group, N'-aryl-N-aryl ureido group, N', N'-diaryl-N-alkyl ureido group, N ', N'-diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl ureido group, N'-alkyl-N'-aryl-N-aryl ureido , Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl- N-aryloxy carbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, aryloxy carbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO 3 H)及The conjugated base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfina Moyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfone Famoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (-SO 2 NHSO 2 (alkyl)) and its conjugation base group, N- aryl sulfonylsulfamoyl group (-SO 2 NHS 2 (aryl)) and its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO 2 (alkyl)) and its conjugated base group, N- aryl sulfonyl carbamoyl group (-CONHSO 2 (aryl)) and its conjugated base group , Alkoxysilyl group (-Si (Oalkyl) 3 ), aryloxysilyl group (-Si (Oaryl) 3 ), hydroxysilyl group (-Si (OH) 3 ) and its conjugate base group, phosphono group (-PO 3 H) 2) and its conjugated base group, a dialkyl phosphono group (-PO 3 (alkyl) 2), diaryl phosphono group (-PO 3 (aryl) 2), alkyl aryl phosphono group (-PO 3 (alkyl) (aryl )), monoalkyl phosphono group (-PO 3 H (alkyl)) and its conjugated base group Monoarylphosphono group (-PO 3 H (aryl)) and its conjugated base group, a phosphonooxy group (-OPO 3 H 2) and its conjugated base group, a dialkyl phosphono group (-OPO 3 (alkyl) 2) , Diaryl phosphonooxy group (-OPO 3 (aryl) 2 ), alkyl aryl phosphonooxy group (-OPO 3 (alkyl) (aryl)), monoalkyl phosphonooxy group (-OPO 3 H (alkyl)) and the same Conjugated base groups, monoarylphosphonooxy groups (—OPO 3 H (aryl)) and conjugated base groups thereof, cyano groups, nitro groups, aryl groups, alkenyl groups and alkynyl groups.
In addition, these substituents may combine with each other or with a substituted hydrocarbon group to form a ring, if possible.
一般式(II)中のR11及びR12はそれぞれ独立に水素原子若しくはアルキル基を表すか、または共にアルキル基であり互いに結合して環を形成していることが好ましく、R11及びR12は共に水素原子であるか、または共にアルキル基であり互いに結合して環を形成していることが好ましい。 R 11 and R 12 in general formula (II) each independently represent a hydrogen atom or an alkyl group, or are both alkyl groups and are preferably bonded to each other to form a ring, R 11 and R 12 It is preferred that both are hydrogen atoms, or are both alkyl groups and bonded to each other to form a ring.
接着性の観点から、一般式(II)で表される繰り返し単位は、下記一般式(V)で表される繰り返し単位であることが好ましい。一般式(V)で表される繰り返し単位による接着性の向上は、水酸基を有する接着剤層と極性を近づける効果によると推定する。 From the viewpoint of adhesion, the repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (V). The adhesion improvement by the repeating unit represented by the general formula (V) is presumed to be due to the effect of bringing the polarity close to the adhesive layer having a hydroxyl group.
一般式(V)中、R10は水素原子又は炭素数1~20のアルキル基を表し、R11及びR12はそれぞれ独立に、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基、又は置換もしくは無置換のヘテロアリール基を表し、R11とR12とは連結していてもよい。X11は-(C=O)O-、-O(C=O)-、-(C=O)NH-、-O-、-CO-、-CH2-からなる群より選択される少なくとも1つから構成される2価の連結基を表す。X12は-(C=O)O-、-O(C=O)-、-(C=O)NH-、-O-、-CO-、-NH-、-O(C=O)-NH-、-O(C=O)-O-、-CH2-から選択される連結基を少なくとも1つ含み、かつ置換もしくは無置換の芳香環を少なくとも1つ含む2価の連結基を表す。ただし、上記X11と上記X12の合計炭素数は7以上である。 In formula (V), R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R 11 and R 12 may be linked. X 11 is at least one selected from the group consisting of-(C = O) O-, -O (C = O)-,-(C = O) NH-, -O-, -CO-, -CH 2- It represents a divalent linking group composed of one. X 12 is — (C = O) O—, —O (C = O) —, — (C = O) NH—, —O—, —CO—, —NH—, —O (C = O) — NH -, - O (C = O) -O -, - CH 2 - comprises at least one linking group selected from, and represents a divalent linking group or a substituted or unsubstituted aromatic ring containing at least one . However, the total number of carbon atoms in the X 11 and the X 12 is 7 or more.
一般式(V)中のX11としては、-(C=O)O-、-O(C=O)-、-(C=O)NH-が好ましく、-(C=O)O-が最も好ましい。
X12は、芳香環を1~5個含むことが好ましく、芳香環を2~4個含むことが更に好ましく、芳香環を2~3個含むことが最も好ましい。
一般式(V)中のR10、R11及びR12の好ましい範囲はそれぞれ、一般式(II)中のR10、R11及びR12と同様である。
As X 11 in the general formula (V),-(C = O) O-, -O (C = O)-,-(C = O) NH- is preferable, and-(C = O) O- is Most preferred.
X 12 preferably contains 1 to 5 aromatic rings, more preferably 2 to 4 aromatic rings, and most preferably 2 to 3 aromatic rings.
Each preferred range of R 10, R 11 and R 12 in the general formula (V) are the same as R 10, R 11 and R 12 in the general formula (II).
一般式(II)又は(V)で表される繰り返し単位は、下記一般式(VI)で表される繰り返し単位であることがより好ましい。 The repeating unit represented by Formula (II) or (V) is more preferably a repeating unit represented by the following Formula (VI).
一般式(VI)中、R10は水素原子又は炭素数1~20のアルキル基を表し、R11及びR12はそれぞれ独立に、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基、又は置換もしくは無置換のヘテロアリール基を表し、R11とR12とは連結していてもよい。X21は-(C=O)O-、または-(C=O)NH-を表す。X22は-(C=O)O-、-O(C=O)-、-(C=O)NH-、-O-、-CO-、-NH-、-O(C=O)-NH-、-O(C=O)-O-、-CH2-から選択される連結基を少なくとも1つ含む2価の連結基であり、X22は置換もしくは無置換の芳香環を含んでいてもよい。 In formula (VI), R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted group R 11 represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R 11 and R 12 may be linked. X 21 represents — (C = O) O— or — (C = O) NH—. X 22 represents — (C = O) O—, —O (C = O) —, — (C = O) NH—, —O—, —CO—, —NH—, —O (C = O) — A divalent linking group containing at least one linking group selected from NH-, -O (C = O) -O-, -CH 2- , and X 22 includes a substituted or unsubstituted aromatic ring It may be
一般式(VI)中のR10、R11及びR12の好ましい範囲はそれぞれ、一般式(II)中のR10、R11及びR12と同様である。 Each preferred range of the general R 10 in formula (VI), R 11 and R 12 are the same as R 10, R 11 and R 12 in the general formula (II).
一般式(II)、(V)又は(VI)で表される繰り返し単位は単量体の重合により得ることができる。一般式(II)、(V)又は(VI)で表される繰り返し単位を与える好ましい単量体の具体例を示すが、これらに限定されるものではない。 The repeating units represented by the general formulas (II), (V) or (VI) can be obtained by polymerization of monomers. Specific examples of preferable monomers giving the repeating unit represented by the general formula (II), (V) or (VI) are shown, but not limited thereto.
また、共重合体(a)は、必要に応じて、一般式(I)で表される繰り返し単位及び一般式(II)で表される繰り返し単位以外の繰り返し単位(その他の繰り返し単位)を有していてもよい。 Further, the copolymer (a) optionally has a repeating unit (other repeating units) other than the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) It may be done.
その他の繰り返し単位を与える他の種類のモノマーとしては、PolymerHandbook 2nd ed.,J.Brandrup,Wiley lnterscience(1975) Chapter2 Page1~483に記載のものを用いることが出来る。例えばアクリル酸、メタクリル酸、アクリル酸エステル類、メタクリル酸エステル類、アクリルアミド類、メタクリルアミド類、アリル化合物、ビニルエーテル類、ビニルエステル類、イタコン酸ジアルキル類、フマール酸のジアルキルエステル類又はモノアルキルエステル類等から選ばれる付加重合性不飽和結合を1個有する化合物等を挙げることができる。 Other types of monomers that give other repeating units are described in Polymer Handbook 2nd ed. , J. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1-43. For example, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, dialkyl esters of fumaric acid or monoalkyl esters The compound etc. which have one addition polymerization unsaturated bond chosen from etc. can be mentioned.
その他の繰り返し単位を与える単量体として具体的には、以下の単量体を挙げることができる。
アクリル酸エステル類:
アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、クロルエチルアクリレート、2-ヒドロキシエチルアクリレート、トリメチロールプロパンモノアクリレート、ベンジルアクリレート、メトキシベンジルアクリレート、フェノキシエチルアクリレート、フルフリルアクリレート、テトラヒドロフルフリルアクリレート、2-アクリロイルオキシエチルサクシネート、アクリル酸2-カルボキシエチル等、
メタクリル酸エステル類:
メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、クロルエチルメタクリレート、2-ヒドロキシエチルメタクリレート、トリメチロールプロパンモノメタクリレート、ベンジルメタクリレート、メトキシベンジルメタクリレート、フェノキシエチルメタクリレート、フルフリルメタクリレート、テトラヒドロフルフリルメタクリレート、エチレングリコールモノアセトアセタートモノメタクリレート、2-メタクリロイロキシエチルフタル酸、2-メタクリロイルオキシエチルサクシネート、2-メタクリロイロキシエチルヘキサヒドロフタル酸、メタクリル酸2-カルボキシエチル等、
Specifically, the following monomers can be mentioned as a monomer which gives other repeating units.
Acrylic esters:
Methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2- Acryloyl oxyethyl succinate, 2-carboxyethyl acrylate, etc.,
Methacrylic acid esters:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol Monoacetoacetate monomethacrylate, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-carboxyethyl methacrylate, etc.
アクリルアミド類:
アクリルアミド、N-アルキルアクリルアミド(アルキル基としては炭素数1~3のもの、例えばメチル基、エチル基、プロピル基)、N,N-ジアルキルアクリルアミド(アルキル基としては炭素数1~6のもの)、N-ヒドロキシエチル-N-メチルアクリルアミド、N-2-アセトアミドエチル-N-アセチルアクリルアミドなど。
メタクリルアミド類:
メタクリルアミド、N-アルキルメタクリルアミド(アルキル基としては炭素数1~3のもの、例えばメチル基、エチル基、プロピル基)、N,N-ジアルキルメタクリルアミド(アルキル基としては炭素数1~6のもの)、N-ヒドロキシエチル-N-メチルメタクリルアミド、N-2-アセトアミドエチル-N-アセチルメタクリルアミドなど。
アリル化合物:
アリルエステル類(例えば酢酸アリル、カプロン酸アリル、カプリル酸アリル、ラウリン酸アリル、パルミチン酸アリル、ステアリン酸アリル、安息香酸アリル、アセト酢酸アリル、乳酸アリルなど)、アリルオキシエタノールなど
Acrylamides:
Acrylamide, N-alkyl acrylamide (having 1 to 3 carbon atoms as alkyl, such as methyl, ethyl and propyl), N, N-dialkyl acrylamide (having 1 to 6 carbons as alkyl), N-hydroxyethyl-N-methyl acrylamide, N-2-acetamidoethyl-N-acetyl acrylamide and the like.
Methacrylamides:
Methacrylamide, N-alkyl methacrylamide (having 1 to 3 carbon atoms as alkyl, such as methyl, ethyl and propyl), N, N-dialkyl methacrylamide (having 1 to 6 carbons as alkyl) N-hydroxyethyl-N-methyl methacrylamide, N-2-acetamidoethyl-N-acetyl methacrylamide and the like.
Allylic compound:
Allyl esters (eg allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate etc.), allyloxyethanol etc.
ビニルエーテル類:
アルキルビニルエーテル(例えばヘキシルビニルエーテル、オクチルビニルエーテル、デシルビニルエーテル、エチルヘキシルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、クロルエチルビニルエーテル、1-メチル-2,2-ジメチルプロピルビニルエーテル、2-エチルブチルビニルエーテル、ヒドロキシエチルビニルエーテル、ジエチレングリコールビニルエーテル、ジメチルアミノエチルビニルエーテル、ジエチルアミノエチルビニルエーテル、ブチルアミノエチルビニルエーテル、ベンジルビニルエーテル、テトラヒドロフルフリルビニルエーテルなど
ビニルエステル類:
ビニルアセテート、ビニルブチレート、ビニルイソブチレート、ビニルトリメチルアセテート、ビニルジエチルアセテート、ビニルバレート、ビニルカプロエート、ビニルクロルアセテート、ビニルジクロルアセテート、ビニルメトキシアセテート、ビニルブトキシアセテート、ビニルラクテート、ビニル-β―フェニルブチレート、ビニルシクロヘキシルカルボキシレートなど。
Vinyl ethers:
Alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. Vinyl esters:
Vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl- β-phenyl butyrate, vinyl cyclohexyl carboxylate and the like.
イタコン酸ジアルキル類:
イタコン酸ジメチル、イタコン酸ジエチル、イタコン酸ジブチルなど。
フマール酸のジアルキルエステル類又はモノアルキルエステル類:ジブチルフマレートなど。
Itaconic acid dialkyls:
Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.
Dialkyl esters or monoalkyl esters of fumaric acid: dibutyl fumarate and the like.
その他の繰り返し単位を与える単量体としては、クロトン酸、イタコン酸、アクリロニトリル、メタクリロニトリル、マレイロニトリル、スチレン、4-ビニル安息香酸、スチレンマクロマー(東亜合成社製AS-6S)、メチルメタクリレートマクロマー(東亜合成社製AA-6)なども挙げられる。また、重合後のポリマーを高分子反応にて構造を変換することも可能である。 As monomers giving other repeating units, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene, 4-vinylbenzoic acid, styrene macromer (AS-6S manufactured by Toagosei Co., Ltd.), methyl methacrylate Macromer (AA-6 manufactured by Toa Gosei Co., Ltd.) may also be mentioned. It is also possible to convert the structure of the polymer after polymerization by polymer reaction.
また、共重合体(a)は、熱架橋性基を有していることが好ましい。熱架橋性基とは、加熱により架橋反応を起こして架橋する基であり、その具体例としてはカルボキシル基、オキサゾリン基、ヒドロキシル基、イソシアネート基、マレイミド基、アセトアセトキシ基、エポキシ基、アミノ等が挙げられる。共重合体(a)は、熱架橋性基を有する繰り返し単位を含むことが好ましい。 The copolymer (a) preferably has a thermally crosslinkable group. The thermally crosslinkable group is a group which causes a crosslinking reaction by heating to crosslink, and specific examples thereof include a carboxyl group, an oxazoline group, a hydroxyl group, an isocyanate group, a maleimide group, an acetoacetoxy group, an epoxy group, amino and the like. It can be mentioned. The copolymer (a) preferably contains a repeating unit having a thermally crosslinkable group.
共重合体(a)は、光学フィルム中に含まれる他の化合物、とりわけスチレン系樹脂と熱架橋することが特に好ましい。共重合体(a)及びスチレン系樹脂がそれぞれ互いに反応性を示す熱架橋性基を有することで、共重合体(a)を光学フィルムの表面に固定化することができ、光学フィルムと他の層、膜、フィルム、または他の物品との、より高い接着性を発現することが可能となる。 The copolymer (a) is particularly preferably thermally crosslinked with other compounds contained in the optical film, in particular, a styrenic resin. The copolymer (a) can be immobilized on the surface of the optical film by the copolymer (a) and the styrenic resin each having a thermally crosslinkable group which is mutually reactive, and the optical film and the other films can be immobilized. It is possible to develop higher adhesion with layers, membranes, films or other articles.
共重合体(a)中の、一般式(I)で表される繰り返し単位の含有量は、共重合体(a)全質量に対して、5~95質量%が好ましく、8~90質量%がより好ましく、10~85質量%が更に好ましい。 The content of the repeating unit represented by the general formula (I) in the copolymer (a) is preferably 5 to 95% by mass, and 8 to 90% by mass, based on the total mass of the copolymer (a) Is more preferable, and 10 to 85% by mass is more preferable.
共重合体(a)中の、一般式(II)で表される繰り返し単位の含有量は、共重合体(a)全質量に対して、0.5~80質量%が好ましく、1~75質量%がより好ましく、2~70質量%が更に好ましい。 The content of the repeating unit represented by the general formula (II) in the copolymer (a) is preferably 0.5 to 80% by mass, based on the total mass of the copolymer (a), and 1 to 75 % By mass is more preferable, and 2 to 70% by mass is even more preferable.
共重合体(a)中の、熱架橋性基を有する繰り返し単位の含有量は、共重合体(a)全質量に対して、0.5~80質量%が好ましく、1~75質量%がより好ましく、2~70質量%が更に好ましい。 The content of the repeating unit having a thermally crosslinkable group in the copolymer (a) is preferably 0.5 to 80% by mass, and preferably 1 to 75% by mass, based on the total mass of the copolymer (a). More preferably, 2 to 70% by mass is more preferable.
共重合体(a)の重量平均分子量(Mw)は、1000~200000が好ましく、1800~150000がより好ましく、2000~150000が更に好ましく、2500~140000が特に好ましく、20000~120000が極めて好ましい。
共重合体(a)の数平均分子量(Mn)は、500~160000が好ましく、600~120000がより好ましく、600~100000が更に好ましく、1000~80000が特に好ましく、2000~60000が極めて好ましい。
共重合体(a)の分散度(Mw/Mn)は、1.00~18.00が好ましく、1.00~16.00がより好ましく、1.00~14.00が更に好ましく、1.00~12.00が特に好ましく、1.00~10.00が極めて好ましい。
なお、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により下記の条件で測定された値である。
[溶離液] N-メチル-2-ピロリドン(NMP)
[装置名] EcoSEC HLC-8320GPC(東ソー株式会社製)
[カラム] TSKgel SuperAWM-H(東ソー株式会社製)
[カラム温度] 40℃
[流速] 0.50ml/min
The weight average molecular weight (Mw) of the copolymer (a) is preferably 1000 to 200000, more preferably 1800 to 150000, still more preferably 2000 to 150000, particularly preferably 2500 to 140000, and very preferably 20000 to 120000.
The number average molecular weight (Mn) of the copolymer (a) is preferably 500 to 160000, more preferably 600 to 120000, still more preferably 600 to 100000, particularly preferably 1000 to 80000, and very preferably 2000 to 60000.
The dispersion degree (Mw / Mn) of the copolymer (a) is preferably 1.00 to 18.00, more preferably 1.00 to 16.00, still more preferably 1.00 to 14.00, and 1. 00 to 12.00 are particularly preferred, and 1.00 to 10.00 are very particularly preferred.
The weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography (GPC) under the following conditions.
[Eluent] N-methyl-2-pyrrolidone (NMP)
[Equipment name] EcoSEC HLC-8320GPC (made by Tosoh Corporation)
[Column] TSKgel Super AWM-H (made by Tosoh Corporation)
[Column temperature] 40 ° C
[Flow rate] 0.50 ml / min
共重合体(a)は、公知の方法で合成することができる。 The copolymer (a) can be synthesized by a known method.
共重合体(a)の具体例を以下に示すが、これらに限定されるものではない。 Although the specific example of a copolymer (a) is shown below, it is not limited to these.
本発明の光学フィルムは上記共重合体(a)を含有してもよいし、含有しなくてもよいが、含有する場合、上記共重合体(a)は、光学フィルムの機能を損なわず、接着剤との接着を強化する観点から、本発明の光学フィルムの全固形分(溶剤を除いた全成分)を100質量%とした場合に、0.0001~40質量%含有されることが好ましく、0.001~20質量%含有されることがより好ましく、0.005~10質量%含有されることが更に好ましい。 The optical film of the present invention may or may not contain the copolymer (a), but when it is contained, the copolymer (a) does not impair the function of the optical film, From the viewpoint of strengthening the adhesion to the adhesive, when the total solid content (all components excluding the solvent) of the optical film of the present invention is 100% by mass, the content is preferably 0.0001 to 40% by mass. The content is more preferably 0.001 to 20% by mass, and still more preferably 0.005 to 10% by mass.
<偏光子に対する光学フィルムの接着性改良樹脂>
偏光子に対する光学フィルムの接着性改良成分として、上記共重合体(a)とは異なる接着性改良樹脂を含んでいてもよい。接着性改良樹脂は熱架橋性基を有することが好ましく、また接着性改良樹脂はスチレン系モノマーに由来する繰り返し単位を含むものからなることが好ましい。熱架橋性基については、前述の共重合体(a)において説明したものと同様である。スチレン系樹脂が熱架橋性基を有していて、かつ、共重合体(a)が熱架橋性基を有していると、共重合体(a)を機能性膜の表面に固定化することができ、より高い接着性を発現することが可能となる。この場合、加熱により熱架橋性基を反応させることで共重合体(a)を機能性膜の表面に固定化することができるため、分子内に反応性基を有する化合物(モノマー)を含有させ、かつこのモノマーを紫外線等の電離放射線照射によって硬化させることにより共重合体(a)を機能性膜の表面に固定化するプロセスが不要となるので好ましい。
<Adhesive improvement resin of optical film to polarizer>
An adhesion improving resin different from the copolymer (a) may be contained as an adhesion improving component of the optical film to the polarizer. The adhesion improving resin preferably has a heat-crosslinkable group, and the adhesion improving resin preferably comprises a repeating unit derived from a styrenic monomer. The thermally crosslinkable group is the same as that described for the above-mentioned copolymer (a). When the styrene resin has a thermally crosslinkable group and the copolymer (a) has a thermally crosslinkable group, the copolymer (a) is immobilized on the surface of the functional film It is possible to develop higher adhesion. In this case, since the copolymer (a) can be immobilized on the surface of the functional film by reacting the thermally crosslinkable group by heating, a compound (monomer) having a reactive group in the molecule is contained. And, since the process of fixing the copolymer (a) to the surface of the functional film becomes unnecessary by curing the monomer by irradiation of ionizing radiation such as ultraviolet rays, it is preferable.
以下に、熱架橋性基を有するスチレン系樹脂の具体例を挙げるが、本発明はこれに限定されない。 Although the specific example of the styrene resin which has a thermally crosslinkable group is given to the following, this invention is not limited to this.
接着性改良樹脂は1種単独で用いてもよいし、接着性改良樹脂として、繰り返し単位の組成、分子量等が異なる複数種類のものを併用することもできる。
接着性改良樹脂は、公知のアニオン、塊状、懸濁、乳化または溶液重合方法により得ることができる。また、接着性改良樹脂においては、共役ジエンやスチレン系単量体のベンゼン環の不飽和二重結合が水素添加されていてもよい。水素添加率は核磁気共鳴装置(NMR)によって測定できる。
接着性改良樹脂としては市販品を用いることもでき、例えば、エポクロス RPS-1005:スチレン-オキサゾリン共重合体(日本触媒製)などが挙げられる。
The adhesion-improving resin may be used alone or in combination of two or more kinds having different repeating unit compositions, molecular weights and the like as the adhesion-improving resin.
The adhesion improving resin can be obtained by known anionic, bulk, suspension, emulsion or solution polymerization methods. In addition, in the adhesion improving resin, the unsaturated double bond of the benzene ring of a conjugated diene or a styrenic monomer may be hydrogenated. The hydrogenation rate can be measured by nuclear magnetic resonance (NMR).
A commercial item can also be used as the adhesion improving resin, and examples thereof include Epocross RPS-1005: styrene-oxazoline copolymer (manufactured by Nippon Shokubai).
本発明の光学フィルムは上記接着性改良樹脂を含有してもよいし、含有しなくてもよいが、含有する場合、上記接着性改良樹脂は、本発明の光学フィルムの全固形分に対して、0.0001~60質量%含有されることが好ましく、0.001~55質量%含有されることがより好ましく、0.005~50質量%含有されることが更に好ましい。 The optical film of the present invention may or may not contain the adhesion improving resin, but when it is contained, the adhesion improving resin is relative to the total solid content of the optical film of the present invention. The content is preferably 0.0001 to 60% by mass, more preferably 0.001 to 55% by mass, and still more preferably 0.005 to 50% by mass.
<光学フィルムの構成>
本発明の光学フィルムは、単膜であっても、2層以上の積層構造を有していてもよい。
<Configuration of optical film>
The optical film of the present invention may be a single film or have a laminated structure of two or more layers.
<膜厚>
本発明において好ましい光学フィルムの膜厚は、3~20μmであり、3~15μmがより好ましく、4~10μmがさらに好ましく、4~7μmが特に好ましく、4~6μmが最も好ましい。膜厚を4μm以上とすることで高温高湿下での偏光子伸長に対し十分に光学フィルムが伸長することで偏光板の破壊を抑制することが可能となり、10μm以下とすることで偏光板を薄層化できる点で好ましい。また、液晶表示装置に実装した場合に環境変化に伴う液晶表示装置の光ムラを低減する効果や、温湿度変化に伴う液晶パネルの反りを小さくするような効果も期待できるため、好ましい。
<Film thickness>
The film thickness of the optical film preferable in the present invention is 3 to 20 μm, more preferably 3 to 15 μm, still more preferably 4 to 10 μm, particularly preferably 4 to 7 μm, and most preferably 4 to 6 μm. By setting the film thickness to 4 μm or more, it is possible to sufficiently suppress the destruction of the polarizing plate by the optical film extending sufficiently to the polarizer extension under high temperature and high humidity, and by setting the thickness to 10 μm or less It is preferable at the point which can be thinned. In addition, it is preferable because the effect of reducing light unevenness of the liquid crystal display device due to environmental change and the effect of reducing warpage of the liquid crystal panel due to temperature change can be expected when the liquid crystal display device is mounted.
<光学フィルムの作製>
本発明の光学フィルムは、公知の溶液製膜法、溶融押出し法を用いて作製することができる。また、基材上に光学フィルムを積層する場合は、基材と同時に作製してもよい(共流延や共押出し)。また別途準備した仮支持体上に公知の方法で光学フィルム形成用塗布液による塗布層を形成する方法で準備することができ、適宜基材にポリマー溶液または塗布層が積層された状態で、適宜仮支持体ごと延伸することもできる。特にコーティング法を用いることが好ましい。
<Production of optical film>
The optical film of the present invention can be produced using a known solution film forming method or melt extrusion method. Moreover, when laminating | stacking an optical film on a base material, you may produce simultaneously with a base material (co-casting or co-extrusion). In addition, it can be prepared by a method of forming a coating layer with a coating solution for forming an optical film by a known method on a temporary support prepared separately, and in a state where a polymer solution or a coating layer is appropriately laminated on a substrate, The temporary support can also be stretched. In particular, it is preferable to use a coating method.
光学フィルムは、仮支持体上に、以下のコーティング法によって形成することができる。ディップコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、グラビアコート法、スライドコート法やエクストルージョンコート法(ダイコート法)(特開2003-164788号明細書参照)、マイクログラビアコート法等の公知の方法が用いられ、その中でもマイクログラビアコート法、ダイコート法が好ましい。コーティング法により光学フィルムを形成する場合、溶剤を揮発させる乾燥工程、熱架橋性基を架橋させる熱架橋工程を適宜用いることができる。 The optical film can be formed on the temporary support by the following coating method. Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, slide coating method, extrusion coating method (die coating method) (refer to JP-A-2003-164788), A known method such as a microgravure coating method is used, and among them, the microgravure coating method and the die coating method are preferable. When forming an optical film by a coating method, the drying process which volatilizes a solvent, and the thermal crosslinking process which bridge | crosslinks a thermally crosslinkable group can be used suitably.
<仮支持体の材料>
本発明の転写フィルムに用いられる仮支持体を形成する材料としては、機械的強度、表面粗さ、熱安定性等の観点に加え、光学フィルムとの接着性(接着力)で選定することができる。
<Material of temporary support>
As a material for forming a temporary support used in the transfer film of the present invention, in addition to the viewpoints of mechanical strength, surface roughness, thermal stability, etc., it may be selected by adhesion (adhesive force) with the optical film. it can.
このような仮支持体としては、公知の素材やフィルムを適宜使用することができる。具体的な材料として、ポリエステル系ポリマー、オレフィン系ポリマー、シクロオレフィン系ポリマー、(メタ)アクリル系ポリマー、セルロース系ポリマー、ポリアミド系ポリマー等を挙げることができる。
とりわけ、ポリエステル系ポリマー、オレフィン系ポリマーが基材フィルムの材料として好ましく、ポリエステル系ポリマーがより好ましく、ポリエステル系ポリマーの中でも特にポリエチレンテレフタレート(PET)が好ましい。
A well-known raw material and film can be used suitably as such a temporary support body. Specific examples of the material include polyester polymers, olefin polymers, cycloolefin polymers, (meth) acrylic polymers, cellulose polymers, and polyamide polymers.
In particular, polyester-based polymers and olefin-based polymers are preferable as the material of the base film, polyester-based polymers are more preferable, and among polyester-based polymers, polyethylene terephthalate (PET) is particularly preferable.
仮支持体の表面エネルギーは、特に限定されることはないが、光学フィルムの材料やコーティング溶液の表面エネルギーと、仮支持体の光学フィルムを形成させる側の表面の表面エネルギーとの関係性を調整することによって、光学フィルムと仮支持体との間の接着力を調整することができる。表面エネルギー差を小さくすれば、接着力が上昇する傾向があり、表面エネルギー差を大きくすれば、接着力が低下する傾向があり、適宜設定することができる。 Although the surface energy of the temporary support is not particularly limited, the relationship between the surface energy of the material of the optical film and the coating solution and the surface energy of the surface of the temporary support on which the optical film is formed is adjusted. By doing this, the adhesion between the optical film and the temporary support can be adjusted. If the surface energy difference is reduced, the adhesive force tends to increase, and if the surface energy difference is increased, the adhesive force tends to decrease and can be set appropriately.
水及びヨウ化メチレンの接触角値からOwensの方法を用いて、仮支持体の表面エネルギーを計算することが出来る。接触角の測定には、例えば、DM901(協和界面科学(株)製、接触角計)を用いることができる。
仮支持体の光学フィルムを形成する側の表面エネルギーは、41.0~48.0mN/mであることが好ましく、42.0~48.0mN/mであることが、より好ましい。表面エネルギーが41.0mN/m以上であると、光学フィルムの厚みの均一性を高められるため好ましく、48.0mN/m以下であると、光学フィルムを仮支持体との剥離力を適切な範囲に制御しやすいため、好ましい。
From the contact angle values of water and methylene iodide, the surface energy of the temporary support can be calculated using the method of Owens. For example, DM 901 (a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.) can be used to measure the contact angle.
The surface energy of the temporary support on the side of forming the optical film is preferably 41.0 to 48.0 mN / m, and more preferably 42.0 to 48.0 mN / m. It is preferable that the surface energy is 41.0 mN / m or more, because the uniformity of the thickness of the optical film can be enhanced, and the peeling force of the optical film to the temporary support is suitably within the range of 48.0 mN / m or less. Because it is easy to control
仮支持体表面には、光学フィルムとの接着性を制御するため、適宜離型剤等を予め塗布しておいてもよい。光学フィルムは、後工程で接着剤や粘着剤を介して偏光子と貼合させた後、仮支持体を剥離して用いることができる。なお、仮支持体に光学フィルムが積層された状態で、適宜仮支持体ごと延伸して、光学特性や力学物性を調整することができる。 On the surface of the temporary support, in order to control the adhesion to the optical film, a release agent may be applied in advance. The optical film can be used after peeling off the temporary support after being bonded to the polarizer through an adhesive or a pressure-sensitive adhesive in a later step. The optical properties and mechanical properties can be adjusted by appropriately stretching the temporary support together with the optical film laminated on the temporary support.
<仮支持体の表面凹凸>
本発明において、仮支持体の光学フィルムを形成する側の表面は、算術平均粗さ(Ra)が、40nm以下であることが好ましく、0.1~38nmであることがより好ましく、1~36nmであることが更に好ましい。
本発明における算術平均粗さ(Ra)は、日本工業規格(JIS) B0601:2013に基づくものである。
Raを40nm以下とすることで、光学フィルム側の凹部深さが小さくなり、高温高湿下における偏光子の伸長による偏光板の破壊を抑制することができる。また、光学フィルムの表示特性に関連するヘイズ、光線透過率、分光特性、等の視野内のムラを抑制する観点からも好ましい。また、Raを0.1nm以上にすることで、ロール形態でのブロッキングを防ぐことができる。本発明のRaは、例えば、非接触表面・層断面形状計測システムVertScan 2.0((株)菱化システム製)を用い、縦465.48μm、横620.64μm四方を測定することで得ることができる。また、別の指標として仮支持体の光学フィルム側の表面凸部の高さが0.1~10.0μmであることが好ましい。仮支持体の表面凸部の高さは、例えば、仮支持体の断面像を光学顕微鏡で観察し、平たん部から突き出している凸部の高さを観察することで、測定することができる。表面凸部を10.0μm以下とすることで、光学フィルム側の凹部深さが小さくなり、高温高湿下における偏光子の伸長による破壊を抑制することができる。
<Surface unevenness of temporary support>
In the present invention, the surface of the temporary support on which the optical film is to be formed preferably has an arithmetic average roughness (Ra) of 40 nm or less, more preferably 0.1 to 38 nm, and 1 to 36 nm. It is further preferred that
Arithmetic mean roughness (Ra) in the present invention is based on Japanese Industrial Standard (JIS) B0601: 2013.
By setting Ra to 40 nm or less, the recess depth on the optical film side becomes small, and it is possible to suppress the breakage of the polarizing plate due to the extension of the polarizer under high temperature and high humidity. Moreover, it is preferable also from a viewpoint of suppressing the nonuniformity in the visual field of the haze related to the display characteristic of an optical film, light transmittance, a spectral characteristic, etc. Moreover, blocking in a roll form can be prevented by Ra being 0.1 nm or more. The Ra of the present invention can be obtained, for example, by measuring 465.48 μm long and 620.64 μm wide using a non-contact surface / layer cross-sectional shape measurement system VertScan 2.0 (manufactured by Ryoka Systems Co., Ltd.) Can. Further, as another index, the height of the surface convex portion on the optical film side of the temporary support is preferably 0.1 to 10.0 μm. The height of the surface convex portion of the temporary support can be measured, for example, by observing the cross-sectional image of the temporary support with an optical microscope and observing the height of the convex portion protruding from the flat portion. . By setting the surface convex portion to 10.0 μm or less, the depth of the concave portion on the optical film side can be reduced, and the breakage due to the extension of the polarizer under high temperature and high humidity can be suppressed.
<仮支持体の膜厚>
光学フィルムを、コーティング法で形成させるために用いられる仮支持体は、膜厚が5~100μmであることが好ましく、10~75μmがより好ましく、15~55μmが更に好ましい。膜厚が5μm以上であると、十分な機械強度を確保しやすく、カール、シワ、座屈等の故障が生じにくいため、好ましい。また、膜厚が100μm以下であると、本発明の光学フィルムと仮支持体との転写フィルムを、例えば長尺のロール形態で保管する場合に、転写フィルムにかかる面圧を適正な範囲に調整しやすく、接着の故障が生じにくいため、好ましい。適宜、両端に厚み出し加工を付与することもできる。
<Film thickness of temporary support>
The thickness of the temporary support used to form the optical film by the coating method is preferably 5 to 100 μm, more preferably 10 to 75 μm, and still more preferably 15 to 55 μm. When the film thickness is 5 μm or more, sufficient mechanical strength is easily secured, and a failure such as curl, wrinkle, or buckling does not easily occur, which is preferable. In addition, when the transfer film of the optical film of the present invention and the temporary support is stored, for example, in the form of a long roll, the surface pressure applied to the transfer film is adjusted to an appropriate range as the film thickness is 100 μm or less. It is preferable because it is easy to cause and adhesion failure does not easily occur. Thicknessing processing can also be given to both ends as appropriate.
<厚み出し加工>
本発明の転写フィルムに用いられる仮支持体には、両端に厚み出し加工を付与する。厚み出し加工(ナーリングと呼ぶこともある)は、仮支持体の片側または両側からエンボス加工等で基材に凹凸を付与することを意味し、公知の方法を用いることができる。付与される厚み出し加工の高さは、光学フィルムの厚みに応じて適宜調整することができるが、例えば、0.2~5.5μmであり、0.5~5.0μmが好ましく、1.0~4.5μmがより好ましく、1.5~4.0μmがさらに好ましい。厚み出し加工の高さは、仮支持体単独または光学フィルムを積層した後、最も加圧された部分の厚み出し加工部を切り出し、凹凸高さを厚み計で測定して求める。
厚み出し加工の位置は、基材の両端から基材に対し0~10%の位置が好ましく、0.1~7%がより好ましく、0.3~5%がさらに好ましい。また、厚み出し加工の幅は、3~40mmが好ましく、5~30mmがより好ましく、10~25mmがさらに好ましい。
<Thicking processing>
The temporary support used in the transfer film of the present invention is provided with a thickening process at both ends. Thickening (also referred to as knurling) means to impart unevenness to a substrate by embossing or the like from one side or both sides of a temporary support, and a known method can be used. The height of the thickness setting processing to be applied can be appropriately adjusted according to the thickness of the optical film, and is, for example, 0.2 to 5.5 μm, and preferably 0.5 to 5.0 μm. 0 to 4.5 μm is more preferable, and 1.5 to 4.0 μm is more preferable. After laminating the temporary support alone or the optical film, the height of the thickness forming process is obtained by cutting out the thickness forming part of the most pressed part and measuring the height of unevenness with a thickness meter.
The position of thickness processing is preferably 0 to 10% relative to the substrate from both ends of the substrate, more preferably 0.1 to 7%, and still more preferably 0.3 to 5%. The width of the thickness forming process is preferably 3 to 40 mm, more preferably 5 to 30 mm, and still more preferably 10 to 25 mm.
<転写フィルム>
光学フィルムが塗工された転写フィルムは、少なくとも仮支持体と光学フィルムから構成され、一体化したものとして転写フィルムと呼称する。
転写フィルムは、光学フィルムと他の層、膜、フィルムまたは他の物品とを接着することができ、特に接着剤層を介して光学フィルムと偏光子を接着することができ、得られた偏光板としては仮支持体を光学フィルムから剥離することもでき、あるいは剥離せず偏光板の一部としてそのまま用いることもできるが、偏光板の薄型化の観点からは、光学フィルムから仮支持体を剥離して使用することが好ましい。
<Transfer film>
The transfer film on which the optical film is coated is composed of at least a temporary support and an optical film, and is referred to as a transfer film as one integrated.
The transfer film can adhere the optical film to other layers, films, films or other articles, and in particular can bond the optical film to the polarizer through the adhesive layer, and the obtained polarizing plate Although the temporary support can be peeled off from the optical film or can be used as it is as a part of the polarizing plate without peeling off, the temporary support can be peeled off from the optical film from the viewpoint of thinning the polarizing plate. It is preferable to use it.
<光学フィルムと仮支持体との剥離力>
本発明の偏光板に用いられる光学フィルムを、コーティング法で形成させる場合、光学フィルムと仮支持体との間の剥離力は、上記光学フィルムの材料、仮支持体の材料、光学フィルムの内部歪み等を調整して制御することができる。この剥離力は、例えば、仮支持体を光学フィルムの表面に対して90°方向に剥がす試験で測定することができ、300mm/分の速度で測定したときの剥離力が、0.001~5N/25mmが好ましく、0.01~3N/25mmがより好ましく、0.05~1N/25mmがさらに好ましい。0.001N/25mm以上であれば、仮支持体の剥離工程以外での剥離を防ぐことができ、5N/25mm以下であれば、剥離工程における剥離不良(例えば、ジッピングや、光学フィルムの割れ)を防ぐことができる。
<Peeling Force Between Optical Film and Temporary Support>
When the optical film used in the polarizing plate of the present invention is formed by a coating method, the peeling force between the optical film and the temporary support is determined by the material of the optical film, the material of the temporary support, and the internal strain of the optical film. Etc. can be adjusted and controlled. The peeling force can be measured, for example, by a test in which the temporary support is peeled in the direction of 90 ° with respect to the surface of the optical film, and the peeling force when measured at a speed of 300 mm / min is 0.001 to 5N. / 25 mm is preferable, 0.01 to 3 N / 25 mm is more preferable, and 0.05 to 1 N / 25 mm is more preferable. If it is 0.001 N / 25 mm or more, peeling of the temporary support in the peeling step can be prevented, and if it is 5 N / 25 mm or less, peeling failure in the peeling step (eg, dipping or cracking of the optical film) You can prevent.
<偏光板>
本発明における偏光板は、少なくとも、偏光子、および、本発明の光学フィルムを含む。また、上記偏光板は、偏光子と本発明の光学フィルムが接着剤層を介して貼り合わされていてもよい。
<Polarizer>
The polarizing plate in the present invention includes at least a polarizer and the optical film of the present invention. In the polarizing plate, the polarizer and the optical film of the present invention may be bonded via an adhesive layer.
<偏光子>
偏光子には、ヨウ素系偏光子、二色性染料を用いる染料系偏光子やポリエン系偏光子がある。ヨウ素系偏光子および染料系偏光子は、一般にポリビニルアルコール系フィルムを用いて製造する。本発明には、いずれの偏光子を用いてもよい。例えば偏光子はポリビニルアルコール(PVA)と二色性分子から構成することが好ましい。ポリビニルアルコール(PVA)と二色性分子から構成される偏光子については例えば特開2009-237376号公報の記載を参照することができる。偏光子の膜厚は、通常、1~50μmであればよく、2~30μmが好ましく、3~20μmがより好ましい。
<Polarizer>
The polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. The iodine based polarizer and the dye based polarizer are generally produced using a polyvinyl alcohol based film. Any polarizer may be used in the present invention. For example, the polarizer is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule. For the polarizer composed of polyvinyl alcohol (PVA) and a dichroic molecule, the description in JP-A-2009-237376 can be referred to, for example. The film thickness of the polarizer is usually 1 to 50 μm, preferably 2 to 30 μm, and more preferably 3 to 20 μm.
<偏光板保護フィルム>
偏光子に本発明の光学フィルムが貼合された面の反対面には、さらに本発明の光学フィルムを貼合してもよいし、従来知られている偏光板保護フィルムを貼合してもよい。
従来知られている偏光板保護フィルムについては、光学特性及び材料のいずれについても特に制限はないが、セルロースエステル樹脂、アクリル樹脂、および/または環状オレフィン樹脂、ポリエステル系樹脂を含む(あるいは主成分とする)フィルムを好ましく用いることができ、光学的に等方性のフィルムを用いても、光学的に異方性の位相差フィルムを用いてもよい。
従来知られている偏光板保護フィルムについて、セルロースエステル樹脂を含むものとしては、例えばフジタックTD40UC(富士フイルム(株)製)などを利用することができる。
従来知られている偏光板保護フィルムについて、アクリル樹脂を含むものとしては、特許第4570042号公報に記載のスチレン系樹脂を含有する(メタ)アクリル樹脂を含む偏光板保護フィルム、特許第5041532号公報に記載のグルタルイミド環構造を主鎖に有する(メタ)アクリル樹脂を含む偏光板保護フィルム、特開2009-122664号公報に記載のラクトン環構造を有する(メタ)アクリル系樹脂を含む偏光板保護フィルム、特開2009-139754号公報に記載のグルタル酸無水物単位を有する(メタ)アクリル系樹脂を含む偏光板保護フィルムを利用することができる。
従来知られている偏光板保護フィルムについて、環状オレフィン樹脂を含むものとしては、特開2009-237376号公報の段落[0029]以降に記載の環状オレフィン系樹脂フィルム、特許第4881827号公報、特開2008-063536号公報に記載のRthを低減する添加剤を含有する環状オレフィン樹脂フィルムを利用することができる。
従来知られている偏光板保護フィルムについて、ポリエステル樹脂を含むものとしては、ポリエチレンテレフタレートからなるコスモシャインSRF(東洋紡(株))、等を上げることができる。
<Polarizer protective film>
The optical film of the present invention may be further bonded to the opposite surface of the surface to which the optical film of the present invention is bonded to the polarizer, or even if a polarizing plate protective film known in the prior art is bonded. Good.
The conventionally known polarizing plate protective film is not particularly limited with respect to any of the optical properties and materials, but includes a cellulose ester resin, an acrylic resin, and / or a cyclic olefin resin, a polyester resin (or a main component Film) can be preferably used, and an optically isotropic film or an optically anisotropic retardation film may be used.
As a polarizing plate protective film conventionally known, as a thing containing cellulose ester resin, Fujitac TD40UC (made by Fujifilm Co., Ltd.) etc. can be utilized, for example.
The polarizing plate protective film conventionally known includes, as a film containing an acrylic resin, a polarizing plate protective film containing a (meth) acrylic resin containing a styrene resin described in Japanese Patent No. 4570042, Japanese Patent No. 5041532 A polarizing plate protective film containing a (meth) acrylic resin having a glutarimide ring structure described in claim 1 in the main chain, a polarizing plate containing a (meth) acrylic resin having a lactone ring structure described in JP2009-122664A A film, a polarizing plate protective film containing a (meth) acrylic resin having a glutaric anhydride unit described in JP-A-2009-139754 can be used.
As the polarizing plate protective film conventionally known, as a film containing cyclic olefin resin, cyclic olefin resin film described in paragraph [0029] or later of JP 2009-237376 A, JP 4881827 A, JP JP The cyclic olefin resin film containing the additive which reduces Rth of the 2008-063536 gazette can be utilized.
As a film containing a polyester resin, a conventionally known polarizing plate protective film can be exemplified by Cosmo Shine SRF (Toyobo Co., Ltd.) made of polyethylene terephthalate.
<偏光子への光学フィルムの貼り合わせ>
光学フィルムは、偏光板の保護フィルムとして用いられる。偏光板は、公知の方法で作製することができ、偏光子の搬送方向と、上記転写フィルムの搬送方向とが平行となるように貼り合わせて作製されることが好ましい。
Bonding Optical Film to Polarizer
An optical film is used as a protective film of a polarizing plate. The polarizing plate can be produced by a known method, and is preferably produced by bonding so that the transport direction of the polarizer and the transport direction of the transfer film are parallel.
このとき、光学フィルムには表面処理(特開平6-94915号公報、同6-118232号公報にも記載)を施して親水化してもよく、例えば、グロー放電処理、コロナ放電処理、又は、アルカリ鹸化処理などを施すことが好ましい。上記表面処理としてはコロナ放電処理が最も好ましく用いられる。 At this time, the optical film may be subjected to surface treatment (described in JP-A-6-94915 and JP-A-6-118232) to make it hydrophilic, and for example, glow discharge treatment, corona discharge treatment, or alkali It is preferable to carry out saponification treatment and the like. Corona discharge treatment is most preferably used as the surface treatment.
本発明における転写フィルムは、偏光板加工工程で接着剤や粘着剤を介して偏光子と積層させた後、仮支持体を剥離し、光学フィルムのみを偏光板に残して用いることができる。 The transfer film in the present invention can be used by laminating the polarizer with a polarizer in the polarizing plate processing step via an adhesive or a pressure-sensitive adhesive, peeling off the temporary support, leaving only the optical film on the polarizing plate.
<接着剤層>
接着剤層は接着剤から形成されたものであればよい。接着剤としては、水酸基を有する樹脂を含む接着剤が好ましく、ポリビニルアルコール系接着剤のほか、エポキシ系の活性エネルギー線硬化型接着剤、例えば特開2004-245925号公報に示されるような、分子内に芳香環を含まないエポキシ化合物を含有し、加熱又は活性エネルギー線の照射により硬化する接着剤、特開2008-174667号公報記載の(メタ)アクリル系化合物の合計量100質量部中に(a1)分子中に(メタ)アクリロイル基を2以上有する(メタ)アクリル系化合物と、(b1)分子中に水酸基を有し、重合性二重結合をただ1個有する(メタ)アクリル系化合物と、(c1)フェノールエチレンオキサイド変性アクリレートまたはノニルフェノールエチレンオキサイド変性アクリレートとを含有する活性エネルギー線硬化型接着剤などが挙げられる。これらの中で、ポリビニルアルコール系接着剤が最も好ましい。
なお、ポリビニルアルコール系接着剤は変性または未変性ポリビニルアルコールを含む接着剤である。ポリビニルアルコール系接着剤は、変性または未変性ポリビニルアルコールのほか、架橋剤を含有していてもよい。接着剤の具体例としては、ポリビニルアルコールまたはポリビニルアセタール(例、ポリビニルブチラール)の水溶液や、ビニル系ポリマー(例、ポリ塩化ビニル、ポリ酢酸ビニル、ポリブチルアクリレート)のラテックスが挙げられる。特に好ましい接着剤は、ポリビニルアルコールの水溶液である。このとき、ポリビニルアルコールは完全鹸化されたものが好ましい。
また、エポキシ系の活性エネルギー線硬化型接着剤は、活性エネルギー線の照射によりエポキシ基が開環し、水酸基を生じるので共重合体(a)と架橋することができる。そのため、本発明においてはエポキシ系の活性エネルギー線硬化型接着剤も水酸基含有接着剤として含み、適宜用いることができる。
<Adhesive layer>
The adhesive layer may be formed of an adhesive. As the adhesive, an adhesive containing a resin having a hydroxyl group is preferable, and in addition to a polyvinyl alcohol-based adhesive, an epoxy-based active energy ray-curable adhesive, for example, a molecule as shown in JP-A 2004-245925 An adhesive containing an epoxy compound which does not contain an aromatic ring and curing by heating or irradiation of active energy rays, the total amount of (meth) acrylic compounds described in JP-A-2008-174667 is 100 parts by mass ( a1) A (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule, and (b) a (meth) acrylic compound having a hydroxyl group in the molecule and having only one polymerizable double bond , (C1) containing phenol ethylene oxide modified acrylate or nonyl phenol ethylene oxide modified acrylate Such as sexual energy ray-curable adhesive. Among these, polyvinyl alcohol adhesives are most preferred.
The polyvinyl alcohol-based adhesive is an adhesive containing modified or non-modified polyvinyl alcohol. The polyvinyl alcohol-based adhesive may contain a crosslinking agent in addition to the modified or unmodified polyvinyl alcohol. Specific examples of the adhesive include aqueous solutions of polyvinyl alcohol or polyvinyl acetal (eg, polyvinyl butyral), and latexes of vinyl polymers (eg, polyvinyl chloride, polyvinyl acetate, polybutyl acrylate). A particularly preferred adhesive is an aqueous solution of polyvinyl alcohol. At this time, polyvinyl alcohol is preferably completely saponified.
Further, the epoxy-based active energy ray-curable adhesive can be crosslinked with the copolymer (a) because the epoxy group is opened by irradiation of active energy rays to form a hydroxyl group. Therefore, in the present invention, an epoxy-type active energy ray-curable adhesive is also included as a hydroxyl group-containing adhesive and can be used appropriately.
エポキシ系の活性エネルギー線硬化型接着剤は、例えば、特開2012-140610号公報、特開2012-140610号公報、特開2013-213214号公報、特開2015-40283号公報、特開2015-143352号公報、特開2015-187744号公報に記載のものを、適宜用いることができる。 For example, epoxy-based active energy ray-curable adhesives are disclosed in JP-A-2012-140610, JP-A-2012-140610, JP-A-2013-213214, JP-A-2015-40283, and JP-A-2015-. Those described in JP-A-143,352 and JP-A-2015-187744 can be used as appropriate.
<熱架橋性基の重合>
前述の本発明の光学フィルムが有する熱架橋性基の重合のための熱処理は、転写フィルムにおける光学フィルムの空気界面側表面に偏光子を貼り合わせる工程で、行うことができる。また偏光子を貼り合わせたのち、さらに熱架橋工程として熱処理時間を与えることで、光学フィルム―偏光子間の接着を向上することができる。
Polymerization of Thermally Crosslinkable Group
The heat treatment for polymerization of the thermally crosslinkable group of the optical film of the present invention described above can be carried out in the step of bonding a polarizer to the air interface side surface of the optical film in the transfer film. Moreover, after laminating | stacking a polarizer, the adhesion | attachment between an optical film and a polarizer can be improved by giving heat processing time as a thermal crosslinking process further.
熱架橋工程は、熱架橋性基の反応を促進させるために加温する工程であり、光学フィルムの性質を損なうものでなければ特に制限はないが、好ましくは40~200℃、更に好ましくは50~130℃である。反応をより進行させやすくする観点で50℃以上が好ましく、また、基材に用いる樹脂の変形を抑える観点で130℃以下であることが好ましい。
加温に要する時間は、使用する熱架橋性部位基の種類、及び量により異なるが、好ましくは5秒~1時間であり、より好ましくは10秒~30分であり、更に好ましくは15秒~5分である。反応をより進行させやすくする観点で15秒以上が好ましく、生産性を高くする観点で5分以下が好ましい。
The thermal crosslinking step is a heating step to accelerate the reaction of the thermal crosslinking group, and is not particularly limited as long as it does not impair the properties of the optical film, but preferably 40 to 200 ° C., more preferably 50. ~ 130 ° C. The temperature is preferably 50 ° C. or more from the viewpoint of facilitating the progress of the reaction, and is preferably 130 ° C. or less from the viewpoint of suppressing the deformation of the resin used for the substrate.
The time required for heating varies depending on the type and amount of the thermally crosslinkable site group used, but is preferably 5 seconds to 1 hour, more preferably 10 seconds to 30 minutes, still more preferably 15 seconds to 5 minutes. 15 seconds or more are preferable in the viewpoint which makes reaction advance more easily, and 5 minutes or less are preferable in the viewpoint which heightens productivity.
<偏光板の製造方法>
本発明の偏光板の製造方法は、
仮支持体上に塗布層を形成し、乾燥することにより、上記仮支持体上に光学フィルムを形成した転写フィルムを作成する工程、
上記転写フィルムにおける上記光学フィルムの空気界面側表面に偏光子を貼り合わせる工程、
上記転写フィルムから上記仮支持体を剥離する工程を有する偏光板の製造方法であって、
上記光学フィルムが、ブタジエンに由来する構成単位を含む共重合体を上記光学フィルムの全固形分に対して25~45質量%含み、
上記光学フィルムが、ポリエステル系添加剤を上記光学フィルムの全固形分に対して0.1~10質量%含み、
上記光学フィルムの厚さが、4~10μmであり、
上記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上であり、
上記仮支持体の上記光学フィルムを形成する側の表面の算術平均粗さが、40nm以下である、偏光板の製造方法である。
<Method of manufacturing polarizing plate>
The manufacturing method of the polarizing plate of the present invention is
A step of forming a coating layer on a temporary support and drying to form a transfer film having an optical film formed on the temporary support,
Attaching a polarizer to the air interface side surface of the optical film in the transfer film;
It is a manufacturing method of the polarizing plate which has the process of exfoliating the above-mentioned temporary support from the above-mentioned transfer film,
The optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
The optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film;
The thickness of the optical film is 4 to 10 μm,
The elongation at break of the optical film is 2.5% or more in an environment of 25 ° C. in a sample with a thickness of 30 μm and a width of 10 mm,
It is a manufacturing method of a polarizing plate whose arithmetic mean roughness of the surface of the side which forms the above-mentioned optical film of the above-mentioned temporary support body is 40 nm or less.
本発明の偏光板の製造方法において用いられる仮支持体、偏光子は前述したものと同様である。
また、光学フィルム形成用の塗布液について、ブタジエンに由来する構成単位を含む共重合体、ポリエステル系添加剤、その他の成分などの塗布液に含まれる成分又は含んでもよい成分は前述したものと同様である。また、塗布液の塗布方法も前述したものと同様である。
光学フィルムの厚さ、破断伸度なども前述したものと同様である。
The temporary support and the polarizer used in the method for producing a polarizing plate of the present invention are the same as those described above.
In addition, regarding the coating solution for forming an optical film, the component contained in the coating solution such as a copolymer containing a structural unit derived from butadiene, a polyester-based additive, other components, etc. or a component which may be included is the same as described above. It is. The coating method of the coating solution is also the same as described above.
The thickness of the optical film, the breaking elongation and the like are also the same as those described above.
本発明の偏光板の製造方法において、仮支持体上に形成された塗布層の乾燥方法は特に限定されず公知の方法で行うことができる。
また、転写フィルムにおける光学フィルム側表面に偏光子を貼り合わせる工程は、公知の方法で行うことができるが、好ましくは前述したものと同様である。なお、上記光学フィルム側表面は、通常は光学フィルムの空気界面側表面である。
上記転写フィルムから上記仮支持体を剥離する工程は、特に限定されず公知の方法で行うことができる。
In the method for producing a polarizing plate of the present invention, the method for drying the coating layer formed on the temporary support is not particularly limited and can be carried out by a known method.
Moreover, although the process of bonding a polarizer together on the optical film side surface in a transfer film can be performed by a well-known method, Preferably it is the same as that of what was mentioned above. The optical film side surface is usually the air interface side surface of the optical film.
The step of peeling the temporary support from the transfer film is not particularly limited and can be performed by a known method.
[表示装置]
本発明は、上記本発明の偏光板を含む表示装置にも関する。表示装置について特に制限はなく、液晶セルを含む液晶表示装置であっても、有機EL層を含む有機EL画像表示装置であっても、またプラズマ画像表示装置であってもよい。上記本発明の偏光板は、例えば、表示面側に配置することができる。表示装置の構成については、公知の表示装置のいずれの構成も採用することができる。
本発明の液晶表示装置は、さらにバックライトを有し、上記偏光板が上記バックライト側、あるいは視認側に配置されたことが好ましい。バックライトとしては特に制限は無く、公知のバックライトを用いることができる。本発明の液晶表示装置は、バックライト、バックライト側偏光板、液晶セル、視認側偏光板の順で積層されたことが好ましい。
その他の構成については、公知の液晶表示装置のいずれの構成も採用することができる。液晶セルの方式(モード)についても特に制限はなく、TN(Twisted Nematic)方式の液晶セル、横電界スイッチングIPS(In-Plane Switching)方式の液晶セル、FLC(Ferroelectric Liquid Crystal)方式の液晶セル、AFLC(Anti-ferroelectric Liquid Crystal)方式の液晶セル、OCB(Optically Compensatory Bend)方式の液晶セル、STN(Supper Twisted Nematic)方式の液晶セル、VA(Vertically Aligned)方式の液晶セルおよびHAN(Hybrid Aligned Nematic)方式の液晶セル等の様々な表示方式の液晶表示装置として構成することができる。その中でも、本発明の液晶表示装置は、上記液晶セルはIPS方式であることが好ましい。
その他の構成については、公知の液晶表示装置のいずれの構成も採用することができる。
[Display device]
The present invention also relates to a display device including the polarizing plate of the present invention. The display device is not particularly limited, and may be a liquid crystal display device including a liquid crystal cell, an organic EL image display device including an organic EL layer, or a plasma image display device. The polarizing plate of the present invention can be disposed, for example, on the display surface side. As a configuration of the display device, any configuration of a known display device can be adopted.
It is preferable that the liquid crystal display device of the present invention further has a backlight, and the polarizing plate is disposed on the backlight side or the viewing side. There is no restriction | limiting in particular as a backlight, A well-known backlight can be used. The liquid crystal display device of the present invention is preferably laminated in the order of the backlight, the backlight side polarizing plate, the liquid crystal cell, and the viewing side polarizing plate.
As other configurations, any configuration of a known liquid crystal display device can be adopted. There is also no particular limitation on the mode (mode) of the liquid crystal cell, and a TN (Twisted Nematic) mode liquid crystal cell, a horizontal electric field switching IPS (In-Plane Switching) mode liquid crystal cell, and an FLC (Ferroelectric Liquid Crystal) mode liquid crystal cell Liquid crystal cell of AFLC (Anti-ferroelectric Liquid Crystal) system, liquid crystal cell of OCB (Optically Compensatory Bend) system, liquid crystal cell of STN (Supper Twisted Nematic) system, liquid crystal cell of VA (Vertically Aligned) system, and HAN (Hybrid Aligned Nematic) As a liquid crystal display device of various display methods such as a liquid crystal cell of the can do. Among them, in the liquid crystal display device of the present invention, the liquid crystal cell is preferably an IPS system.
As other configurations, any configuration of a known liquid crystal display device can be adopted.
本発明の液晶表示装置の製造方法は、上記本発明の偏光板の製造方法によって製造された偏光板の上記光学フィルム側を液晶セル側に貼り合わせる工程を有する、液晶表示装置の製造方法である。 The method for producing a liquid crystal display device of the present invention is a method for producing a liquid crystal display device, comprising the step of bonding the optical film side of the polarizing plate produced by the method for producing a polarizing plate of the present invention to the liquid crystal cell side. .
以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本発明の範囲は以下に示す具体例に限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.
<合成例1>
(含フッ素共重合体(A-19)の合成例)
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を備えた500ミリリットル三口フラスコに、シクロヘキサノン23.3gを仕込んで、78℃まで昇温した。次いで、2-(パーフルオロヘキシル)エチルアクリレート59.10g(141.3ミリモル)、4-(4-アクリロイルオキシブトキシ)ベンゾイルオキシフェニルボロン酸11.00g(28.6ミリモル)、アクリル酸28.53g(299.1ミリモル)、1,3-プロパンジオール2.39g(31.5ミリモル)、シクロヘキサノン157.7g、イソプロパノール52.5g及び「V-601」(和光純薬(株)製)5.73gからなる混合溶液を、180分で滴下が完了するように等速で滴下した。滴下完了後、さらに1時間攪拌を続けた後、V-601を1.00g添加し、90℃まで昇温し、更に3時間攪拌を続け、含フッ素共重合体(A-19)のシクロヘキサノン溶液330.0gを得た。この共重合体の重量平均分子量(Mw)は5,700(ゲルパーミエーションクロマトグラフィー(EcoSEC HLC-8320GPC(東ソー株式会社製))により溶離液NMP、流速0.50ml/min、温度40℃の測定条件にてポリスチレン換算で算出、使用カラムはTSKgel SuperAWM-H×3本(東ソー株式会社製))であった。また、得られた重合体の1H-NMRスペクトルにて構造を同定し、組成比を決定した。
1H-NMR(CDCl3) δ:3.8~4.5(2H、4H、2-(パーフルオロヘキシル)エチルアクリレートに由来する繰り返し単位中のメチレン基由来、化合物II-12に由来する繰り返し単位のメチレン基由来、化合物II-12に由来する繰り返し単位のホウ素に隣接するメチレン基由来)、6.8~7.3ならびに7.6~8.2(8H、化合物II-12に由来する繰り返し単位の芳香環由来)。
Synthesis Example 1
(Synthesis example of fluorine-containing copolymer (A-19))
In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 23.3 g of cyclohexanone was charged, and the temperature was raised to 78 ° C. Then, 59.10 g (141.3 mmol) of 2- (perfluorohexyl) ethyl acrylate, 11.00 g (28.6 mmol) of 4- (4-acryloyloxybutoxy) benzoyloxyphenylboronic acid, 28.53 g of acrylic acid (299.1 mmol), 2.39 g (31.5 mmol) of 1,3-propanediol, 157.7 g of cyclohexanone, 52.5 g of isopropanol and 5.73 g of "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.) The mixed solution consisting of the above was dropped at an equal speed so that the dropping was completed in 180 minutes. After completion of the dropwise addition, stirring is further continued for 1 hour, 1.00 g of V-601 is added, the temperature is raised to 90 ° C., and stirring is continued for further 3 hours, and a solution of fluorine-containing copolymer (A-19) in cyclohexanone I got 330.0 g. The weight average molecular weight (Mw) of this copolymer was measured at 5,700 (gel permeation chromatography (EcoSEC HLC-8320 GPC (made by Tosoh Corp.)) as eluent NMP, flow rate 0.50 ml / min, temperature 40 ° C. Under the conditions, it was calculated in terms of polystyrene, and the column used was TSKgel Super AWM-H × 3 (made by Tosoh Corp.). Further, the structure was identified by 1 H-NMR spectrum of the obtained polymer, and the composition ratio was determined.
1 H-NMR (CDCl 3 ) δ: 3.8 to 4.5 (2H, 4H, methylene group in repeating units derived from 2- (perfluorohexyl) ethyl acrylate, derived from compound II-12 Derived from the methylene group of the unit, derived from the methylene group adjacent to the boron of the repeating unit derived from the compound II-12), 6.8 to 7.3 and 7.6 to 8.2 (8 H, derived from the compound II-12) Derived from the aromatic ring of the repeating unit).
含フッ素共重合体(A-19) Fluorinated copolymer (A-19)
含フッ素共重合体(A-19)の成分割合は、1H-NMRスペクトルにて構造を同定した結果、以下の割合であった。
2-(パーフルオロヘキシル)エチルアクリレートに由来する繰り返し単位25重量部、4-(4-アクリロイルオキシブトキシ)ベンゾイルオキシフェニルボロン酸1,3―ジプロパノールエステルに由来する繰り返し単位5重量部、アクリル酸に由来する繰り返し単位70重量部。
The component ratio of the fluorine-containing copolymer (A-19) was the following ratio as a result of the structure identification in the 1 H-NMR spectrum.
25 parts by weight of a repeating unit derived from 2- (perfluorohexyl) ethyl acrylate, 5 parts by weight of a repeating unit derived from 4- (4-acryloyloxybutoxy) benzoyloxyphenylboronic acid 1,3-dipropanol ester, acrylic acid 70 parts by weight of a repeating unit derived from
[実施例1~12、比較例1~7]
<光学フィルム形成用の塗布液の調製>
表1~2に示す組成で、光学フィルム形成用の塗布液1~19を調製した。表1~2において、「%」とは、「質量%」を表し、溶媒における数値は、塗布液全量に含まれる全溶媒中の各溶媒の含有率を表し、その他の成分における数値は、塗布液中の溶媒を除く成分(全固形分)中の含有率を表す。また、光学フィルム形成用塗布液1~19の全固形分濃度は、すべて14.3質量%であった。
[Examples 1 to 12, Comparative Examples 1 to 7]
<Preparation of Coating Solution for Forming Optical Film>
Coating solutions 1-19 for forming an optical film were prepared with the compositions shown in Tables 1-2. In Tables 1 and 2, "%" represents "% by mass", the numerical values in the solvent represent the content of each solvent in all the solvents contained in the total amount of the coating liquid, and the numerical values in the other components represent the coating It represents the content in the components (total solids) excluding the solvent in the liquid. In addition, the total solid concentration of the coating solutions 1 to 19 for forming an optical film was 14.3% by mass.
表1~2に記載の化合物を以下に示す。 The compounds described in Tables 1 to 2 are shown below.
(a)ブタジエンに由来する構成単位を含む共重合体
・アサフレックス810(旭化成(株)製)
・クリアレン220M(デンカ(株)製)
・TR2250((JSR(株)製)
(A) Copolymer containing a structural unit derived from butadiene-Asaflex 810 (manufactured by Asahi Kasei Co., Ltd.)
・ Clearen 220M (made by Denka Co., Ltd.)
・ TR 2250 (made by JSR Corporation)
(b)ポリエステル系添加剤
・バイロン550(東洋紡(株)製)
・バイロンGK680(東洋紡(株)製)
(B) Polyester-based additive Byron 550 (Toyobo Co., Ltd.)
・ Byron GK 680 (made by Toyobo Co., Ltd.)
(c)その他の成分
・F-552:市販フッ素系表面改質剤(DIC(株)社製、製品名:メガファックF-552)
・SGP-10:ポリスチレン(PSジャパン製)
・エポクロス RPS-1005:スチレン-オキサゾリン共重合体(日本触媒製)
(C) Other components ・ F-552: Commercially available fluorine-based surface modifier (made by DIC Corporation, product name: Megafac F-552)
・ SGP-10: Polystyrene (made by PS Japan)
・ Epocross RPS-1005: Styrene-Oxazoline Copolymer (manufactured by Nippon Shokubai)
溶媒
・酢酸エチル
・トルエン
Solvent ・ Ethyl acetate ・ Toluene
<光学フィルムの塗設1:光学フィルムA1~A19の作製>
市販のポリエチレンテレフタレートフィルム、エンブレットS38(膜厚38μm、ユニチカ(株)製)を基材として用い、塗布液1~19を使用し、それぞれ光学フィルムA1~A19を、膜厚が30μmとなるように作製した。具体的には、特開2006-122889号公報実施例1記載のスロットダイを用いたダイコート法で、基材上に、搬送速度60m/分の条件で各塗布液を塗布し、100℃で60秒乾燥させた。その後、巻き取った。このようにして、光学フィルムA1~A19を作製した。なお、上記ポリエチレンテレフタレートフィルムの光学フィルムを形成する側の表面のRaは34nmであった。
Coating of Optical Film 1: Preparation of Optical Film A1 to A19
Using commercially available polyethylene terephthalate film, Emblet S38 (film thickness 38 μm, manufactured by UNITIKA CO., LTD.) As a base material and using coating liquids 1 to 19 so that the optical films A1 to A19 each have a film thickness of 30 μm It was made. Specifically, each coating solution is applied on a substrate at a transfer speed of 60 m / min by a die coating method using a slot die described in JP-A-2006-122889, Example 1; Dried for a second. Then it was rolled up. Thus, optical films A1 to A19 were produced. In addition, Ra of the surface of the side which forms the optical film of the said polyethylene terephthalate film was 34 nm.
作製した光学フィルムA1~A19の膜厚、及び、破断伸度を下記の方法で評価した。 The film thicknesses and breaking elongations of the produced optical films A1 to A19 were evaluated by the following methods.
<膜厚>
光学フィルムの膜厚は、接触式膜厚計 KG30001(アンリツ(株)製)を用いて作製した積層体(転写フィルム)の膜厚を測定し、そこから同様に測定した基材厚みを引いて算出した。光学フィルムA1~A19の膜厚はすべて30.0μmであった。
<Film thickness>
The film thickness of the optical film is obtained by measuring the film thickness of a laminate (transfer film) manufactured using a contact film thickness meter KG30001 (manufactured by Anritsu Co., Ltd.), and subtracting the substrate thickness similarly measured therefrom. Calculated. The film thicknesses of the optical films A1 to A19 were all 30.0 μm.
<破断伸度>
上記で作製した光学フィルムA1~A19について、破断伸度測定を、下記に従い行った。即ち、引っ張り試験機テンシロンRTC-1210A((株)オリエンテック)を用い、乾燥状態(25℃、相対湿度60%)で、試料を幅10mm、長さ120mmに切り出し、光学フィルムをポリエチレンテレフタレートフィルムから剥離し、準備する。この試料を、引っ張り速度300mm/分、ロードセル50Nの設定で、破断伸度を測定する。各試料について5回測定し、最大値と最小値を除いた3回の結果を平均し、破断伸度とする。
<Breaking elongation>
The elongation at break measurement of the optical films A1 to A19 prepared above was performed according to the following. That is, using a tensile tester Tensilon RTC-1210A (Orientech Co., Ltd.), a sample is cut out to a width of 10 mm and a length of 120 mm in a dry state (25 ° C., relative humidity 60%), and an optical film is made of polyethylene terephthalate film. Peel and prepare. The breaking elongation of this sample is measured at a tension rate of 300 mm / min and a load cell 50N setting. The measurement is made 5 times for each sample, and the results of three times excluding the maximum value and the minimum value are averaged to give a breaking elongation.
<光学フィルムの塗設2:光学フィルム1~19の作製>
市販のポリエチレンテレフタレートフィルム、ルミラー(R)S105(膜厚38μm、東レ株式会社製)を基材(仮支持体)として用い、塗布液1~19を使用し、それぞれ光学フィルム1~19を、膜厚が5.0μmとなるように作製した。具体的には、特開2006-122889号公報実施例1記載のスロットダイを用いたダイコート法で、基材上に、搬送速度60m/分の条件で各塗布液を塗布し、100℃で60秒乾燥させた。その後、巻き取った。このようにして、ポリエチレンテレフタレートフィルム仮支持体付きの光学フィルム1~19を作製した。なお、上記ポリエチレンテレフタレートフィルムの光学フィルムを形成する側の表面のRaは34nmであった。
<Coating of optical film 2: Preparation of optical films 1 to 19>
A commercially available polyethylene terephthalate film, Lumirror (R) S105 (film thickness 38 μm, manufactured by Toray Industries, Inc.) is used as a substrate (temporary support), and coating liquids 1 to 19 are used to form optical films 1 to 19, respectively. It produced so that thickness might be set to 5.0 micrometers. Specifically, each coating solution is applied on a substrate at a transfer speed of 60 m / min by a die coating method using a slot die described in JP-A-2006-122889, Example 1; Dried for a second. Then it was rolled up. Thus, optical films 1 to 19 with a polyethylene terephthalate film temporary support were produced. In addition, Ra of the surface of the side which forms the optical film of the said polyethylene terephthalate film was 34 nm.
<剥離面評価(剥離跡の有無)>
上記で作製した光学フィルム1~19について、以下の方法で剥離面を評価した。即ち、縦50mmx横50mmx厚さ0.7mmのガラス基板にアクリル系粘着剤(厚さ20μm)を貼り付ける。次いで、上記光学フィルム(厚さ5.0μm、ポリエチレンテレフタレートフィルム仮支持体付き)を、光学フィルムが粘着剤と隣り合うように貼り付ける。この仮支持体を剥離した後、光学フィルムに対し、垂直位置を90°として、45~30°の角度で、照明を入れながら観察する。剥離面が白っぽくなっている場合(剥離跡が「あり」の場合)、品質に問題があると判断する。
<Peeling surface evaluation (presence of peeling mark)>
The peeled surfaces of the optical films 1 to 19 produced above were evaluated by the following method. That is, an acrylic adhesive (20 μm in thickness) is attached to a glass substrate of 50 mm in length × 50 mm in width × 0.7 mm in thickness. Then, the optical film (thickness 5.0 μm, with a polyethylene terephthalate film temporary support) is attached such that the optical film is adjacent to the adhesive. After peeling off the temporary support, the optical film is observed with illumination at an angle of 45 to 30 °, with the vertical position being 90 °. If the peeled surface is whitish (if the peeling mark is "presence"), it is judged that there is a problem with the quality.
下記表3に、各実施例及び比較例で使用した光学フィルム形成用塗布液の種類、光学A1~A19の破断伸度、及び光学フィルム1~19の剥離跡の評価結果を示す。 Table 3 below shows the evaluation results of the type of coating solution for forming an optical film, the elongation at break of optics A1 to A19, and the peeling marks of optical films 1 to 19 used in each example and comparative example.
剥離跡が「なし」であった光学フィルムが得られた塗布液を用いて、次の偏光板の作製及び液晶表示装置への実装評価を行った。 Using the coating liquid from which the optical film in which the peeling mark was "none" was obtained, preparation of the following polarizing plate and the mounting evaluation to a liquid crystal display device were performed.
[実施例101~112、比較例106及び107]
上記塗布液1~4、7、9、12~19を用いて、上記光学フィルムの塗設2と同様にして、ポリエチレンテレフタレートフィルム仮支持体付きの光学フィルム1~4、7、9、12~19を作製した。
[Examples 101 to 112, Comparative Examples 106 and 107]
Using the above coating solutions 1-4, 7, 9, 12 to 19 in the same manner as the coating 2 of the above optical film, an optical film 1 to 4, 7, 9, 12 to with a polyethylene terephthalate film temporary support 19 was produced.
<偏光板保護フィルムの作製>
〔ポリメチルメタクリレートフィルムの作製〕
特開2015-227458号公報の実施例1に従い、厚さ40μmのポリメチルメタクリレートフィルムを作製した。
<Preparation of polarizing plate protective film>
[Preparation of polymethyl methacrylate film]
According to Example 1 of JP-A-2015-227458, a polymethyl methacrylate film having a thickness of 40 μm was produced.
(表面処理)
上記で作製したポリメチルメタクリレートフィルムについて、下記条件でコロナ放電処理を行った。
電極:VETAPONE社製 Coron-Plus
ジェネレーター:CP1C
出力:900W
フィルム搬送速度:6m/分
上記処理を行ったポリメチルメタクリレートフィルムについて、幅1340mm、長さ100mのロール形態のフィルムを得た。
(surface treatment)
About the polymethyl methacrylate film produced above, corona discharge treatment was performed under the following conditions.
Electrode: VETAPONE Coron-Plus
Generator: CP1C
Output: 900 W
Film conveyance speed: 6 m / min About the polymethyl methacrylate film which performed the said process, the film of the roll form of width 1340 mm and length 100 m was obtained.
〔ポリエチレンテレフタレートフィルムの作製〕
特開2017-201417号公報の偏光子保護フィルム1の作製方法に従い、厚さ80μmのポリエチレンテレフタレートフィルムを作製した。
[Preparation of polyethylene terephthalate film]
According to the method for producing a polarizer protective film 1 of JP-A-2017-201417, a polyethylene terephthalate film having a thickness of 80 μm was produced.
(表面処理)
上記で作製したポリエチレンテレフタレートフィルムについて、下記条件でコロナ放電処理を行った。
電極:VETAPONE社製 Coron-Plus
ジェネレーター:CP1C
出力:900W
フィルム搬送速度:6m/分
上記処理を行ったポリエチレンテレフタレートフィルムについて、幅1340mm、長さ100mのロール形態のフィルムを得た。
(surface treatment)
About the polyethylene terephthalate film produced above, corona discharge treatment was performed under the following conditions.
Electrode: VETAPONE Coron-Plus
Generator: CP1C
Output: 900 W
Film conveyance speed: 6 m / min About the polyethylene terephthalate film which performed the said process, the film of the roll form of width 1340 mm and length 100 m was obtained.
〔セルロースアセテートフィルムの作製〕
(フィルムの表面処理)
セルロースアセテートフィルム(富士フイルム(株)製、フジタックTD40UC)を37℃に調温した1.5mol/Lの水酸化ナトリウム水溶液(けん化液)に1分間浸漬した後、フィルムを水洗し、その後、0.05mol/Lの硫酸水溶液に30秒浸漬した後、更に水洗浴を通した。そして、エアナイフによる水切りを3回繰り返し、水を落とした後に70℃の乾燥ゾーンに15秒間滞留させて乾燥し、鹸化処理したセルロースアセテートフィルムを作製した。
[Production of Cellulose Acetate Film]
(Surface treatment of film)
After immersing a cellulose acetate film (Fuji Film Co., Ltd., Fujitac TD40 UC) in a 1.5 mol / L aqueous solution of sodium hydroxide (saponification liquid) adjusted to 37 ° C. for 1 minute, the film is washed with water and then 0 After immersion in a 0.5 mol / L aqueous solution of sulfuric acid for 30 seconds, it was further passed through a water washing bath. Then, water drainage was repeated three times, and after removing water, the film was retained in a drying zone at 70 ° C. for 15 seconds and dried to prepare a saponified cellulose acetate film.
(偏光子の作製)
特開2001-141926号公報の実施例1に従い、2対のニップロール間に周速差を与え、長手方向に延伸し、厚さ18μmの偏光子を作製した。
(Preparation of polarizer)
According to Example 1 of Japanese Patent Application Laid-Open No. 2001-141926, a circumferential speed difference was given between two pairs of nip rolls, and the film was stretched in the longitudinal direction to prepare a polarizer with a thickness of 18 μm.
(貼り合わせ)
このようにして得た偏光子と、仮支持体付きの光学フィルム1~4、7、9、12~19と、上記鹸化処理したセルロースアセテートフィルムを用い、下記接着剤1を用いて、偏光子の吸収軸と各フィルムの長手方向とが平行になるようにロールツーロールで積層した。ここで、偏光子の一方の面は、仮支持体付きの光学フィルム1~4、7、9、12~19のいずれか1つの塗布面(光学フィルム側表面)が偏光子側となるようにし、偏光子の他方の面は、上記鹸化処理したセルロースアセテートフィルムと積層した。
(Pasted together)
A polarizer was obtained using the following adhesive 1 using the thus obtained polarizer, the optical films 1 to 4, 7, 9, 12 to 19 with a temporary support, and the saponified cellulose acetate film. The film was laminated by roll-to-roll so that the absorption axis of the film and the longitudinal direction of each film were parallel. Here, one surface of the polarizer is such that the coated surface (optical film side surface) of any one of the optical films 1 to 4, 7, 9 and 12 to 19 with a temporary support is on the polarizer side. The other side of the polarizer was laminated with the saponified cellulose acetate film.
・接着剤1:
ポリビニルアルコール(株式会社クラレ製、PVA-117H)3%水溶液を接着剤として用いた。
接着剤1を用いた場合、積層後70℃20分間の乾燥により硬化させた。
・接着剤2:
以下に示す組成の紫外線硬化型接着剤を作製した。
セロキサイド2021P 25質量部
アロンオキセタンOXT-221 50質量部
リカレジン DME-100 25質量部
光酸発生剤1 5質量部
Adhesive 1:
A 3% aqueous solution of polyvinyl alcohol (PVA-117H, manufactured by Kuraray Co., Ltd.) was used as an adhesive.
When Adhesive 1 was used, it was cured by drying at 70 ° C. for 20 minutes after lamination.
・ Adhesive 2:
The ultraviolet curable adhesive of the composition shown below was produced.
Celloxide 2021P 25 parts by mass Aron oxetane OXT-221 50 parts by mass Rika Resin DME-100 25 parts by mass Photoacid generator 1 5 parts by mass
・セロキサイド2021P:3,4-エポキシシクロヘキシルメチル-3,4'-エポキシシクロヘキサンカルボン酸[ダイセル(株)製]
・アロンオキセタンOXT-221:3-エチル-3-[(3-エチルオキセタン-3-イル)メトキシメチル]オキセタン[東亜合成(株)製]
・リカレジン DME-100:1,4-シクロヘキサンジメタノールジグリシジルエーテル[新日本理化(株)製]
・光酸発生剤1:CPI 100P[サンアプロ(株)製]
接着剤2を用いた場合、30℃の条件で、160W/cmの空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて、照度200mW/cm2、照射量160mJ/cm2の紫外線を照射して硬化させた。
・ Ceroxide 2021 P: 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylic acid (manufactured by Daicel Co., Ltd.)
Aron oxetane OXT-221: 3-ethyl-3-[(3-ethyl oxetan-3-yl) methoxymethyl] oxetane (manufactured by Toagosei Co., Ltd.)
· Rica resin DME-100: 1,4-cyclohexanedimethanol diglycidyl ether [manufactured by Shin Nippon Rika Co., Ltd.]
-Photo acid generator 1: CPI 100P [San Apro Co., Ltd. product]
When Adhesive 2 is used, an ultraviolet ray with an illuminance of 200 mW / cm 2 and an irradiation amount of 160 mJ / cm 2 is irradiated at a temperature of 30 ° C. using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) And allowed to cure.
上記貼り合わせに続けて、基材(仮支持体)であるポリエチレンテレフタレートフィルムを、セパレータの剥離装置と同様の装置を用いて連続剥離し、偏光板を作製した。 Following the above bonding, the polyethylene terephthalate film as a substrate (temporary support) was continuously peeled off using the same apparatus as the separator peeling apparatus to produce a polarizing plate.
<液晶表示装置への実装評価1>
IPSモードの液晶テレビ(スリム型55型液晶テレビ、バックライトとセルのクリアランスが0.5mm)のフロント側偏光板およびリア側偏光板として、上記作製した偏光板を、上記作製した光学フィルム側が液晶セル側に配置されるように、粘着剤を介して液晶セルに貼合した。得られた液晶テレビを、60℃・相対湿度90%の環境で3日間保持した後に、25℃・相対湿度60%の環境に移し、黒表示状態で点灯して偏光板破壊による光漏れ欠陥を評価した。偏光板破壊による光漏れについて評価した結果を表4に示す。
(正面方向の偏光板の割れによる光漏れ欠陥評価(高温高湿下での偏光板の破壊故障))
装置正面から観察した場合の黒表示時の光漏れ欠陥(言い換えると、偏光板の割れ)を観察し、以下の基準で評価した。
A:光漏れが観察されない。
B:光漏れが観察される。
<Mounting evaluation 1 for liquid crystal display>
The above-prepared polarizing plate was used as a front side polarizing plate and rear side polarizing plate of an IPS mode liquid crystal television (slim type 55 type liquid crystal television, backlight and cell clearance 0.5 mm) It was bonded to the liquid crystal cell via an adhesive so as to be disposed on the cell side. The obtained liquid crystal television is kept in an environment of 60 ° C. and relative humidity 90% for 3 days, then transferred to an environment of 25 ° C. and relative humidity 60% and lighted in a black display state to cause light leakage defects due to the polarization plate breakage. evaluated. Table 4 shows the results of evaluation of light leakage due to breakage of the polarizing plate.
(Evaluation of light leakage defects due to cracking of the polarizing plate in the front direction (destruction failure of the polarizing plate under high temperature and high humidity))
The light leakage defect (in other words, the crack of the polarizing plate) at the time of black display when observed from the front of the device was observed and evaluated according to the following criteria.
A: No light leakage is observed.
B: Light leakage is observed.
実施例1~12は、破断伸度はいずれも4.1%以上であり、偏光板の光漏れ欠陥が無いものであった。比較例1~5は、剥離跡が観察されるものであり、偏光板に用いる光学フィルムとしては、破棄されるレベルのものであった。
次に、実施例101~112は、黒表示状態で点灯して光漏れ欠陥が確認されない満足のいく品質のものであった。比較例106、107は、光漏れ欠陥が確認された。これは高温高湿下での偏光子の伸長により、光学フィルムが破壊された(すなわち偏光板が破壊された)ことが原因と考えられる。
In each of Examples 1 to 12, the elongation at break was 4.1% or more, and there was no light leakage defect of the polarizing plate. In Comparative Examples 1 to 5, peeling marks were observed, and the optical film used for the polarizing plate was at a level to be discarded.
Next, Examples 101 to 112 were of satisfactory quality in which light leakage defects were not confirmed by lighting in a black display state. The light leakage defect was confirmed in Comparative Examples 106 and 107. It is considered that this is because the optical film is broken (i.e., the polarizing plate is broken) by the extension of the polarizer under high temperature and high humidity.
[実施例201~203、比較例201及び202]
実施例201~203、および比較例201~202の光学フィルムを膜厚及び使用する仮支持体を変更した以外は光学フィルム1と同様にして得た。膜厚は、表5に記載の膜厚で作製した。仮支持体はエンブレットS38であり、表面凹凸(Ra(nm))は表中に記載のとおり34nmであった。
上記光学フィルムを用いた以外は、実施例101と同様にして偏光板を作製した。
作製した偏光板を用いて、上記液晶表示装置への実装評価1及び下記液晶表示装置への実装評価2を行った。
[Examples 201 to 203, Comparative Examples 201 and 202]
The optical films of Examples 201 to 203 and Comparative Examples 201 to 202 were obtained in the same manner as the optical film 1 except that the film thickness and the temporary support used were changed. The film thickness was produced with the film thickness described in Table 5. The temporary support was Emblet S38, and the surface asperity (Ra (nm)) was 34 nm as described in the table.
A polarizing plate was produced in the same manner as in Example 101 except that the above-mentioned optical film was used.
Using the produced polarizing plate, evaluation 1 for mounting on the liquid crystal display device and evaluation 2 for mounting on the following liquid crystal display device were performed.
<液晶表示装置への実装評価2>
IPSモードの液晶テレビ(スリム型55型液晶テレビ、バックライトとセルのクリアランスが0.5mm)のフロント側偏光板およびリア側偏光板として、上記作製した偏光板を、上記作製した光学フィルムが液晶セル側に配置されるように、粘着剤を介して液晶セルに貼合した。得られた液晶テレビを、60℃・相対湿度90%の環境で3日間保持した後に、25℃・相対湿度60%の環境に移し、黒表示状態で点灯させ続け、24時間後に目視観察して、パネル反りに起因する光ムラ(輝度ムラ)を評価した。
(正面方向の輝度ムラレベル)
装置正面から観察した場合の黒表示時の光ムラ(言い換えると、輝度ムラ)を観察し、以下の基準で評価した。
A:照度100lxの環境下でムラが全く視認されない
B:照度100lxの環境下でムラがほとんど視認されない
C:照度100lxの環境下で淡いムラが視認される
D:照度100lxの環境下で明確なムラが視認される
E:照度300lxの環境下で明確なムラが視認される
実用上問題が無いのはA、Bの基準である。Aの基準であることが好ましい。
<Mounting evaluation 2 for liquid crystal display>
The optical film produced as described above for the polarizing plate produced as the front side polarizing plate and rear side polarizing plate of an IPS mode liquid crystal television (slim type 55 type liquid crystal television, the clearance between the backlight and the cell is 0.5 mm) It was bonded to the liquid crystal cell via an adhesive so as to be disposed on the cell side. The obtained liquid crystal television is kept in an environment of 60 ° C. and relative humidity 90% for 3 days, then transferred to an environment of 25 ° C. and relative humidity 60% and kept on in a black state, and visually observed 24 hours later The light unevenness (brightness unevenness) caused by the panel warpage was evaluated.
(Uneven brightness level in the front direction)
Light unevenness (in other words, brightness unevenness) at the time of black display when observed from the front of the device was observed and evaluated according to the following criteria.
A: No unevenness is visually recognized at all under an environment of 100 lx B: Almost no unevenness is recognized under an environment of 100 lx C: Light unevenness is observed under an environment of 100 lx D: Clear under an environment of 100 lx Unevenness is visually recognized E: A clear unevenness is visually recognized under an environment of illuminance of 300 lx. It is preferable that it is a standard of A.
実施例201~203は、光漏れ欠陥がなく、輝度ムラもない、満足のいく品質であった。比較例201は、光学フィルムの膜厚が薄く、仮支持体の表面凹凸により膜厚が特に薄くなった部分が、割れたため光漏れ欠陥を生じた、と考えている。また、比較例202は、光学フィルムの膜厚が厚くなったため、輝度ムラを発生した、と考えている。 Examples 201 to 203 were of satisfactory quality with no light leakage defect and no luminance unevenness. In Comparative Example 201, it is considered that the film thickness of the optical film is thin, and a portion where the film thickness is particularly thin due to the surface unevenness of the temporary support is cracked and thus a light leakage defect is generated. Moreover, in Comparative Example 202, it is considered that uneven brightness was generated because the film thickness of the optical film was increased.
[実施例204、比較例203]
実施例101において、仮支持体をテオネックスQ51(Ra9nm、膜厚38μm、帝人デュポンフィルム(株)製)とするほかは、同様の作業を行い、光学フィルム20(膜厚5.0μm)を得た。
実施例101において、仮支持体をOPU-1(Ra76nm、膜厚38μm、三井化学東セロ(株))とするほかは、同様の作業を行い、光学フィルム21(膜厚5.0μm)を得た。
上記光学フィルムを用いた以外は実施例101と同様にして、実施例204及び比較例203の偏光板を作製し、液晶表示装置への実装評価1及び液晶表示装置への実装評価2を行った。結果を以下に示す。
[Example 204, Comparative Example 203]
The same procedure as in Example 101 was repeated except that the temporary support was changed to Theonex Q51 (Ra 9 nm, film thickness 38 μm, Teijin DuPont Film Co., Ltd.), to obtain an optical film 20 (film thickness 5.0 μm) .
The same operation as in Example 101 was conducted except that the temporary support was changed to OPU-1 (Ra 76 nm, film thickness 38 μm, Mitsui Chemicals Tosoh Co., Ltd.), to obtain an optical film 21 (film thickness 5.0 μm) .
The polarizing plates of Example 204 and Comparative Example 203 were produced in the same manner as in Example 101 except that the above optical film was used, and the evaluation of mounting on a liquid crystal display device 1 and the evaluation of mounting on a liquid crystal display device 2 were performed. . The results are shown below.
実施例204は、光漏れ欠陥がなく、輝度ムラもない、満足のいく品質であった。比較例203は、仮支持体の表面凹凸が大きく、光学フィルムの膜厚が特に薄くなった部分が、割れたため光漏れ欠陥を生じた、と考えている。 Example 204 was of satisfactory quality with no light leakage defects and no luminance unevenness. Comparative Example 203 is considered to have caused a light leakage defect because the surface asperity of the temporary support was large and the portion where the film thickness of the optical film was particularly thin was broken.
[実施例205~209]
<偏光板の作製>
実施例101において、偏光板保護フィルムを、セルロースアセテートフィルムに代えて上述のポリメチルメタクリレートフィルムとするほかは同様の作業を行い、偏光板301を得た。
実施例101において、偏光板保護フィルムを、セルロースアセテートフィルムに代えて上述のポリエチレンテレフタレートフィルムとするほかは同様の作業を行い、偏光板302を得た。
実施例101において、接着剤を、接着剤1に代えて接着剤2にし、紫外線を照射して硬化するほかは同様の作業を行い、偏光板303を得た。
実施例101において、偏光板保護フィルムを、セルロースアセテートフィルムに代えて上述のポリメチルメタクリレートフィルムとし、接着剤を、接着剤1に代えて接着剤2にし、紫外線を照射して硬化するほかは同様の作業を行い、偏光板304を得た。
実施例101において、偏光板保護フィルムを、セルロースアセテートフィルムに代えて上述のポリエチレンテレフタレートフィルムとし、接着剤を、接着剤1に代えて接着剤2にし、紫外線を照射して硬化するほかは同様の作業を行い、偏光板305を得た。
上記偏光板を用いて、実施例205~209の液晶表示装置への実装評価1及び2を行った。結果を以下に示す。
[Examples 205 to 209]
<Production of Polarizing Plate>
A polarizing plate 301 was obtained in the same manner as in Example 101 except that the polarizing plate protective film was replaced with a cellulose acetate film to make the above-mentioned polymethyl methacrylate film.
A polarizing plate 302 was obtained in the same manner as in Example 101 except that the polarizing plate protective film was replaced with a cellulose acetate film to make the above-mentioned polyethylene terephthalate film.
In Example 101, the adhesive was changed to the adhesive 2 instead of the adhesive 1, and the same operation was performed except that the ultraviolet ray was irradiated and cured to obtain a polarizing plate 303.
In Example 101, the polarizing plate protective film is replaced with a cellulose acetate film to make the above-mentioned polymethyl methacrylate film, and the adhesive is replaced with the adhesive 1 to make the adhesive 2, and the same procedure is followed except that curing is performed by irradiating ultraviolet light. The following operation was performed to obtain a polarizing plate 304.
Example 101 is the same as Example 101 except that the polarizing plate protective film is replaced with a cellulose acetate film to form the above-mentioned polyethylene terephthalate film, and the adhesive is replaced by the adhesive 1 to form the adhesive 2 and irradiated with ultraviolet light to cure. The work was performed to obtain a polarizing plate 305.
The evaluations 1 and 2 of mounting to the liquid crystal display devices of Examples 205 to 209 were performed using the above polarizing plates. The results are shown below.
実施例205~209は、光漏れ欠陥なく、輝度ムラもない、満足のいく品質であった。 Examples 205 to 209 had satisfactory quality with no light leakage defect and no luminance unevenness.
上記表3から7より、本発明の光学フィルムは、高温高湿下の偏光板の破壊を抑制する効果が高いことが分かった。また、本発明の光学フィルムを有する偏光板を具備する液晶表示装置は、輝度ムラを抑えられることが分かった。 From Tables 3 to 7 above, it was found that the optical film of the present invention is highly effective in suppressing the breakage of the polarizing plate under high temperature and high humidity. Moreover, it turned out that the liquid crystal display which comprises the polarizing plate which has an optical film of this invention can suppress a brightness nonuniformity.
本発明により、高温高湿下における破壊故障が抑制され、かつ画像表示装置に適用した際に輝度ムラを抑制できる偏光板の製造方法及び上記偏光板を有する液晶表示装置の製造方法、並びに、高温高湿下において偏光板の破壊故障を抑制でき、かつ画像表示装置に適用した際に輝度ムラを抑制できる光学フィルムを提供することができる。 According to the present invention, a method of manufacturing a polarizing plate capable of suppressing breakage failure under high temperature and high humidity and suppressing unevenness in luminance when applied to an image display device, a method of manufacturing a liquid crystal display device having the above polarizing plate, and The optical film which can suppress the destructive failure of a polarizing plate under high humidity, and can suppress a brightness nonuniformity when it applies to an image display can be provided.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
本出願は、2017年11月15日出願の日本特許出願(特願2017-220289)に基づくものであり、その内容はここに参照として取り込まれる。
Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (No. 2017-220289) filed on Nov. 15, 2017, the contents of which are incorporated herein by reference.
Claims (5)
前記転写フィルムにおける前記光学フィルムの空気界面側表面に偏光子を貼り合わせる工程、
前記転写フィルムから前記仮支持体を剥離する工程を有する偏光板の製造方法であって、
前記光学フィルムが、ブタジエンに由来する構成単位を含む共重合体を前記光学フィルムの全固形分に対して25~45質量%含み、
前記光学フィルムが、ポリエステル系添加剤を前記光学フィルムの全固形分に対して0.1~10質量%含み、
前記光学フィルムの厚さが、4~10μmであり、
前記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上であり、
前記仮支持体の前記光学フィルムを形成する側の表面の算術平均粗さが、40nm以下である、偏光板の製造方法。 A step of forming a coating layer on a temporary support and drying to form a transfer film having an optical film formed on the temporary support;
Attaching a polarizer to the air interface side surface of the optical film in the transfer film;
It is a manufacturing method of a polarizing plate which has a process of exfoliating said temporary support from said transfer film,
The optical film contains 25 to 45% by mass of a copolymer containing a structural unit derived from butadiene based on the total solid content of the optical film,
The optical film contains 0.1 to 10% by mass of a polyester-based additive based on the total solid content of the optical film,
The thickness of the optical film is 4 to 10 μm,
The elongation at break of the optical film is 2.5% or more in an environment of 25 ° C. in a sample with a thickness of 30 μm and a width of 10 mm,
The manufacturing method of the polarizing plate whose arithmetic mean roughness of the surface of the side which forms the said optical film of the said temporary support body is 40 nm or less.
前記ブタジエンに由来する構成単位を含む共重合体の含有量が、前記光学フィルムの全固形分に対して25~45質量%であり、
前記ポリエステル系添加剤の含有量が、前記光学フィルムの全固形分に対して0.1~10質量%であり、
前記光学フィルムの厚さが、4~10μmであり、
前記光学フィルムの破断伸度が、厚さ30μm、幅10mmの試料において、25℃の環境下で2.5%以上である、光学フィルム。 An optical film comprising a copolymer containing a structural unit derived from butadiene, and a polyester-based additive,
The content of the copolymer containing a structural unit derived from butadiene is 25 to 45% by mass with respect to the total solid content of the optical film,
The content of the polyester-based additive is 0.1 to 10% by mass with respect to the total solid content of the optical film,
The thickness of the optical film is 4 to 10 μm,
The optical film whose breaking elongation of the said optical film is 2.5% or more in a 25 degreeC environment in the sample of thickness 30 micrometers and width 10 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019554206A JP6999690B2 (en) | 2017-11-15 | 2018-11-12 | Method for manufacturing polarizing plate and method for manufacturing liquid crystal display device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017220289 | 2017-11-15 | ||
| JP2017-220289 | 2017-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2019098159A1 true WO2019098159A1 (en) | 2019-05-23 |
Family
ID=66539014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2018/041863 Ceased WO2019098159A1 (en) | 2017-11-15 | 2018-11-12 | Method for manufacturing polarizing plate, method for manufacturing liquid crystal display device, and optical film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6999690B2 (en) |
| WO (1) | WO2019098159A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05170940A (en) * | 1991-12-24 | 1993-07-09 | Daicel Chem Ind Ltd | Polystyrenic resin film |
| JP2006152036A (en) * | 2004-11-25 | 2006-06-15 | Techno Polymer Co Ltd | Thermoplastic resin composition and molded article |
| JP2013141820A (en) * | 2012-01-12 | 2013-07-22 | Toagosei Co Ltd | Production process of optical film or sheet |
| JP2017083740A (en) * | 2015-10-30 | 2017-05-18 | コニカミノルタ株式会社 | Optical film and method for producing the same |
| JP2017142489A (en) * | 2016-02-05 | 2017-08-17 | 富士フイルム株式会社 | Method for manufacturing polarizing plate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003220673A (en) * | 2003-02-07 | 2003-08-05 | Mitsubishi Plastics Ind Ltd | Heat shrinkable polystyrene-based laminated film |
| JP2006124435A (en) * | 2004-10-26 | 2006-05-18 | Sekisui Chem Co Ltd | Maleimide-based copolymer resin film |
| JP2006259623A (en) * | 2005-03-18 | 2006-09-28 | Sekisui Chem Co Ltd | Optical film, retardation film, polarizer protective film and polarizing plate |
| JP2013182070A (en) * | 2012-02-29 | 2013-09-12 | Techno Polymer Co Ltd | Polarizer protective film and polarizing plate |
-
2018
- 2018-11-12 JP JP2019554206A patent/JP6999690B2/en active Active
- 2018-11-12 WO PCT/JP2018/041863 patent/WO2019098159A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05170940A (en) * | 1991-12-24 | 1993-07-09 | Daicel Chem Ind Ltd | Polystyrenic resin film |
| JP2006152036A (en) * | 2004-11-25 | 2006-06-15 | Techno Polymer Co Ltd | Thermoplastic resin composition and molded article |
| JP2013141820A (en) * | 2012-01-12 | 2013-07-22 | Toagosei Co Ltd | Production process of optical film or sheet |
| JP2017083740A (en) * | 2015-10-30 | 2017-05-18 | コニカミノルタ株式会社 | Optical film and method for producing the same |
| JP2017142489A (en) * | 2016-02-05 | 2017-08-17 | 富士フイルム株式会社 | Method for manufacturing polarizing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6999690B2 (en) | 2022-02-10 |
| JPWO2019098159A1 (en) | 2020-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102126761B1 (en) | Copolymer, and composition | |
| JP6043799B2 (en) | Optical film and method for manufacturing the same, polarizing plate, and liquid crystal display device | |
| KR102214909B1 (en) | Composition, optical film, polarizing plate, display device, and method of manufacturing the composition | |
| TWI744387B (en) | Liquid crystal composition, optical film, polarizing plate, and image display device | |
| US11939462B2 (en) | Functional film, polarizing plate, and display device | |
| JP6327289B2 (en) | Polarizing plate protective film, production method thereof, polarizing plate and image display device | |
| CN114456724B (en) | Laminate body | |
| WO2017057255A1 (en) | Polarizing plate protective film, method for manufacturing same, polarizing plate, and image display device | |
| JP2022013705A (en) | Polarization plate having retardation layer and adhesive layer, and picture display unit using the polarization plate having retardation layer and adhesive layer | |
| TW201447399A (en) | Optical film, polarizing plate, image display device, and optical film fabrication method | |
| WO2021186946A1 (en) | Polarizing plate with retardation layer and adhesive layer, and image display device using polarizing plate with retardation layer and adhesive layer | |
| TW201520283A (en) | Polarizing plate and image display apparatus comprising the same | |
| JP6724370B2 (en) | Optical film, method of manufacturing optical film, polarizing plate and image display device | |
| JP2017122855A (en) | Optical film, method for manufacturing optical film, polarizing plate, and image display device | |
| WO2022004284A1 (en) | Polarizing plate equipped with retardation layer and adhesive layer, and image display device using polarizing plate equipped with retardation layer and adhesive layer | |
| WO2019098159A1 (en) | Method for manufacturing polarizing plate, method for manufacturing liquid crystal display device, and optical film | |
| WO2018003662A1 (en) | Copolymer and composition | |
| WO2023074388A1 (en) | Retardation layer-equipped polarizing plate and image display device | |
| JP7592662B2 (en) | Polarizing plate with phase difference layer and image display device | |
| WO2020217535A1 (en) | Polarization plate and liquid crystal display device | |
| WO2021084625A1 (en) | Polarizing plate, method for manufacturing polarizing plate, and liquid crystal display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18879036 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2019554206 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 18879036 Country of ref document: EP Kind code of ref document: A1 |