WO2014199934A1 - Polarizing plate, method for producing polarizing plate, transfer material for production of polarizing plate, and transfer material - Google Patents

Polarizing plate, method for producing polarizing plate, transfer material for production of polarizing plate, and transfer material Download PDF

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Publication number
WO2014199934A1
WO2014199934A1 PCT/JP2014/065185 JP2014065185W WO2014199934A1 WO 2014199934 A1 WO2014199934 A1 WO 2014199934A1 JP 2014065185 W JP2014065185 W JP 2014065185W WO 2014199934 A1 WO2014199934 A1 WO 2014199934A1
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layer
cycloolefin polymer
film
group
polarizing plate
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PCT/JP2014/065185
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French (fr)
Japanese (ja)
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昌孝 長谷川
英章 香川
和宏 沖
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富士フイルム株式会社
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Publication of WO2014199934A1 publication Critical patent/WO2014199934A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

Definitions

  • the present invention relates to a polarizing plate manufacturing method and a polarizing plate.
  • the present invention also relates to a transfer material used in a method for manufacturing a polarizing plate, and a method for manufacturing the transfer material.
  • An object of the present invention is to provide a polarizing plate having a small film thickness. This invention makes it a subject to provide the manufacturing method of the polarizing plate which has especially a low birefringent thin film polymer film as a protective film.
  • the present inventors tried to produce a thinner protective film under the above-mentioned problems.
  • a conventional film forming method such as a casting method or an extrusion method at an ultra-low speed
  • the thin film is broken when transported in a subsequent process such as drying or stretching.
  • a cycloolefin polymer film can be formed as a thin film by coating and forming on a temporary support and can be peeled off from the temporary support without defects.
  • the present invention was completed by further study. That is, the present invention provides the following [1] to [14].
  • a method for producing a polarizing plate comprising the following (1) to (3): (1) applying a composition containing a cycloolefin polymer on a temporary support to form a cycloolefin polymer-containing layer; (2) laminating the cycloolefin polymer-containing layer and a film containing a polarizer; (3) Peeling off the temporary support.
  • the cycloolefin polymer-containing layer is formed by coating a composition containing a cycloolefin polymer directly on the surface of the temporary support.
  • a polarizing plate comprising a polarizer and a cycloolefin polymer-containing layer having a thickness of 20 ⁇ m or less that is directly bonded to the polarizer via an adhesive layer.
  • a method for producing a transfer material for producing a polarizing plate including apply
  • the present invention provides a method for producing a polarizing plate. According to the present invention, a polarizing plate having a low-birefringence thin film polymer film as a protective film can be easily produced.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the “polarizing plate” is cut into a necessary size such as a size to be incorporated in a long polarizing plate and a liquid crystal device (in this specification, “cutting”
  • the term “including punching” and “cutting out” is used to include both polarizing plates.
  • polarizer sometimes referred to as “polarizing film” and “polarizing plate” are used separately, but “polarizing plate” is a laminate having a film on at least one side of “polarizer”. Means.
  • description with "(meth) acrylate” represents the meaning of "any one or both of an acrylate and a methacrylate.” The same applies to “(meth) acrylic acid” and the like.
  • Re ( ⁇ ) and Rth ( ⁇ ) represent in-plane retardation and retardation in the thickness direction at a wavelength ⁇ , respectively.
  • Re ( ⁇ ) is measured by making light having a wavelength of ⁇ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). In selecting the measurement wavelength ⁇ nm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.
  • Rth ( ⁇ ) is calculated by the following method.
  • Rth ( ⁇ ) is Re ( ⁇ )
  • the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) (if there is no slow axis, any film surface in-plane
  • the direction of the axis of rotation is the film normal direction), and from the normal direction to 50 degrees on one side, the light of wavelength ⁇ nm is incident from each inclined direction in steps of 10 degrees to measure a total of 6 points.
  • KOBRA 21ADH or WR is calculated based on the retardation value, the assumed average refractive index value, and the input film thickness value.
  • Re ( ⁇ ) represents a retardation value in a direction inclined by an angle ⁇ from the normal direction.
  • nx represents the refractive index in the slow axis direction in the plane
  • ny represents the refractive index in the direction perpendicular to nx in the plane
  • nz represents the refractive index in the direction perpendicular to nx and ny.
  • d is the film thickness.
  • Formula (12): Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d
  • nx represents the refractive index in the slow axis direction in the plane
  • ny represents the refractive index in the direction perpendicular to nx in the plane
  • nz represents the refractive index in the direction perpendicular to nx and ny.
  • d is the film thickness.
  • Rth ( ⁇ ) is calculated by the following method.
  • Rth ( ⁇ ) is Re ( ⁇ )
  • the in-plane slow axis (determined by KOBRA 21ADH or WR) is tilt axis (rotary axis) from ⁇ 50 degrees to +50 degrees with respect to the film normal direction.
  • KOBRA 21ADH or WR is measured based on the measured retardation value, the assumed average refractive index, and the input film thickness value. Is calculated.
  • the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer.
  • the average refractive index values of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59).
  • the KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness.
  • Nz (nx ⁇ nz) / (nx ⁇ ny) is further calculated from the calculated nx, ny, and nz.
  • a measurement wavelength is 550 nm.
  • Re (550) is indicated.
  • the angle for example, an angle such as “90 °”
  • the relationship for example, “orthogonal”, “parallel”, “crossing at 45 °”, etc.
  • the range of allowable error is included.
  • it means that the angle is within the range of strict angle ⁇ 10 °, and the error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less.
  • the retardation being substantially 0 means that Re (550) ⁇ 10 nm and Rth (550) ⁇ 10 nm, preferably Re (550) ⁇ 5 nm and Rth (550) ⁇ 5 nm.
  • the method for producing a polarizing plate of the present invention includes forming a cycloolefin polymer-containing layer by directly applying a composition containing a cycloolefin polymer to the surface of the temporary support.
  • a laminate including a temporary support, a cycloolefin polymer-containing layer, and other layers as necessary can be used as a transfer material in the production method of the present invention.
  • the transfer material will be described.
  • the transfer material has a cycloolefin polymer-containing layer directly provided on at least one surface of the temporary support and, if necessary, another layer, and the cycloolefin polymer-containing layer is transferred to another substrate ( It is a material used for transfer onto a film (which usually contains a polarizer).
  • FIG. 1 shows schematic sectional views of some examples of the transfer material of the present invention. The drawing shows an example in which an optically anisotropic layer and / or an acrylic polymer layer is further included in addition to a temporary support and a transfer material having a cycloolefin polymer-containing layer. In addition to the layers shown in the figure, other layers such as an adhesive layer and an alignment layer for aligning liquid crystal molecules may be included.
  • the temporary support may be transparent or opaque and is not particularly limited.
  • the polymer constituting the temporary support include cellulose esters (eg, cellulose acetate such as triacetyl cellulose (TAC), cellulose propionate, cellulose butyrate), polyolefin (eg, norbornene-based polymer), poly (meta ) Acrylic acid esters (eg, polymethyl methacrylate), polycarbonates, polyesters and polysulfones, and norbornene polymers.
  • the transparent support is preferably a transparent and low birefringent material, and from the viewpoint of low birefringence, cellulose ester and norbornene are preferred.
  • the temporary support may be an unstretched film or a stretched film.
  • the stretching may be uniaxial stretching or biaxial stretching.
  • Uniaxial stretching is preferably longitudinal uniaxial stretching using the rotation difference between two or more rolls, or tenter stretching in which both ends of the film are gripped and stretched in the width direction.
  • the film may be stretched in the vertical and horizontal directions.
  • the cycloolefin polymer-containing layer is formed by a method including applying a composition containing a cycloolefin polymer on a temporary support.
  • a composition containing a cycloolefin polymer on a temporary support.
  • the temporary support is directly on the surface of the temporary support or on the temporary support.
  • the meaning of either or both of the surfaces provided with any layer (film) is included.
  • the composition containing a cycloolefin polymer may contain other components such as additives and solvents as necessary.
  • the film thickness of the cycloolefin polymer-containing layer is not particularly limited, and may be, for example, 1 ⁇ m to 100 ⁇ m.
  • the cycloolefin polymer-containing layer can be 25 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 9 ⁇ m or less, 8 ⁇ m or less, etc. by being provided by coating film formation.
  • the cycloolefin polymer-containing layer can be easily peeled off from the temporary support without any defects after forming, a thin film protective film can be easily formed on the polarizing plate using the above transfer material. Can do.
  • the cycloolefin polymer-containing layer after peeling easily maintains a self-supporting property even if it becomes a thin film, it can be adhered to a polarizer or the like after the temporary support is peeled off, and the handleability is also good.
  • a cycloolefin polymer represents a polymer having a cycloolefin structure, and so-called cycloolefin polymer (COP) and cycloolefin copolymer (COC) are both types of cycloolefin polymers.
  • cycloolefin polymers include (1) norbornene polymers, (2) monocyclic cycloolefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, (5) Norbornene-based addition (co) polymers and hydrides of (1) to (5).
  • a ring-opening (co) polymer containing at least one cyclic repeating unit can also be suitably used.
  • Norbornene-based polymer hydrides are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19807, JP-A-2003-115767, or JP-A-2004-309979. As disclosed in each publication of No. 1, etc., it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation.
  • the norbornene-based resin is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250 or Zeonex 280 by Nippon Zeon Co., Ltd. These are commercially available under the trade name, and these can be used.
  • Norbornene-based addition (co) polymers are disclosed in JP-A-10-7732, JP-T 2002-504184, U.S. Published Patent No. 200429129157A1 or WO2004 / 070463A1. It is obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds.
  • Tg glass transition temperatures
  • APL8008T Tg70 ° C
  • APL6013T Tg125 ° C
  • APL6015T Grades such as Tg145 ° C
  • Pellets such as TOPAS 8007, 6013, and 6015 are sold by Polyplastics Co., Ltd. The Appearn 3000 is available from Ferrania.
  • the cycloolefin polymer unit content in the cycloolefin polymer is preferably 5 to 95% by mass.
  • the glass transition temperature (Tg) of the cycloolefin polymer is not limited, but a high-Tg cycloolefin polymer polymer such as 200 to 400 ° C. can also be used.
  • Preferable examples of the cycloolefin polymer include cycloolefin polymers represented by the following general formula (21) or (22).
  • R 1 to R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6, for example 1 to 3) (for example, a chain or cyclic group). Represents an alkyl group, an alkenyl group, or an alkynyl group. l, m, and n represent an integer of 0 to 4, and are typically 1.
  • R 11 to R 12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6, for example 1 to 3) (for example, a chain or cyclic group). Represents an alkyl group, an alkenyl group, or an alkynyl group. o represents an integer of 0 to 4, and is typically 1.
  • a cycloolefin polymer content layer can be formed by apply
  • the composition containing a cycloolefin polymer can be applied by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method, or the like.
  • the same coating method can be used when forming an optically anisotropic layer, an acrylic polymer layer, an alignment layer, and the like described later by coating.
  • the micro-gravure coating method, the wire bar coating method, and the die coating method see US Pat. No.
  • 2,681,294, JP-A-2006-122889 are more preferable, and the die coating method is particularly preferable. Particularly preferred.
  • FIG. 1 shows an example of a coating process that can be used in the manufacturing method of the present invention.
  • the film 12 temporary support or the like
  • the coating apparatus 10 is disposed so as to be opposed to the coating liquid supply unit (hereinafter referred to as a coating head) 14 that applies the coating liquid fed from the coating liquid tank by a pump or the like to the film 12 and the coating head 14.
  • the cylindrical backup roller 15 that supports the film 12 at the time of coating on the outer peripheral surface, and the support column 16 that rotatably supports the rotation shaft of the backup roller 15 via a bearing.
  • the coating head 14 is disposed so as to be opposed to the film 12 in which the tip of the coating head is in close contact with the continuously running film 12.
  • the distance between the coating head 14 and the film 12 is configured to be adjustable.
  • the coating head 14 is fed from a coating solution tank by a pump, and the coating amount for obtaining a required coating film thickness can be controlled by adjusting the coating solution delivery amount of the pump.
  • a metering pump as the pump since the supply flow rate of the coating liquid is stabilized.
  • various pumps such as a gear pump and a roller pump are used.
  • the application process is preferably performed in an environment with good dust-freeness and optimum temperature and humidity.
  • the drying process after coating, the UV irradiation process when forming the optically anisotropic layer, and the rubbing process when forming the alignment film are also performed as a series of processes upstream or downstream of the coating process, and are equally good. It is preferably carried out in an environment of a dust-free degree and an optimum temperature and humidity.
  • the coating process and the like are preferably performed in a clean room, and in particular, the coating apparatus 10 is preferably installed in an environment with a high degree of cleanliness. For this purpose, a mode in which a downflow clean room or a clean bench is used together can be employed.
  • Examples of the coating apparatus 10 include an extrusion type coater, a bar coater (also referred to as “rod coater”, including a Mayer bar coater), a gravure coater (direct gravure coater, gravure kiss coater, etc.), a roll coater (transfer roll). Coaters, reverse roll coaters, etc.), die coaters, fountain coaters, slide hoppers, and the like.
  • a bar coater also referred to as “rod coater”, including a Mayer bar coater
  • a gravure coater direct gravure coater, gravure kiss coater, etc.
  • a roll coater transfer roll.
  • Coaters, reverse roll coaters, etc. die coaters, fountain coaters, slide hoppers, and the like.
  • a drying step for drying the coating film it is preferable to apply a drying step for drying the coating film.
  • a drying apparatus used in the drying process a general drying apparatus can be used without limitation.
  • a convection drying method using hot air a radiation drying method using radiant heat such as infrared rays, or the like can be used.
  • hot air When hot air is used, drying of the coating film is controlled by adjusting the temperature and speed of the hot air.
  • a slit nozzle a nozzle having a slit-like opening shape in the width direction of a belt-like support
  • a punching nozzle a porous flat plate nozzle
  • the solvent used for preparing the coating liquid when forming the cycloolefin polymer-containing layer and the optically anisotropic layer, acrylic polymer layer, alignment layer, etc. described later by coating is an organic solvent or water. Or a mixed solvent thereof is preferably used.
  • organic solvents examples include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane), alkyl alcohols (eg, , Methanol, ethanol, propanol). Two or more kinds of solvents may be mixed and used. Among the above, alkyl halides, esters, ketones and mixed solvents thereof are preferable.
  • alkyl halides, esters, ketones and mixed solvents thereof are prefer
  • the transfer material may include an optically anisotropic layer.
  • the polarizing plate manufactured by the manufacturing method of this invention may contain the optically anisotropic layer.
  • the temporary support can be peeled off during transfer by using a transfer material having a cycloolefin polymer-containing layer.
  • favorable peelability is obtained by the cycloolefin polymer-containing layer, it is possible to use various temporary supports as compared with the case where the cycloolefin polymer-containing layer is not included. Therefore, in order to inspect the transfer material with a surface inspection machine, it is possible to select a temporary support that is less likely to cause rainbow unevenness or the like.
  • the optically anisotropic layer is a layer having optical properties that are not isotropic in that there is at least one incident direction in which retardation is not substantially zero when the retardation is measured.
  • the optically anisotropic layer used in the present invention is formed by irradiating a polymerizable composition containing a liquid crystal compound with light to polymerize the liquid crystal compound.
  • the polymerizable composition includes a liquid crystal compound having at least one polymerizable group, as long as the liquid crystal compound is polymerized by the polymerizable group by light irradiation.
  • the polymerizable composition is preferably applied on a temporary support. In particular, it is preferable that the film as the temporary support is applied directly to the surface subjected to the rubbing treatment or directly to the alignment layer.
  • the coating layer is further dried at room temperature or the like, or heated (for example, heating at 50 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C.), whereby the liquid crystal compound molecules in the layer can be aligned. It is only necessary to form an optically anisotropic layer by irradiating it with light and fixing it by polymerization.
  • the film thickness of the optically anisotropic layer is 10 ⁇ m or less, less than 8 ⁇ m, 7 ⁇ m or less, 6 ⁇ m or less, 5 ⁇ m or less, 4 ⁇ m or less, 3 ⁇ m or less, 2 ⁇ m or less, 1.9 ⁇ m or less, 1.8 ⁇ m or less, 1.7 ⁇ m or less, 1 .6 ⁇ m or less, 1.5 ⁇ m or less, 1.4 ⁇ m or less, 1.3 ⁇ m or less, 1.2 ⁇ m or less, 1.1 ⁇ m or less, or 1 ⁇ m or less, 0.2 ⁇ m or more, 0.3 ⁇ m or more, 0.4 ⁇ m or more, 0 It may be 0.5 ⁇ m or more, 0.6 ⁇ m or more, 0.7 ⁇ m or more, 0.8 ⁇ m or more, or 0.9 ⁇ m or more. It is also preferable that the optically anisotropic layer is transparent (for example, the light transmittance is 80% or more).
  • the polarizing plate of the present invention may contain two or more optically anisotropic layers. Two or more optically anisotropic layers may be in direct contact with each other in the normal direction, or other layers such as an alignment layer may be sandwiched therebetween.
  • the polymerizable compositions forming two or more layers may be the same or different.
  • optically anisotropic layers it may be a combination of layers formed from a composition containing a rod-like liquid crystal compound, or a combination of layers formed from a composition containing a discotic liquid crystal compound, A combination of a layer formed from a composition containing a rod-like liquid crystal compound and a layer formed from a composition containing a discotic liquid crystal compound may be used.
  • the transfer material includes two or more optically anisotropic layers
  • the previously prepared optically anisotropic layer may function as an alignment layer of the optically anisotropic layer formed later. .
  • the previously produced optically anisotropic layer may be rubbed.
  • the oxidative surface treatment is preferably a corona discharge treatment or a plasma treatment.
  • the total thickness of the optically anisotropic layers is preferably the above film thickness.
  • the two optically anisotropic layers may have a function as a ⁇ / 4 retardation plate, for example.
  • the ⁇ / 4 retardation plate functions as a circularly polarizing plate in combination with a polarizer (linear polarizer).
  • Retardation plates have a great many applications, and are already used for reflective LCDs, transflective LCDs, brightness enhancement films, organic EL display devices, touch panels, and the like.
  • an organic EL (organic electroluminescence) element has a structure in which layers having different refractive indexes are laminated or a structure using a metal electrode, so that external light is reflected at the interface of each layer, causing problems such as a decrease in contrast and reflection. May occur. Therefore, conventionally, a circularly polarizing plate composed of a phase difference plate and a polarizing film has been used for an organic EL display device, an LCD display device, and the like in order to suppress adverse effects due to external light reflection.
  • liquid crystal compound examples include a rod-like liquid crystal compound and a disk-like liquid crystal compound.
  • rod-like liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
  • high-molecular liquid crystalline molecules can also be used.
  • the rod-like liquid crystal compound is more preferably fixed in orientation by polymerization, and examples of the polymerizable rod-like liquid crystal compound include Makromol. Chem. 190, 2255 (1989), Advanced Materials, 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648, 5,770,107, WO 95/22586, 95/24455, 97/97 No. 0600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and Japanese Patent Application No. 2001-64627 These compounds can be used.
  • the polymerizable rod-like liquid crystal compound is preferably a polymerizable rod-like liquid crystal compound represented by the following general formula (1).
  • Q 1 and Q 2 are each independently a polymerizable group.
  • the polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization.
  • the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.
  • preferred polymerizable groups include acryl groups and methacryl groups.
  • both Q 1 and Q 2 in the general formula (1) are an acryl group or a methacryl group.
  • L 1 and L 4 are each independently a divalent linking group.
  • L 1 and L 4 each independently comprises —O—, —S—, —CO—, —NR—, —C ⁇ N—, a divalent chain group, a divalent cyclic group, and combinations thereof.
  • a divalent linking group selected from the group is preferred.
  • R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.
  • R is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom.
  • bivalent coupling group which consists of a combination is shown below.
  • the left side is coupled to Q (Q 1 or Q 2 ), and the right side is coupled to Cy (Cy 1 or Cy 3 ).
  • L-1 —CO—O—divalent chain group —O— L-2: —CO—O—divalent chain group —O—CO— L-3: —CO—O—divalent chain group —O—CO—O— L-4: —CO—O—divalent chain group—O—divalent cyclic group— L-5: —CO—O—divalent chain group —O—divalent cyclic group —CO—O— L-6: —CO—O—divalent chain group —O—divalent cyclic group —O—CO— L-7: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group— L-8: —CO—O—divalent chain group—O—divalent cyclic group—divalent chain group —CO—O— L-9: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group—O—CO— L-10: —CO
  • the divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group.
  • An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred.
  • the alkylene group may have a branch.
  • the alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
  • the alkylene part of the substituted alkylene group is the same as the above alkylene group.
  • the substituent examples include a halogen atom.
  • the alkenylene group may have a branch.
  • the alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
  • the alkylene part of the substituted alkylene group is the same as the above alkylene group.
  • Examples of the substituent include a halogen atom.
  • the alkynylene group may have a branch.
  • the alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
  • the alkynylene part of the substituted alkynylene group is the same as the above alkynylene group.
  • Examples of the substituent include a halogen atom.
  • Specific examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.
  • the definition and examples of the divalent cyclic group are the same as those of Cy 1 , Cy 2 and Cy 3 described later.
  • L 2 and L 3 are each independently a single bond or a divalent linking group.
  • L 2 and L 3 each independently comprises —O—, —S—, —CO—, —NR—, —C ⁇ N—, a divalent chain group, a divalent cyclic group, and combinations thereof. It is preferably a divalent linking group or a single bond selected from the group.
  • R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom.
  • the divalent chain group and the divalent cyclic group have the same definitions as L 1 and L 4 .
  • Preferred divalent linking groups as L 2 or L 3 include —COO—, —OCO—, —OCOO—, —OCONR—, —COS—, —SCO—, —CONR—, —NRCO—, —CH 2. CH 2 —, —C ⁇ C—COO—, —C ⁇ N—, —C ⁇ N—N ⁇ C—, and the like.
  • n is 0, 1, 2, or 3.
  • two L 3 may be the same or different, and two Cy 2 may be the same or different.
  • n is preferably 1 or 2, and more preferably 1.
  • Cy 1 , Cy 2 and Cy 3 are each independently a divalent cyclic group.
  • the ring contained in the cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.
  • the ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
  • the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring.
  • Examples of the aromatic ring include a benzene ring and a naphthalene ring.
  • Examples of the aliphatic ring include a cyclohexane ring.
  • Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
  • As the cyclic group having a benzene ring 1,4-phenylene is preferable.
  • As the cyclic group having a naphthalene ring naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable.
  • the cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene.
  • cyclic group having a pyridine ring pyridine-2,5-diyl is preferable.
  • the cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.
  • the cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms.
  • Examples of the polymerizable rod-like liquid crystal compound represented by the general formula (1) are shown below, but examples of the polymerizable rod-like liquid crystal compound are not limited to these.
  • M 1 and M 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, a cyano group, a halogen, —SCN, — CF 3 , a nitro group, or Q 1 is represented, but at least one of M 1 and M 2 represents a group other than Q 1 .
  • Q 1, L 1, L 2, L 3, L 4, Cy 1, Cy 2, Cy 3 and n have the same meanings as the group represented by the general formula (1).
  • P and q are 0 or 1.
  • M 1 and M 2 are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a cyano group, more preferably , An alkyl group having 1 to 4 carbon atoms, or a phenyl group, and p and q are preferably 0.
  • the preferable mixing ratio (mass ratio) of the compound represented by the general formula (2) in the mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the compound represented by the general formula (2) Is 0.1% to 40%, more preferably 1% to 30%, and still more preferably 5% to 20%.
  • the discotic liquid crystal compounds are disclosed in various literatures (C. Destrade et al., Mol. Cryst. Liq. Cryst., Vol. 71, page 111 (1981); edited by The Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal). Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985): J. Zhang et al., J. Chem. Am. Chem. Soc., Vol. 116, page 2655 (1994)).
  • the polymerization of the discotic liquid crystal compound is described in JP-A-8-27284.
  • the photocurable discotic liquid crystal compound is preferably a compound represented by the following formula (3).
  • D (-LP) n (In the general formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.) Preferred specific examples of the discotic core (D), the divalent linking group (L), and the polymerizable group (P) in the formula (3) are (D1) to (D1) described in JP-A-2001-4837, respectively. (D15), (L1) to (L25), (P1) to (P18), and the contents described in the publication can be preferably used. As the discotic liquid crystal compound, it is also preferable to use a compound represented by the general formula (DI) described in JP-A-2007-2220.
  • the liquid crystal compound is 80% by mass or more, 90% by mass or more, or 95% by mass or more, and 99.99% by mass or less, 99.98% with respect to the solid content mass (the mass excluding the solvent) of the polymerizable composition. It should just be contained in the mass% or less and 99.97 mass% or less.
  • the compound containing an acrylic group or a methacryl group is 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, and 99.99% by mass or less, 99.98% by mass or less. 99.97% by mass or less.
  • the liquid crystal compound may be fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, and twist alignment.
  • horizontal alignment means that in the case of a rod-like liquid crystal, the molecular long axis and the horizontal plane of the transparent support are parallel, and in the case of a disc-like liquid crystal, the disc surface of the core of the disc-like liquid crystal compound.
  • the horizontal plane of the transparent support is parallel, but it is not required to be strictly parallel, and in this specification, an inclination angle with the horizontal plane is less than 10 degrees.
  • the optically anisotropic layer used in the present invention preferably contains a rod-shaped liquid crystal compound fixed in a horizontally aligned state.
  • the polymerization reaction of the liquid crystal compound may be a photopolymerization reaction.
  • the photopolymerization reaction may be either radical polymerization or cationic polymerization, but radical polymerization is preferred.
  • radical photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon-substituted aromatics.
  • An acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (described in US Pat. Nos.
  • the amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.
  • Light irradiation for the polymerization of the liquid crystal compound is preferably performed using ultraviolet rays.
  • the irradiation energy is preferably 10 mJ / cm 2 to 10 J / cm 2 , and more preferably 25 to 1000 mJ / cm 2 .
  • the illuminance is preferably 10 to 2000 mW / cm 2 , more preferably 20 to 1500 mW / cm 2 , and still more preferably 40 to 1000 mW / cm 2 .
  • the irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm.
  • light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions.
  • the compounds represented by the general formulas (1) to (3) and the general formula (4) described in paragraphs “0098” to “0105” of JP2009-69793A are described.
  • the molecule of the liquid crystal compound can be substantially horizontally aligned by containing at least one of a fluorine-containing homopolymer or copolymer using the monomer (1).
  • the inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.
  • the addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass, based on the mass of the liquid crystal compound.
  • the compounds represented by the general formulas (1) to (4) described in paragraphs “0098” to “0105” of JP-A-2009-69793 may be used alone or in combination of two or more. You may use together.
  • the polymerizable composition containing a liquid crystal compound may contain a pyridinium compound represented by the formula (I) described in JP-A-2006-113500.
  • the pyridinium compound can function as an alignment layer interface-side vertical alignment agent.
  • the molecules of the discotic liquid crystalline compound can be aligned substantially vertically in the vicinity of the alignment layer.
  • the polymerizable composition containing a liquid crystal compound may contain a boronic acid compound represented by the general formula (I) described in JP2013-05201A.
  • the polymerizable composition containing a liquid crystal compound may contain other necessary additives, but preferably does not contain a so-called chiral agent.
  • the optically anisotropic layer may be formed from a layer of a polymerizable composition applied to the surface of the alignment layer.
  • the alignment layer is provided on the surface of a temporary support (stretched film) or an undercoat layer coated on the temporary support.
  • the alignment layer functions to define the alignment of the liquid crystal compound in the polymerizable composition provided thereon.
  • the orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer.
  • Preferable examples of the alignment layer include phenol resin, epoxy resin, fluororesin, polyethylene resin, and polypropylene resin.
  • an organic material containing a hydrophilic group such as a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group is preferable.
  • a hydrophilic group such as a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • an acrylic resin, a polyvinyl alcohol resin, a polyester resin, an amino resin, or the like can be used.
  • a layer subjected to a rubbing treatment of an organic compound preferably a polymer
  • a photo-alignment layer that exhibits liquid crystal orientation by polarized irradiation represented by azobenzene polymer or polyvinyl cinnamate an oblique deposition layer of an inorganic compound, and a micro
  • a cumulative film formed by Langmuir-Blodgett method LB film
  • LB film Langmuir-Blodgett method
  • the alignment layer preferably contains polyvinyl alcohol, and it is particularly preferable that the alignment layer can be cross-linked with at least one of the upper and lower alignment layers.
  • a photo-alignment layer and a microgroove are preferable.
  • the photo-alignment layer is particularly preferably a material that exhibits orientation by dimerization, such as polyvinyl cinnamate, and the microgroove is particularly preferably an embossing treatment of a master roll prepared in advance by machining or laser processing.
  • the rubbing treatment applied to the layer such as the lower layer of the optically anisotropic layer such as the alignment layer can be generally performed by rubbing the surface of the film mainly composed of a polymer with paper or cloth in a certain direction.
  • a general method of rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).
  • the rubbing density (L) is quantified by the following formula (A).
  • Formula (A) L Nl (1 + 2 ⁇ rn / 60v)
  • N is the number of rubbing
  • l is the contact length of the rubbing roller
  • r is the radius of the roller
  • n is the number of rotations (rpm) of the roller
  • v is the stage moving speed (second speed).
  • the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can reverse this.
  • the description in Japanese Patent No. 4052558 can also be referred to as conditions for the rubbing process.
  • the transfer material may include an acrylic polymer layer.
  • the polarizing plate manufactured by the manufacturing method of this invention may contain the acrylic polymer layer.
  • the material for forming the acrylic polymer layer is generally less expensive than the material for forming the cycloolefin polymer-containing layer, but as a transfer material for providing the acrylic polymer layer on the film containing the polarizer, it is directly applied to the surface of the temporary support. Even if the present inventors tried to produce a transfer material having a configuration provided with an acrylic polymer layer, it was difficult to peel the acrylic polymer layer without any defects.
  • a transparent and low birefringent protective film having a film thickness required for the structure can be formed.
  • the transfer material may include an optically anisotropic layer together with the acrylic polymer layer.
  • the layer order of the acrylic polymer layer and the optically anisotropic layer is not particularly limited.
  • a cycloolefin polymer-containing layer, an acrylic polymer layer, and an optically anisotropic layer may be included in this order, and the acrylic polymer layer may also serve as an alignment layer for forming the optically anisotropic layer.
  • the acrylic polymer layer a layer formed by applying a polymerizable composition containing a (meth) acrylate monomer to the surface of a lower layer such as a cycloolefin polymer-containing layer or an optically anisotropic layer, and curing the applied layer. It may be a layer formed by applying an acrylic polymer-containing composition and drying this coating layer, or may be a layer in which a separately prepared acrylic polymer film is provided by adhesion or the like. Good.
  • the acrylic polymer layer is preferably a transparent material having low birefringence. What is optically isotropic may be used. Optically isotropic means that the in-plane retardation (Re (550)) has an absolute value of 10 nm or less and the thickness direction retardation (Rth) has an absolute value of 10 nm or less.
  • the (meth) acrylate in the polymerizable composition containing (meth) acrylate for forming the acrylic polymer layer is not particularly limited as long as it is a compound containing an acryloyl group or a methacryloyl group.
  • the compound may have one acryloyl group or methacryloyl group, or two or more (for example, 2, 3, 4, etc.).
  • the molecular weight of the (meth) acrylate may be about 5000 or less, preferably 3000 or less, more preferably 2000 or less, and particularly preferably 1000 or less.
  • (meth) acrylate includes (meth) acrylic acid and various esters thereof (such as methyl (meth) acrylate).
  • a polymerizable compound other than (meth) acrylate may be contained.
  • Acrylic polymers include, for example, polymethyl (meth) acrylate, copolymers of (meth) acrylic acid and various esters thereof, copolymers of styrene and (meth) acrylic acid or various (meth) acrylic esters, vinyltoluene and ( Mention may be made of (meth) acrylic acid or copolymers of various (meth) acrylic acid esters.
  • Preferred examples include copolymers of methyl (meth) acrylate and (meth) acrylic acid, copolymers of allyl (meth) acrylate and (meth) acrylic acid, benzyl (meth) acrylate and (meth) acrylic acid, and others. And multi-component copolymers with other monomers. These polymers may be used alone or in combination of two or more.
  • the acrylic polymer layer may be either one obtained by thermal polymerization of (meth) acrylate and other monomers, or one obtained by photopolymerization, but one obtained by photopolymerization is particularly preferred.
  • the photopolymerization reaction should just be performed in the coating layer in which the polymeric composition containing (meth) acrylate is directly apply
  • the light irradiation for the photopolymerization reaction may be performed under the same conditions as the light irradiation for the polymerization of the liquid crystal compound described above, and the light irradiation for the polymerization of the liquid crystal compound simultaneously polymerizes the (meth) acrylate. May be.
  • a thermal polymerization initiator or a photopolymerization initiator is appropriately used according to the method.
  • photopolymerization initiators vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, US Pat. No. 2,722,512
  • a polymer having a high Tg may be used as the polymer in the acrylic polymer layer.
  • the Tg is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher.
  • a polar group such as a hydroxyl group, a carboxylic acid group, or an amino group may be introduced.
  • high Tg polymers examples include poly (methyl) acrylate, alkyl (meth) acrylate reactants such as polyethyl (meth) acrylate, copolymers of alkyl (meth) acrylate and (meth) acrylic acid, 2-hydroxyethyl Reaction products of hydroxyl group-containing (meth) acrylates such as (meth) acrylate and 2-hydroxypropyl (meth) acrylate, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates and succinic anhydride, acid anhydrides such as phthalic anhydride And a copolymer of a half ester which is a reaction product with the product.
  • alkyl (meth) acrylate reactants such as polyethyl (meth) acrylate, copolymers of alkyl (meth) acrylate and (meth) acrylic acid
  • 2-hydroxyethyl Reaction products of hydroxyl group-containing (meth) acrylates
  • a layer obtained by polymerizing a layer containing at least one bifunctional or higher polymerizable monomer and a polymerizable polymer by light irradiation or heat may be used.
  • reactive groups include (meth) acryl groups, vinyl groups, allyl groups, epoxy groups, oxetanyl groups, vinyl ether groups, and the like.
  • polymerizable polymers examples include glycidyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol 1,3-di (meth) acrylate-containing acrylate reactants, polymerizability Examples thereof include a copolymer of a group-containing acrylate and (meth) acrylic acid, and a multi-component copolymer of a polymerizable group-containing acrylate and another monomer.
  • the thickness of the acrylic polymer layer is 60 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less, or 15 ⁇ m or less, or 2 ⁇ m or more, 3 ⁇ m or more, 3.5 ⁇ m or more, 4 ⁇ m or more, 4.5 ⁇ m or more, or 5 ⁇ m.
  • the above is preferable.
  • the transfer material may contain other functional layers such as a low moisture permeability layer, a protective layer, an antistatic layer, a hard coat layer, and an adhesive layer.
  • the temporary support of the transfer material described above may be peeled off, and the layer or laminate after peeling off the temporary support may be laminated on a film containing a polarizer.
  • the transfer material may be laminated on a film containing a polarizer, and then the temporary support may be peeled off.
  • the cycloolefin polymer-containing layer may be on the film-side surface containing the polarizer, or the surface of the layer other than the cycloolefin polymer-containing layer may contain the polarizer. It may be on the side surface.
  • the adhesive layer may be a layer containing an adhesive or a pressure-sensitive adhesive. That is, the transfer material and the film containing the polarizer need only be adhered or adhered to each other by an adhesive or an adhesive.
  • the adhesive is not particularly limited, but is an epoxy compound curable adhesive that does not contain an aromatic ring in the molecule, as disclosed in JP-A No. 2004-245925, and is disclosed in JP-A-2008-174667.
  • An active energy ray-curable adhesive comprising a photopolymerization initiator having a molar extinction coefficient of 400 or more at a wavelength of 450 nm and an ultraviolet curable compound as essential components, and a (meth) acrylic compound described in JP-A-2008-174667 (A) a (meth) acrylic compound having 2 or more (meth) acryloyl groups in the molecule and (b) a hydroxyl group in the molecule, and having only a polymerizable double bond (Meth) acrylic compound and (c) phenolethylene oxide modified acrylate or nonylphenol ethylene oxide modified acrylic Such as an active energy ray-curable adhesive containing a chromatography bets and the like.
  • the film containing a polarizer may consist of only a polarizer, and may contain other layers, such as a protective film, other than a polarizer.
  • the film containing a polarizer may contain the polarizer on the outermost surface, and may have other layers on both sides of the polarizer.
  • the surface of the polarizer on the outermost surface may be adhered to the transfer material (or the laminate in which the temporary support is peeled off from the transfer material), or may be adhered to the surface of another layer.
  • the polarizer examples include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer.
  • the iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol 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 reference can be made to, for example, the description in JP-A-2009-237376.
  • the film thickness of a polarizer should just be 50 micrometers or less, 30 micrometers or less are preferable and 20 micrometers or less are more preferable.
  • the polarizing plate may contain a protective film.
  • a protective film may be disposed on the surface opposite to the surface of the polarizer on which the cycloolefin polymer layer or the laminate including this layer is provided by the transfer material.
  • a cellulose acylate polymer film, an acrylic polymer film, or a cycloolefin polymer film can be used as the protective film.
  • the cellulose acylate polymer reference can be made to the description of the cellulose acylate resin in JP2011-237474A.
  • cycloolefin-based polymer film a film formed from the same material as that described for the cycloolefin polymer-containing layer may be used, and JP 2009-175222 A and JP 2009-237376 A may be used. Reference can also be made to the description.
  • the film thickness of a protective film should just be 30 micrometers or less, 20 micrometers or less are preferable and 10 micrometers or less are more preferable.
  • the polarizing plate may include a hard coat layer.
  • the hard coat layer may be included as the outermost layer, and is preferably included in the outermost layer on the optically anisotropic layer side as viewed from the polarizer.
  • the hard coat layer refers to a layer that, when formed, increases the pencil hardness of the transparent support.
  • the pencil hardness (JIS K5400) after laminating the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.
  • the thickness of the hard coat layer is preferably 0.4 to 35 ⁇ m, more preferably 1 to 30 ⁇ m, and most preferably 1.5 to 20 ⁇ m.
  • JP 2012-103689 A For the specific composition, reference can be made to the description in JP 2012-103689 A.
  • the process shown in FIG. 2 is used for coating of the coating liquid when forming the cycloolefin polymer-containing layer, the acrylic polymer layer, the optically anisotropic layer, etc., and an extrusion type coater is used as the coating apparatus. Using. After the coating process, the film was directly subjected to the drying process. A convection drying method using a slit nozzle was used as a drying device, and the drying time was adjusted by controlling the conveyance speed of the film 12 (FIG. 2).
  • ⁇ Preparation of temporary support 1 (cellulose acetate film)> The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
  • Composition of cellulose acetate solution ⁇ Cellulose acetate having an acetylation degree of 60.7 to 61.1% 100 parts by mass of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass of methylene chloride (first solvent) 336 parts by mass Methanol (second solvent) 29 parts by mass 1-butanol (third solvent) 11 parts by mass ⁇ ⁇
  • additive (A) 16 parts by mass of the following additive (A), 92 parts by mass of methylene chloride and 8 parts by mass of methanol were added and stirred while heating to prepare an additive (A) solution.
  • the dope was prepared by mixing 474 parts by mass of the cellulose acetate solution with 25 parts by mass of the additive (A) and stirring sufficiently.
  • the addition amount of the additive (A) was 6.0 parts by mass with respect to 100 parts by mass of cellulose acetate.
  • the obtained dope was cast using a band stretching machine. After the film surface temperature on the band reaches 40 ° C., the film is dried with warm air of 70 ° C. for 1 minute, and the film from the band is dried with 140 ° C. drying air for 10 minutes, and the residual solvent amount is 0.3% by mass.
  • a cellulose acetate film (temporary support 1) was prepared.
  • the obtained long temporary support 1 had a width of 1490 mm and a thickness of 80 ⁇ m.
  • the in-plane retardation (Re) was 8 nm and the thickness direction retardation (Rth) was 78 nm.
  • ⁇ Production of film T3 (temporary support / cycloolefin polymer-containing layer)> (Formation of cycloolefin polymer-containing layer)
  • a cycloolefin polymer coating solution 70 cc / m 2 having the following composition was continuously coated.
  • the conveyance speed of the temporary support 1 was 30 m / min, and it was dried with warm air at 80 ° C. for 60 seconds.
  • a convection drying method using a slit nozzle was used as a drying device, and the drying time was adjusted by controlling the conveyance speed of the film 12 (FIG. 2).
  • the film thickness after drying was 7 ⁇ m.
  • Cycloolefin polymer 2 (Arton, manufactured by JSR) 10 parts by mass Cyclohexane 100 parts by mass ⁇ -
  • ultraviolet rays were irradiated with an integrated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp in an atmosphere with an oxygen concentration of 300 ppm to fix the orientation of the liquid crystal compound.
  • the thickness of the optically anisotropic layer was 1.9 ⁇ m.
  • the average inclination angle of the long axis of the rod-like liquid crystal compound with respect to the film surface was 90 °, and it was confirmed that the liquid crystal compound was aligned perpendicular to the film surface.
  • composition of coating solution for optically anisotropic layer 1 Polymerizable liquid crystal compound (LC-1-1) 80 parts by mass Polymerizable liquid crystal compound (LC-2) 20 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass orientation controller FP2 1 part by mass Alignment aid FP3 0.4 parts by mass Methyl ethyl ketone 193 parts by mass Cyclohexanone 50 parts by mass ⁇ -
  • the optically anisotropic layer 1 was prepared in the same manner as the optically anisotropic layer 1 except that the coating liquid for the optically anisotropic layer 1 was changed to the coating liquid for the optically anisotropic layer 2 described below.
  • the thickness of the optically anisotropic layer was 1.9 ⁇ m.
  • the average inclination angle of the long axis of the rod-like liquid crystal compound with respect to the film surface was 0 °, and it was confirmed that the liquid crystal compound was aligned horizontally with respect to the film surface.
  • composition of coating solution for optically anisotropic layer 2 Polymerizable liquid crystal compound (LC-1-1) 80 parts by mass Polymerizable liquid crystal compound (LC-2) 20 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass polymer (A) 0.6 Part by mass Fluoropolymer (FP1) 0.3 part by mass Methyl ethyl ketone 183 parts by mass Cyclohexanone 40 parts by mass ⁇ ⁇
  • the acrylic polymer layer forming coating solution 8.8 cc / m 2 was continuously applied to the surface of the optically anisotropic layer 2.
  • the film was conveyed at a speed of 30 m / min and dried with warm air at 40 ° C. for 60 seconds.
  • an air-cooled metal halide lamp manufactured by Eye Graphics Co., Ltd.
  • ultraviolet rays having an illuminance of 400 mW / cm 2 and an irradiation amount of 300 mJ / cm 2 were irradiated.
  • the coating layer was cured to form an acrylic polymer layer having a film thickness of 2.6 ⁇ m.
  • the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer, whereby the polarizing plate 1 was obtained.
  • the temporary support 1 could be easily peeled off.
  • the thickness of the polarizing plate 1 was 27 ⁇ m.
  • a polarizing plate 2 was produced in the same manner as the polarizing plate 1 except that the film T1 was replaced with the film T2. After bonding to the polarizer, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 2.
  • the thickness of the polarizing plate 2 was 22 ⁇ m.
  • a polarizing plate 3 was produced in the same manner as the polarizing plate 1 except that the film T1 was replaced with the film T3. After bonding to the polarizer, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be peeled off easily) to obtain the polarizing plate 3.
  • the thickness of the polarizing plate 3 was 27 ⁇ m.
  • a commercially available acrylic adhesive (UV-3300, manufactured by Toagosei Co., Ltd.) was used to attach the surface of the acrylic polymer layer of the film T2 to one side of the polarizing film. After the lamination, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 4. The thickness of the polarizing plate 4 was 29.6 ⁇ m.
  • a commercially available acrylic adhesive (UV-3300, manufactured by Toagosei Co., Ltd.) was used to bond the surface of the acrylic polymer layer of the film T4 to one side of the polarizing film. After the lamination, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 6. The thickness of the polarizing plate 6 was 31.5 ⁇ m.
  • ⁇ Preparation of Polarizing Plates 7 to 12 Affixing the polarizer after peeling the temporary support> (Peeling from temporary support)
  • the films T1 to T6 obtained above were peeled from the temporary support 1 to obtain films T7 to T12.
  • the films T7 to T12 were bonded to the polarizer so that the surfaces of the layers other than the cycloolefin polymer-containing layer were surfaces on the polarizer side.
  • the polarizers 7 to 12 were obtained by bonding the films T7 to T12 in the same manner as the polarizing plates 1 to 6.
  • polarizing plate 7 27 ⁇ m
  • polarizing plate 8 22 ⁇ m
  • polarizing plate 9 27 ⁇ m
  • polarizing plate 10 29.6 ⁇ m
  • polarizing plate 11 31.5 ⁇ m
  • polarizing plate 12 31.5 ⁇ m.
  • the surface inspection of the obtained films T1 to T6 and T13 was performed.
  • FLAT PANEL FP-901-2 manufactured by GUNMA) USHIO
  • the polarizing plate was placed in crossed Nicols and visually inspected.
  • the film T13 showed remarkable rainbow unevenness and could not be inspected, whereas the films T1 to T6 could be inspected without rainbow unevenness.
  • cycloolefin polymer resin sheet T15 A commercially available cycloolefin polymer film “ZEONOR ZF14” (manufactured by Nippon Zeon Co., Ltd.) is stretched at the stretching temperature (Tg is the glass transition temperature of the cyclic olefin resin) and the stretching ratio shown in Table 1 below, and the cyclic olefin resin sheet T15 was obtained.
  • Tg is the glass transition temperature of the cyclic olefin resin
  • Table 1 the stretching ratio shown in Table 1 below

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  • General Physics & Mathematics (AREA)
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Abstract

The present invention provides a method for producing a polarizing plate, which comprises (1) a process for forming a cycloolefin polymer-containing layer by applying a composition that contains a cycloolefin polymer onto a temporary supporting body, (2) a process for laminating the cycloolefin polymer-containing layer and a film that contains a polarizer, and (3) a process for separating the temporary supporting body. A polarizing plate having a small thickness can be produced by this production method.

Description

偏光板および偏光板の製造方法ならびに偏光板の製造のための転写材料および転写材料Polarizing plate, method for producing polarizing plate, transfer material for producing polarizing plate, and transfer material
　本発明は偏光板の製造方法、および偏光板に関する。本発明はまた、偏光板の製造方法に用いられる転写材料、および転写材料の製造方法に関する。 The present invention relates to a polarizing plate manufacturing method and a polarizing plate. The present invention also relates to a transfer material used in a method for manufacturing a polarizing plate, and a method for manufacturing the transfer material.
　スマートフォンやタブレットＰＣ等の市場の拡大により、ディスプレイにもますます薄型化が求められている。この流れの中で、透明で低複屈折性の光学フィルムとして従来から用いられているセルロースアシレート系ポリマーフィルムに加えて、アクリル系ポリマーフィルム、シクロオレフィン系ポリマーフィルムなどの様々なフィルムを偏光板の保護フィルムとして利用することが試みられている（例えば、特許文献１）。これらのポリマーフィルムとしては、通常、ポリマー溶液または溶融ポリマーを用いて流延法または押出法により製膜したフィルムが用いられている。例えば、特許文献２の段落００９１、特許文献３の段落００５４には、シクロオレフィンポリマーフィルムがこれらの方法で製膜されることに関する記載がある。 As the market for smartphones and tablet PCs expands, displays are increasingly required to be thinner. In this trend, in addition to the cellulose acylate polymer film conventionally used as a transparent and low birefringence optical film, various films such as an acrylic polymer film and a cycloolefin polymer film are polarizing plates. Attempts have been made to use it as a protective film (for example, Patent Document 1). As these polymer films, films formed by a casting method or an extrusion method using a polymer solution or a molten polymer are usually used. For example, paragraph 0091 of Patent Document 2 and paragraph 0054 of Patent Document 3 include a description regarding that a cycloolefin polymer film is formed by these methods.
特開２００９－１７５２２２号公報JP 2009-175222 A 特開２００９－２３７３７６号公報JP 2009-237376 A 特開２０１０－１９１３８９号公報JP 2010-191389 A
　本発明は膜厚が小さい偏光板の提供を課題とする。本発明は、特に低複屈折性の薄膜ポリマーフィルムを保護フィルムとして有する偏光板の製造方法の提供を課題とする。 An object of the present invention is to provide a polarizing plate having a small film thickness. This invention makes it a subject to provide the manufacturing method of the polarizing plate which has especially a low birefringent thin film polymer film as a protective film.
　本発明者らは、上記課題の下、より薄い保護フィルムの作製を試みた。しかし、セルロースアシレート系ポリマーフィルムやシクロオレフィン系ポリマーフィルムとして、それぞれについて市販されているフィルムよりも薄いフィルムを従来の製膜法により得ることは困難であった。例えば超低速で流延法や押出法のいずれかの従来の製膜法により、薄膜フィルムを得ることができても、その後の乾燥や延伸などの工程で搬送する時に薄膜フィルムが破断してしまい、最終的にフィルム形状を維持することが困難であった。しかし、その後の検討の結果、仮支持体上に塗布製膜することにより、シクロオレフィン系ポリマーフィルムが薄膜で形成可能であり、かつ、仮支持体から欠陥なく剥離可能であることを見出し、その後、さらに検討を重ね、本発明を完成させた。すなわち、本発明は下記の［１］～［１４］を提供するものである。 The present inventors tried to produce a thinner protective film under the above-mentioned problems. However, it has been difficult to obtain a film thinner than a commercially available film as a cellulose acylate polymer film or a cycloolefin polymer film by a conventional film forming method. For example, even if a thin film can be obtained by a conventional film forming method such as a casting method or an extrusion method at an ultra-low speed, the thin film is broken when transported in a subsequent process such as drying or stretching. Finally, it was difficult to maintain the film shape. However, as a result of subsequent studies, it was found that a cycloolefin polymer film can be formed as a thin film by coating and forming on a temporary support and can be peeled off from the temporary support without defects. The present invention was completed by further study. That is, the present invention provides the following [1] to [14].
［１］偏光板の製造方法であって、下記（１）～（３）を含む製造方法：
（１）仮支持体上にシクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成すること、
（２）上記シクロオレフィンポリマー含有層と偏光子を含むフィルムとを積層すること、
（３）上記仮支持体を剥離すること。
［２］上記（１）において、仮支持体の表面に直接、シクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成する、［１］に記載の製造方法。
［３］上記（１）～（３）をこの順で含み、
上記（２）において、上記仮支持体と上記シクロオレフィンポリマー含有層とを含む転写材料および偏光子を含むフィルムが積層され、
上記（２）において形成された積層体から上記仮支持体を剥離することを含む、［１］または［２］に記載の製造方法。 [1] A method for producing a polarizing plate, comprising the following (1) to (3):
(1) applying a composition containing a cycloolefin polymer on a temporary support to form a cycloolefin polymer-containing layer;
(2) laminating the cycloolefin polymer-containing layer and a film containing a polarizer;
(3) Peeling off the temporary support.
[2] The production method according to [1], wherein in (1), the cycloolefin polymer-containing layer is formed by coating a composition containing a cycloolefin polymer directly on the surface of the temporary support.
[3] The above (1) to (3) are included in this order,
In the above (2), a film including a transfer material and a polarizer including the temporary support and the cycloolefin polymer-containing layer is laminated,
The production method according to [1] or [2], comprising peeling the temporary support from the laminate formed in (2).
［４］上記（１）のシクロオレフィンポリマー含有層の形成が上記シクロオレフィンポリマー含有層の膜厚が２０μｍ以下となるように行われる［１］～［３］のいずれか一項に記載の製造方法。
［５］上記（１）のシクロオレフィンポリマー含有層の形成が上記シクロオレフィンポリマー含有層の膜厚が１５μｍ以下となるように行われる［１］～［３］のいずれか一項に記載の製造方法。 [4] The production according to any one of [1] to [3], wherein the cycloolefin polymer-containing layer (1) is formed so that the thickness of the cycloolefin polymer-containing layer is 20 μm or less. Method.
[5] The production according to any one of [1] to [3], wherein the cycloolefin polymer-containing layer (1) is formed so that the thickness of the cycloolefin polymer-containing layer is 15 μm or less. Method.
［６］上記（２）の積層が上記シクロオレフィンポリマー含有層と上記の偏光子を含むフィルムとが接着層を介して直接接着するように行われる［１］～［５］のいずれか一項に記載の製造方法。
［７］上記積層が上記シクロオレフィンポリマー含有層と上記偏光子とが上記接着層を介して直接接着するように行われる［６］に記載の製造方法。
［８］上記（１）の後かつ上記（２）の前に、光学異方性層およびアクリルポリマー層からなる群から選択される1層以上の層を上記シクロオレフィンポリマー含有層上に形成することを含む［１］～［５］のいずれか一項に記載の製造方法。
［９］［１］～［８］のいずれか一項に記載の製造方法により得られる偏光板であって、膜厚が２０μｍ以下のシクロオレフィンポリマー含有層と偏光子とを含む偏光板。
［１０］偏光子および上記偏光子と接着層を介して直接接着されている膜厚が２０μｍ以下のシクロオレフィンポリマー含有層を含む偏光板。 [6] The stacking of (2) is performed so that the cycloolefin polymer-containing layer and the film containing the polarizer are directly bonded via an adhesive layer. The manufacturing method as described in.
[7] The production method according to [6], wherein the lamination is performed so that the cycloolefin polymer-containing layer and the polarizer are directly bonded via the adhesive layer.
[8] One or more layers selected from the group consisting of an optically anisotropic layer and an acrylic polymer layer are formed on the cycloolefin polymer-containing layer after (1) and before (2). The production method according to any one of [1] to [5].
[9] A polarizing plate obtained by the production method according to any one of [1] to [8], comprising a cycloolefin polymer-containing layer having a thickness of 20 μm or less and a polarizer.
[10] A polarizing plate comprising a polarizer and a cycloolefin polymer-containing layer having a thickness of 20 μm or less that is directly bonded to the polarizer via an adhesive layer.
［１１］偏光板製造のための転写材料の製造方法であって、
仮支持体上にシクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成することを含む製造方法。
［１２］上記シクロオレフィンポリマー含有層の形成が上記シクロオレフィンポリマー含有層の膜厚が２０μｍ以下となるように行われる［１１］に記載の製造方法。
［１３］上記シクロオレフィンポリマー含有層の形成が上記シクロオレフィンポリマー含有層の膜厚が１５μｍ以下となるように行われる［１１］または［１２］に記載の製造方法。
［１４］［１１］～［１３］のいずれか一項に記載の製造方法により得られる偏光板製造のための転写材料であって、膜厚が２０μｍ以下のシクロオレフィンポリマー含有層と仮支持体とを含む転写材料。 [11] A method for producing a transfer material for producing a polarizing plate,
The manufacturing method including apply | coating the composition containing a cycloolefin polymer on a temporary support body, and forming a cycloolefin polymer content layer.
[12] The production method according to [11], wherein the cycloolefin polymer-containing layer is formed so that the thickness of the cycloolefin polymer-containing layer is 20 μm or less.
[13] The production method according to [11] or [12], wherein the cycloolefin polymer-containing layer is formed so that the thickness of the cycloolefin polymer-containing layer is 15 μm or less.
[14] A transfer material for producing a polarizing plate obtained by the production method according to any one of [11] to [13], a cycloolefin polymer-containing layer having a thickness of 20 μm or less, and a temporary support And transfer material.
　本発明により、偏光板の製造方法が提供される。本発明により、低複屈折性の薄膜ポリマーフィルムを保護フィルムとして有する偏光板を容易に製造することができる。 The present invention provides a method for producing a polarizing plate. According to the present invention, a polarizing plate having a low-birefringence thin film polymer film as a protective film can be easily produced.
本発明の製造方法に用いられる転写材料の層構成の例を示す図である。It is a figure which shows the example of the layer structure of the transfer material used for the manufacturing method of this invention. 塗布工程の一例を説明する図である。It is a figure explaining an example of an application process.
　以下、本発明を詳細に説明する。
　なお、本明細書において「～」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。本明細書において「偏光板」とは、特に断らない限り、長尺の偏光板及び液晶装置に組み込まれる大きさなどの必要な大きさに裁断された（本明細書において、「裁断」には「打ち抜き」及び「切り出し」等も含むものとする）偏光板の両者を含む意味で用いられる。また、本明細書では、「偏光子」（「偏光膜」という場合もある）及び「偏光板」を区別して用いるが、「偏光板」は「偏光子」の少なくとも片面にフィルムを有する積層体を意味するものとする。
　また、本明細書において、「（メタ）アクリレート」との記載は、「アクリレート及びメタクリレートのいずれか一方または双方」の意味を表す。「（メタ）アクリル酸」等も同様である。 Hereinafter, the present invention will be described in detail.
In the present specification, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In this specification, unless otherwise specified, the “polarizing plate” is cut into a necessary size such as a size to be incorporated in a long polarizing plate and a liquid crystal device (in this specification, “cutting” The term “including punching” and “cutting out” is used to include both polarizing plates. In this specification, “polarizer” (sometimes referred to as “polarizing film”) and “polarizing plate” are used separately, but “polarizing plate” is a laminate having a film on at least one side of “polarizer”. Means.
Moreover, in this specification, description with "(meth) acrylate" represents the meaning of "any one or both of an acrylate and a methacrylate." The same applies to “(meth) acrylic acid” and the like.
　本明細書において、Ｒｅ（λ）、Ｒｔｈ（λ）は各々、波長λにおける面内のレターデーション及び厚さ方向のレターデーションを表す。Ｒｅ（λ）はＫＯＢＲＡ　２１ＡＤＨ又はＷＲ（王子計測機器（株）製）において波長λｎｍの光をフィルム法線方向に入射させて測定される。測定波長λｎｍの選択にあたっては、波長選択フィルタをマニュアルで交換するか、又は測定値をプログラム等で変換して測定することができる。 In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.
　測定されるフィルムが１軸又は２軸の屈折率楕円体で表されるものである場合には、以下の方法によりＲｔｈ（λ）は算出される。
　Ｒｔｈ（λ）はＲｅ（λ）を、面内の遅相軸（ＫＯＢＲＡ　２１ＡＤＨ又はＷＲにより判断される）を傾斜軸（回転軸）として（遅相軸がない場合にはフィルム面内の任意の方向を回転軸とする）のフィルム法線方向に対して法線方向から片側５０度まで１０度ステップで各々その傾斜した方向から波長λｎｍの光を入射させて全部で６点測定し、その測定されたレターデーション値と平均屈折率の仮定値及び入力された膜厚値を基にＫＯＢＲＡ　２１ＡＤＨ又はＷＲが算出する。 When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) (if there is no slow axis, any film surface in-plane The direction of the axis of rotation is the film normal direction), and from the normal direction to 50 degrees on one side, the light of wavelength λ nm is incident from each inclined direction in steps of 10 degrees to measure a total of 6 points. KOBRA 21ADH or WR is calculated based on the retardation value, the assumed average refractive index value, and the input film thickness value.
　上記において、法線方向から面内の遅相軸を回転軸として、ある傾斜角度にレターデーションの値がゼロとなる方向をもつフィルムの場合には、その傾斜角度より大きい傾斜角度でのレターデーション値はその符号を負に変更した後、ＫＯＢＲＡ　２１ＡＤＨ又はＷＲが算出する。
　なお、遅相軸を傾斜軸（回転軸）として（遅相軸がない場合にはフィルム面内の任意の方向を回転軸とする）、任意の傾斜した２方向からレターデーション値を測定し、その値と平均屈折率の仮定値及び入力された膜厚値を基に、以下の式（１１）及び式（１２）よりＲｔｈを算出することもできる。
　式（１１） In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (when there is no slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (11) and (12).
Formula (11)
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　上記のＲｅ（θ）は法線方向から角度θ傾斜した方向におけるレターデーション値をあらわす。
　式（１１）におけるｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表す。ｄは膜厚である。 The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In formula (11), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. . d is the film thickness.
　式（１２）：Ｒｔｈ＝｛（ｎｘ＋ｎｙ）／２－ｎｚ｝×ｄ
　式（１２）におけるｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表す。ｄは膜厚である。 Formula (12): Rth = {(nx + ny) / 2−nz} × d
In formula (12), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. . d is the film thickness.
　測定されるフィルムが１軸や２軸の屈折率楕円体で表現できないもの、いわゆる光学軸（ｏｐｔｉｃ　ａｘｉｓ）がないフィルムの場合には、以下の方法によりＲｔｈ（λ）は算出される。
　Ｒｔｈ（λ）はＲｅ（λ）を、面内の遅相軸（ＫＯＢＲＡ　２１ＡＤＨ又はＷＲにより判断される）を傾斜軸（回転軸）としてフィルム法線方向に対して－５０度から＋５０度まで１０度ステップで各々その傾斜した方向から波長λｎｍの光を入射させて１１点測定し、その測定されたレターデーション値と平均屈折率の仮定値及び入力された膜厚値を基にＫＯＢＲＡ　２１ＡＤＨ又はＷＲが算出する。
　上記の測定において、平均屈折率の仮定値は　ポリマーハンドブック（ＪＯＨＮ　ＷＩＬＥＹ＆ＳＯＮＳ，ＩＮＣ）、各種光学フィルムのカタログの値を使用することができる。平均屈折率の値が既知でないものについてはアッベ屈折計で測定することができる。主な光学フィルムの平均屈折率の値を以下に例示する：　セルロースアシレート（１．４８）、シクロオレフィンポリマー（１．５２）、ポリカーボネート（１．５９）、ポリメチルメタクリレート（１．４９）、ポリスチレン（１．５９）である。これら平均屈折率の仮定値と膜厚を入力することで、ＫＯＢＲＡ　２１ＡＤＨ又はＷＲはｎｘ、ｎｙ、ｎｚを算出する。この算出されたｎｘ，ｎｙ，ｎｚよりＮｚ＝（ｎｘ－ｎｚ）／（ｎｘ－ｎｙ）が更に算出される。 In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is tilt axis (rotary axis) from −50 degrees to +50 degrees with respect to the film normal direction. In 11 degree steps, light having a wavelength of λ nm is incident from each inclined direction and measured at 11 points, and KOBRA 21ADH or WR is measured based on the measured retardation value, the assumed average refractive index, and the input film thickness value. Is calculated.
In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.
　本明細書では、測定波長について特に付記がない場合は、測定波長は５５０ｎｍである。例えば、単にＲｅと記載されているときは、Ｒｅ（５５０）を示す。
　また、本明細書において、角度（例えば「９０°」等の角度）、およびその関係（例えば「直交」、「平行」、および「４５°で交差」等）については、本発明が属する技術分野において許容される誤差の範囲を含むものとする。例えば、厳密な角度±１０°未満の範囲内であることを意味し、厳密な角度との誤差は、５°以下であることが好ましく、３°以下であることがより好ましい。さらに、レターデーションが実質的に０とは、Ｒｅ（５５０）≦１０ｎｍかつＲｔｈ（５５０）≦１０ｎｍ、好ましくはＲｅ（５５０）≦５ｎｍ以下かつＲｔｈ（５５０）≦５ｎｍであることを意味する。 In this specification, when there is no special mention about a measurement wavelength, a measurement wavelength is 550 nm. For example, when it is simply described as Re, Re (550) is indicated.
Further, in the present specification, regarding the angle (for example, an angle such as “90 °”) and the relationship (for example, “orthogonal”, “parallel”, “crossing at 45 °”, etc.), the technical field to which the present invention belongs. The range of allowable error is included. For example, it means that the angle is within the range of strict angle ± 10 °, and the error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less. Further, the retardation being substantially 0 means that Re (550) ≦ 10 nm and Rth (550) ≦ 10 nm, preferably Re (550) ≦ 5 nm and Rth (550) ≦ 5 nm.
　本発明の偏光板の製造方法は、仮支持体の表面に直接、シクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成することを含む。仮支持体、シクロオレフィンポリマー含有層、および必要に応じて他の層を含む積層体は、本発明の製造方法において、転写材料として用いることができる。以下、転写材料について、説明する。 The method for producing a polarizing plate of the present invention includes forming a cycloolefin polymer-containing layer by directly applying a composition containing a cycloolefin polymer to the surface of the temporary support. A laminate including a temporary support, a cycloolefin polymer-containing layer, and other layers as necessary can be used as a transfer material in the production method of the present invention. Hereinafter, the transfer material will be described.
［転写材料］
　本明細書において、転写材料は、仮支持体の少なくとも一方の表面に直接設けられたシクロオレフィンポリマー含有層および必要に応じて他の層を有し、シクロオレフィンポリマー含有層を、他の基板（通常は偏光子を含むフィルム）上に転写するのに用いられる材料である。図１に本発明の転写材料のいくつかの例の概略断面図を示す。図には、仮支持体およびシクロオレフィンポリマー含有層を有する転写材料の他に、さらに光学異方性層および／またはアクリルポリマー層を含む例が示されている。図に示す層以外に、接着層、液晶性分子の配向のための配向層などの他の層を含んでいてもよい。 [Transfer material]
In the present specification, the transfer material has a cycloolefin polymer-containing layer directly provided on at least one surface of the temporary support and, if necessary, another layer, and the cycloolefin polymer-containing layer is transferred to another substrate ( It is a material used for transfer onto a film (which usually contains a polarizer). FIG. 1 shows schematic sectional views of some examples of the transfer material of the present invention. The drawing shows an example in which an optically anisotropic layer and / or an acrylic polymer layer is further included in addition to a temporary support and a transfer material having a cycloolefin polymer-containing layer. In addition to the layers shown in the figure, other layers such as an adhesive layer and an alignment layer for aligning liquid crystal molecules may be included.
［仮支持体］
　仮支持体は、透明でも不透明でもよく特に限定はない。仮支持体を構成するポリマーの例には、セルロースエステル（例、トリアセチルセルロース（ＴＡＣ）などのセルロースアセテート、セルロースプロピオネート、セルロースブチレート）、ポリオレフィン（例、ノルボルネン系ポリマー）、ポリ（メタ）アクリル酸エステル（例、ポリメチルメタクリレート）、ポリカーボネート、ポリエステルおよびポリスルホン、ノルボルネン系ポリマーが含まれる。製造工程において光学特性を検査する目的には、透明支持体は透明で低複屈折の材料が好ましく、低複屈折性の観点からはセルロースエステルおよびノルボルネン系が好ましい。市販のノルボルネン系ポリマーとしては、アートン（ＪＳＲ（株）製）、ゼオネックス、ゼオノア（以上、日本ゼオン（株）製）などを用いることができる。また安価であるため、ポリカーボネートやポリエチレンテレフタレート（ＰＥＴ）等も好ましく用いられる。 [Temporary support]
The temporary support may be transparent or opaque and is not particularly limited. Examples of the polymer constituting the temporary support include cellulose esters (eg, cellulose acetate such as triacetyl cellulose (TAC), cellulose propionate, cellulose butyrate), polyolefin (eg, norbornene-based polymer), poly (meta ) Acrylic acid esters (eg, polymethyl methacrylate), polycarbonates, polyesters and polysulfones, and norbornene polymers. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and from the viewpoint of low birefringence, cellulose ester and norbornene are preferred. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. In addition, since it is inexpensive, polycarbonate, polyethylene terephthalate (PET), and the like are also preferably used.
　また仮支持体は無延伸フィルムでも延伸フィルムでもよい。延伸フィルムを用いる場合、延伸は一軸延伸であっても二軸延伸であってもよい。一軸延伸は２つ以上のロールの回転差を利用した縦一軸延伸、またはフィルムの両端を把持して幅方向に延伸するテンター延伸が好ましい。さらに、フィルムを縦横方向に延伸したものであってもよい。 The temporary support may be an unstretched film or a stretched film. When using a stretched film, the stretching may be uniaxial stretching or biaxial stretching. Uniaxial stretching is preferably longitudinal uniaxial stretching using the rotation difference between two or more rolls, or tenter stretching in which both ends of the film are gripped and stretched in the width direction. Furthermore, the film may be stretched in the vertical and horizontal directions.
［シクロオレフィンポリマー含有層］
　本発明の製造方法において、シクロオレフィンポリマー含有層は仮支持体上に、シクロオレフィンポリマーを含む組成物を塗布することを含む方法により形成される。なお、本明細書において、「仮支持体上」等、何等かの層「上」という場合には、仮支持体であれば、仮支持体の直接の表面、または、仮支持体の上に何らかの層（膜）を設けた表面のいずれか、または両方の意味が含まれる。
　シクロオレフィンポリマーを含む組成物は、必要に応じて添加剤や溶媒等の他の成分を含んでいてもよい。 [Cycloolefin polymer-containing layer]
In the production method of the present invention, the cycloolefin polymer-containing layer is formed by a method including applying a composition containing a cycloolefin polymer on a temporary support. In this specification, when referring to any layer “on”, such as “on the temporary support”, the temporary support is directly on the surface of the temporary support or on the temporary support. The meaning of either or both of the surfaces provided with any layer (film) is included.
The composition containing a cycloolefin polymer may contain other components such as additives and solvents as necessary.
　シクロオレフィンポリマー含有層の膜厚は特に限定されず、例えば１μｍ～１００μｍであればよい。本発明の方法においては、塗布製膜で設けられることにより、シクロオレフィンポリマー含有層は、２５μｍ以下、２０μｍ以下、１５μｍ以下、１０μｍ以下、９μｍ以下、８μｍ以下等であることができる。そして、シクロオレフィンポリマー含有層は形成後、仮支持体から、欠陥等なく、容易に剥離することができるため、上記の転写材料を用いて、偏光板に薄膜の保護フィルムを容易に形成することができる。また、剥離後のシクロオレフィンポリマー含有層は薄膜になっても自己支持性を維持しやすいため、仮支持体の剥離後に偏光子等に接着させることも可能であり取扱い性もよい。 The film thickness of the cycloolefin polymer-containing layer is not particularly limited, and may be, for example, 1 μm to 100 μm. In the method of the present invention, the cycloolefin polymer-containing layer can be 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 9 μm or less, 8 μm or less, etc. by being provided by coating film formation. And, since the cycloolefin polymer-containing layer can be easily peeled off from the temporary support without any defects after forming, a thin film protective film can be easily formed on the polarizing plate using the above transfer material. Can do. In addition, since the cycloolefin polymer-containing layer after peeling easily maintains a self-supporting property even if it becomes a thin film, it can be adhered to a polarizer or the like after the temporary support is peeled off, and the handleability is also good.
［シクロオレフィンポリマー］
　本明細書において、シクロオレフィンポリマーとは、シクロオレフィン構造を有するポリマーを表し、いわゆるシクロオレフィンポリマー（ＣＯＰ）およびシクロオレフィンコポリマー（ＣＯＣ）は、いずれもシクロオレフィンポリマーの一種である。
　シクロオレフィンポリマーの例としては、（１）ノルボルネン系重合体、（２）単環のシクロオレフィンの重合体、（３）環状共役ジエンの重合体、（４）ビニル脂環式炭化水素重合体、（５）ノルボルネン系付加（共）重合体、及び（１）～（５）の水素化物などがあげられる。環状繰り返し単位を少なくとも１種含む開環（共）重合体も好適に使用することができる。 [Cycloolefin polymer]
In this specification, a cycloolefin polymer represents a polymer having a cycloolefin structure, and so-called cycloolefin polymer (COP) and cycloolefin copolymer (COC) are both types of cycloolefin polymers.
Examples of cycloolefin polymers include (1) norbornene polymers, (2) monocyclic cycloolefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, (5) Norbornene-based addition (co) polymers and hydrides of (1) to (5). A ring-opening (co) polymer containing at least one cyclic repeating unit can also be suitably used.
　ノルボルネン系重合体水素化物は、特開平１－２４０５１７号、特開平７－１９６７３６号、特開昭６０－２６０２４号、特開昭６２－１９８０１号、特開２００３－1１５９７６７号あるいは特開２００４－３０９９７９号の各公報等に開示されているように、多環状不飽和化合物を付加重合あるいはメタセシス開環重合したのち水素添加することにより作られる製造することができる。
　ノルボルネン系樹脂は、ＪＳＲ（株）からアートン（Ａｒｔｏｎ）ＧあるいはアートンＦという商品名で発売されており、また日本ゼオン（株）からゼオノア（Ｚｅｏｎｏｒ）ＺＦ１４、ＺＦ１６、ゼオネックス（Ｚｅｏｎｅｘ）２５０あるいはゼオネックス２８０という商品名で市販されており、これらを使用することができる。 Norbornene-based polymer hydrides are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19807, JP-A-2003-115767, or JP-A-2004-309979. As disclosed in each publication of No. 1, etc., it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation.
The norbornene-based resin is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250 or Zeonex 280 by Nippon Zeon Co., Ltd. These are commercially available under the trade name, and these can be used.
　ノルボルネン系付加（共）重合体は、特開平１０－７７３２号公報、特表２００２－５０４１８４号公報、米国公開特許２００４２２９１５７Ａ１号あるいはＷＯ２００４／０７０４６３Ａ１号等に開示されている。ノルボルネン系多環状不飽和化合物同士を付加重合することによって得られる。また、必要に応じ、ノルボルネン系多環状不飽和化合物と、エチレン、プロピレン、ブテン；ブタジエン、イソプレンのような共役ジエン；エチリデンノルボルネンのような非共役ジエン；アクリロニトリル、アクリル酸、メタアクリル酸、無水マレイン酸、アクリル酸エステル、メタクリル酸エステル、マレイミド、酢酸ビニル、塩化ビニルなどの線状ジエン化合物とを付加重合することもできる。中でもエチレンとの共重合体であることが好ましい。このノルボルネン系付加（共）重合体は、三井化学（株）よりアペルの商品名で発売されており、ガラス転移温度（Ｔｇ）の異なる例えばＡＰＬ８００８Ｔ（Ｔｇ７０℃）、ＡＰＬ６０１３Ｔ（Ｔｇ１２５℃）あるいはＡＰＬ６０１５Ｔ（Ｔｇ１４５℃）などのグレードがある。ポリプラスチック（株）よりＴＯＰＡＳ８００７、同６０１３、同６０１５などのペレットが発売されている。Ｆｅｒｒａｎｉａ社からはＡｐｐｅａｒ３０００が発売されている。 Norbornene-based addition (co) polymers are disclosed in JP-A-10-7732, JP-T 2002-504184, U.S. Published Patent No. 200429129157A1 or WO2004 / 070463A1. It is obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, norbornene-based polycyclic unsaturated compounds and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; nonconjugated dienes such as ethylidene norbornene; acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride It is also possible to carry out addition polymerization with linear diene compounds such as acid, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate and vinyl chloride. Among these, a copolymer with ethylene is preferable. This norbornene-based addition (co) polymer is marketed by Mitsui Chemicals, Inc. under the name of Apel, and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C) or APL6015T ( Grades such as Tg145 ° C). Pellets such as TOPAS 8007, 6013, and 6015 are sold by Polyplastics Co., Ltd. The Appearn 3000 is available from Ferrania.
　シクロオレフィンポリマー中、シクロオレフィン重合単位の含有量は５～９５質量％が好ましい。また、シクロオレフィンポリマーのガラス転移温度（Ｔｇ）に制限はないが、例えば２００～４００℃というような高いＴｇのシクロオレフィンポリマーポリマーも用いることができる。
　シクロオレフィンポリマーとして好ましい例としては、以下の一般式（２１）、または（２２）で表されるシクロオレフィンポリマーなどがあげられる。 The cycloolefin polymer unit content in the cycloolefin polymer is preferably 5 to 95% by mass. Further, the glass transition temperature (Tg) of the cycloolefin polymer is not limited, but a high-Tg cycloolefin polymer polymer such as 200 to 400 ° C. can also be used.
Preferable examples of the cycloolefin polymer include cycloolefin polymers represented by the following general formula (21) or (22).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（２１）中、Ｒ1～Ｒ3は、それぞれ独立に、水素原子または炭素原子数１～１０（好ましくは１～６、例えば１～３）の炭化水素基（例えば、鎖状または環状の、アルキル基、アルケニル基、またはアルキニル基）を表す。ｌ、ｍ、nは０～４の整数を表し、典型的には１である。
一般式（２２）中、Ｒ11～Ｒ12は、それぞれ独立に、水素原子または炭素原子数１～１０（好ましくは１～６、例えば１～３）の炭化水素基（例えば、鎖状または環状の、アルキル基、アルケニル基、またはアルキニル基）を表す。ｏは０～４の整数を表し、典型的には１である。 In the general formula (21), R 1 to R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6, for example 1 to 3) (for example, a chain or cyclic group). Represents an alkyl group, an alkenyl group, or an alkynyl group. l, m, and n represent an integer of 0 to 4, and are typically 1.
In the general formula (22), R 11 to R 12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6, for example 1 to 3) (for example, a chain or cyclic group). Represents an alkyl group, an alkenyl group, or an alkynyl group. o represents an integer of 0 to 4, and is typically 1.
［塗布方法］
　シクロオレフィンポリマー含有層はシクロオレフィンポリマーを含む組成物を仮支持体上に塗布し、さらに塗布層を加熱、乾燥することによって形成できる。
　シクロオレフィンポリマーを含む組成物の塗布は、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、ダイコート法等により行うことができる。後述の光学異方性層、アクリルポリマー層、配向層等を塗布により形成する際も同様の塗布方法を用いることができる。
　シクロオレフィンポリマー含有層の形成には特に、このうち、マイクログラビアコート法、ワイヤーバーコート法、ダイコート法（米国特許２６８１２９４号明細書、特開２００６－１２２８８９号公報参照）がより好ましく、ダイコート法が特に好ましい。
　シクロオレフィンポリマー含有層の形成を、塗布方法を用いて行うことで溶液流延法や溶融流延法では達成できない薄膜を形成することができる。 [Coating method]
A cycloolefin polymer content layer can be formed by apply | coating the composition containing a cycloolefin polymer on a temporary support body, and also heating and drying an application layer.
The composition containing a cycloolefin polymer can be applied by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method, or the like. The same coating method can be used when forming an optically anisotropic layer, an acrylic polymer layer, an alignment layer, and the like described later by coating.
Of these, the micro-gravure coating method, the wire bar coating method, and the die coating method (see US Pat. No. 2,681,294, JP-A-2006-122889) are more preferable, and the die coating method is particularly preferable. Particularly preferred.
By forming the cycloolefin polymer-containing layer using a coating method, a thin film that cannot be achieved by the solution casting method or the melt casting method can be formed.
（塗布工程）
　図１に本発明の製造方法で用いることができる塗布工程の一例を表す図を示す。
　送り出し機または前工程から送り出されてきたフィルム１２（仮支持体等）は塗布装置１０において塗布工程に付される。塗布装置１０は、塗布液タンクからポンプ等により送液された塗布液をフィルム１２に塗布する塗布液供給部（以下、塗布ヘッドと呼ぶ。）１４と、塗布ヘッド１４に対向して配置され設けられ、塗布時のフィルム１２を外周面で支持する円筒状のバックアップローラ１５と、バックアップローラ１５の回転軸を、軸受けを介して回転自在に保持する支柱１６により構成されている。塗布ヘッド１４は、塗布ヘッド先端が連続走行するフィルム１２と近接され非接触の状態で対向配置される。塗布ヘッド１４とフィルム１２の間隔は調整できるよう構成されている。塗布ヘッド１４は塗布液タンクからポンプにより送液され、ポンプの塗布液送り出し量を調整することにより、必要な塗布膜厚を得る塗布量を制御することができる。図示しないが、ポンプとしては、塗布液の供給流量が安定化することより、定量ポンプを使用することが好ましい。定量ポンプとしては、たとえば、ギアポンプ、ローラポンプ等、各種のポンプが使用される。 (Coating process)
FIG. 1 shows an example of a coating process that can be used in the manufacturing method of the present invention.
The film 12 (temporary support or the like) fed from the feeder or the previous process is applied to the coating process in the coating apparatus 10. The coating apparatus 10 is disposed so as to be opposed to the coating liquid supply unit (hereinafter referred to as a coating head) 14 that applies the coating liquid fed from the coating liquid tank by a pump or the like to the film 12 and the coating head 14. The cylindrical backup roller 15 that supports the film 12 at the time of coating on the outer peripheral surface, and the support column 16 that rotatably supports the rotation shaft of the backup roller 15 via a bearing. The coating head 14 is disposed so as to be opposed to the film 12 in which the tip of the coating head is in close contact with the continuously running film 12. The distance between the coating head 14 and the film 12 is configured to be adjustable. The coating head 14 is fed from a coating solution tank by a pump, and the coating amount for obtaining a required coating film thickness can be controlled by adjusting the coating solution delivery amount of the pump. Although not shown, it is preferable to use a metering pump as the pump since the supply flow rate of the coating liquid is stabilized. As the metering pump, for example, various pumps such as a gear pump and a roller pump are used.
　　上記塗布工程は、良好な無塵度及び最適な温湿度の環境下で実施されることが好ましい。なお、塗布後の乾燥工程、光学異方性層形成の際の紫外線照射工程、および配向膜作製の際のラビング工程なども、塗布工程の上流または下流で一連の工程として行われ、同様に良好な無塵度及び最適な温湿度の環境下で実施されることが好ましい。上記塗布工程等は、クリーンルーム内で行なわれることが好ましく、特に、塗布装置１０は、クリーン度の高い環境下に設置されることが好ましい。このためには、ダウンフローのクリーンルーム又はクリーンベンチを併用する形態が採用できる。 The application process is preferably performed in an environment with good dust-freeness and optimum temperature and humidity. The drying process after coating, the UV irradiation process when forming the optically anisotropic layer, and the rubbing process when forming the alignment film are also performed as a series of processes upstream or downstream of the coating process, and are equally good. It is preferably carried out in an environment of a dust-free degree and an optimum temperature and humidity. The coating process and the like are preferably performed in a clean room, and in particular, the coating apparatus 10 is preferably installed in an environment with a high degree of cleanliness. For this purpose, a mode in which a downflow clean room or a clean bench is used together can be employed.
　塗布装置１０としては、例えば、エクストルージョン型のコータ、バーコータ（「ロッドコータ」とも称され、メイヤーバーコータをも含む）、グラビアコータ（ダイレクトグラビアコータ、グラビアキスコータ等）、ロールコータ（トランスファロールコータ、リバースロールコータ等）、ダイコータ、ファウンテンコータ、スライドホッパ等を用いることができる。 Examples of the coating apparatus 10 include an extrusion type coater, a bar coater (also referred to as “rod coater”, including a Mayer bar coater), a gravure coater (direct gravure coater, gravure kiss coater, etc.), a roll coater (transfer roll). Coaters, reverse roll coaters, etc.), die coaters, fountain coaters, slide hoppers, and the like.
　塗布工程の後は塗布膜を乾燥させる乾燥工程に付すことが好ましい。乾燥工程に用いる乾燥装置としては、一般的な乾燥装置を限定なく使用することもできる。例えば、熱風による対流乾燥方式、赤外線などの輻射熱による輻射乾燥方式などを用いることができる。熱風を用いる場合には、熱風の温度及び風速を調整して塗膜の乾燥を制御する。また熱風の当て方として、スリットノズル（帯状の支持体の幅方向にスリット状の開口形状を持つノズル）やパンチングノズル（多孔式の平板ノズル）など用いることができる。 After the coating step, it is preferable to apply a drying step for drying the coating film. As a drying apparatus used in the drying process, a general drying apparatus can be used without limitation. For example, a convection drying method using hot air, a radiation drying method using radiant heat such as infrared rays, or the like can be used. When hot air is used, drying of the coating film is controlled by adjusting the temperature and speed of the hot air. Moreover, as a method of applying hot air, a slit nozzle (a nozzle having a slit-like opening shape in the width direction of a belt-like support), a punching nozzle (a porous flat plate nozzle), or the like can be used.
[溶媒]
　本発明の方法において、シクロオレフィンポリマー含有層、および後述の光学異方性層、アクリルポリマー層、配向層等を塗布により形成する際の塗布液の調製に使用する溶媒としては、有機溶媒もしくは水、またはこれらの混合溶媒が好ましく用いられる。有機溶媒の例としては、アミド（例、Ｎ，Ｎ－ジメチルホルムアミド）、スルホキシド（例、ジメチルスルホキシド）、ヘテロ環化合物（例、ピリジン）、炭化水素（例、ベンゼン、ヘキサン）、アルキルハライド（例、クロロホルム、ジクロロメタン）、エステル（例、酢酸メチル、酢酸ブチル）、ケトン（例、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン）、エーテル（例、テトラヒドロフラン、１，２－ジメトキシエタン）、アルキルアルコール（例、メタノール、エタノール、プロパノール）が挙げられる。また、二種類以上の溶媒を混合して使用してもよい。上記の中で、アルキルハライド、エステル、ケトンおよびそれらの混合溶媒が好ましい。 [solvent]
In the method of the present invention, the solvent used for preparing the coating liquid when forming the cycloolefin polymer-containing layer and the optically anisotropic layer, acrylic polymer layer, alignment layer, etc. described later by coating is an organic solvent or water. Or a mixed solvent thereof is preferably used. Examples of organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane), alkyl alcohols (eg, , Methanol, ethanol, propanol). Two or more kinds of solvents may be mixed and used. Among the above, alkyl halides, esters, ketones and mixed solvents thereof are preferable.
［光学異方性層］
　転写材料は光学異方性層を含んでいてもよい。また、本発明の製造方法により製造される偏光板は光学異方性層を含んでいてもよい。
　転写材料を用いて光学異方性層を偏光板に設ける際に、シクロオレフィンポリマー含有層を有する転写材料とすることにより、転写の際の仮支持体の剥離が良好となる。また、シクロオレフィンポリマー含有層により良好な剥離性が得られるため、シクロオレフィンポリマー含有層を含めない場合よりも、様々な仮支持体を使用することが可能である。そのため、転写材料を面検機で検査するために、虹ムラ等が生じにくい仮支持体を選択することが可能になる。 [Optically anisotropic layer]
The transfer material may include an optically anisotropic layer. Moreover, the polarizing plate manufactured by the manufacturing method of this invention may contain the optically anisotropic layer.
When the optically anisotropic layer is provided on the polarizing plate using the transfer material, the temporary support can be peeled off during transfer by using a transfer material having a cycloolefin polymer-containing layer. Moreover, since favorable peelability is obtained by the cycloolefin polymer-containing layer, it is possible to use various temporary supports as compared with the case where the cycloolefin polymer-containing layer is not included. Therefore, in order to inspect the transfer material with a surface inspection machine, it is possible to select a temporary support that is less likely to cause rainbow unevenness or the like.
　光学異方性層は、レターデーションを測定したときにレターデーションが実質的に０でない入射方向が一つでもある、即ち等方性でない光学特性を有する層である。本発明で用いられる光学異方性層は、液晶化合物を含む重合性組成物に光照射して液晶化合物を重合させることにより形成されたものである。重合性組成物は、少なくとも１つの重合性基を有する液晶化合物を含んでおり、光照射により液晶化合物が重合性基により重合するものであればよい。重合性組成物は仮支持体上に塗布されることが好ましい。特に、仮支持体であるフィルムをラビング処理した面に直接、または配向層に直接、塗布されることが好ましい。塗布層をさらに、室温等により乾燥させる、または加熱（例えば　５０℃～１５０℃、好ましくは８０℃～１２０℃の加熱）することにより、層中の液晶化合物分子を配向させることができる。これを光照射して重合固定化することにより、光学異方性層が形成されていればよい。 The optically anisotropic layer is a layer having optical properties that are not isotropic in that there is at least one incident direction in which retardation is not substantially zero when the retardation is measured. The optically anisotropic layer used in the present invention is formed by irradiating a polymerizable composition containing a liquid crystal compound with light to polymerize the liquid crystal compound. The polymerizable composition includes a liquid crystal compound having at least one polymerizable group, as long as the liquid crystal compound is polymerized by the polymerizable group by light irradiation. The polymerizable composition is preferably applied on a temporary support. In particular, it is preferable that the film as the temporary support is applied directly to the surface subjected to the rubbing treatment or directly to the alignment layer. The coating layer is further dried at room temperature or the like, or heated (for example, heating at 50 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C.), whereby the liquid crystal compound molecules in the layer can be aligned. It is only necessary to form an optically anisotropic layer by irradiating it with light and fixing it by polymerization.
　光学異方性層の膜厚は、１０μｍ以下、８μｍ未満、７μｍ以下、６μｍ以下、５μｍ以下、４μｍ以下、３μｍ以下、２μｍ以下、１．９μｍ以下、１．８μｍ以下、１．７μｍ以下、１．６μｍ以下、１．５μｍ以下、１．４μｍ以下、１．３μｍ以下、１．２μｍ以下、１．１μｍ以下または１μｍ以下、また、０．２μｍ以上、０．３μｍ以上、０．４μｍ以上、０．５μｍ以上、０．６μｍ以上、０．７μｍ以上、０．８μｍ以上、０．９μｍ以上であればよい。光学異方性層は透明である（例えば、光透過率が８０％以上）ことも好ましい。 The film thickness of the optically anisotropic layer is 10 μm or less, less than 8 μm, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, 1.9 μm or less, 1.8 μm or less, 1.7 μm or less, 1 .6 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, or 1 μm or less, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0 It may be 0.5 μm or more, 0.6 μm or more, 0.7 μm or more, 0.8 μm or more, or 0.9 μm or more. It is also preferable that the optically anisotropic layer is transparent (for example, the light transmittance is 80% or more).
［２層以上の光学異方性層］
　本発明の偏光板は光学異方性層を２層以上含んでいてもよい。２層以上の光学異方性層は法線方向に互いに直接接していてもよいし、間に配向層等の他の層を挟んでいてもよい。２層以上の層を形成する重合性組成物は互いに同一であってもよく、異なっていてもよい。例えば２層の光学異方性層の組み合わせにおいて、棒状液晶化合物を含む組成物から形成された層同士、または円盤状液晶化合物を含む組成物から形成された層同士の組み合わせであってもよく、棒状液晶化合物を含む組成物から形成された層と円盤状液晶化合物を含む組成物から形成された層との組み合わせであってもよい。転写材料（偏光板）が２層以上の光学異方性層を含むとき、先に作製された光学異方性層が後に形成される光学異方性層の配向層として機能していてもよい。このとき先に作製された光学異方性層はラビングされてもよい。また酸化的表面処理されていてもよい。酸化的表面処理はコロナ放電処理またはプラズマ処理であることが好ましい。光学異方性層を２層以上含むときは、光学異方性層の膜厚の総計が上記の膜厚であることが好ましい。 [Two or more optically anisotropic layers]
The polarizing plate of the present invention may contain two or more optically anisotropic layers. Two or more optically anisotropic layers may be in direct contact with each other in the normal direction, or other layers such as an alignment layer may be sandwiched therebetween. The polymerizable compositions forming two or more layers may be the same or different. For example, in a combination of two optically anisotropic layers, it may be a combination of layers formed from a composition containing a rod-like liquid crystal compound, or a combination of layers formed from a composition containing a discotic liquid crystal compound, A combination of a layer formed from a composition containing a rod-like liquid crystal compound and a layer formed from a composition containing a discotic liquid crystal compound may be used. When the transfer material (polarizing plate) includes two or more optically anisotropic layers, the previously prepared optically anisotropic layer may function as an alignment layer of the optically anisotropic layer formed later. . At this time, the previously produced optically anisotropic layer may be rubbed. Further, it may be subjected to oxidative surface treatment. The oxidative surface treatment is preferably a corona discharge treatment or a plasma treatment. When two or more optically anisotropic layers are included, the total thickness of the optically anisotropic layers is preferably the above film thickness.
　２層の光学異方性層は、例えば、合わせてλ／４位相差板としての機能を有していてもよい。λ／４位相差板は偏光子（直線偏光子）と組み合わされて円偏光板として機能する。
　位相差板は、非常に多くの用途を有しており、既に反射型ＬＣＤ、半透過型ＬＣＤ、輝度向上膜、有機ＥＬ表示装置、タッチパネル等に使用されている。例えば、有機ＥＬ（有機エレクトロルミネッセンス）素子は、屈折率の異なる層を積層する構造や、金属電極を用いる構造を有するため、外光が各層の界面で反射し、コントラスト低下や映り込みの問題などを生じることがある。そこで、従来から、外光反射による悪影響を抑制するために、位相差板と偏光膜とから構成される円偏光板が有機ＥＬ表示装置やＬＣＤ表示装置などに使用されている。 The two optically anisotropic layers may have a function as a λ / 4 retardation plate, for example. The λ / 4 retardation plate functions as a circularly polarizing plate in combination with a polarizer (linear polarizer).
Retardation plates have a great many applications, and are already used for reflective LCDs, transflective LCDs, brightness enhancement films, organic EL display devices, touch panels, and the like. For example, an organic EL (organic electroluminescence) element has a structure in which layers having different refractive indexes are laminated or a structure using a metal electrode, so that external light is reflected at the interface of each layer, causing problems such as a decrease in contrast and reflection. May occur. Therefore, conventionally, a circularly polarizing plate composed of a phase difference plate and a polarizing film has been used for an organic EL display device, an LCD display device, and the like in order to suppress adverse effects due to external light reflection.
［液晶化合物］
　液晶化合物としては、棒状液晶化合物、円盤状液晶化合物があげられる。
　棒状液晶化合物としては、アゾメチン類、アゾキシ類、シアノビフェニル類、シアノフェニルエステル類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類およびアルケニルシクロヘキシルベンゾニトリル類が好ましく用いられる。以上のような低分子液晶性分子だけではなく、高分子液晶性分子も用いることができる。 [Liquid Crystal Compound]
Examples of the liquid crystal compound include a rod-like liquid crystal compound and a disk-like liquid crystal compound.
Examples of the rod-like liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used.
　棒状液晶化合物は重合によって配向を固定することがより好ましく、重合性棒状液晶化合物としては、Ｍａｋｒｏｍｏｌ．　Ｃｈｅｍ．，　１９０巻、２２５５頁（１９８９年）、Ａｄｖａｎｃｅｄ　Ｍａｔｅｒｉａｌｓ　５巻、１０７頁（１９９３年）、米国特許４６８３３２７号、同５６２２６４８号、同５７７０１０７号、WO９５／２２５８６号、同９５／２４４５５号、同９７／００６００号、同９８／２３５８０号、同９８／５２９０５号、特開平１－２７２５５１号、同６－１６６１６号、同７－１１０４６９号、同１１－８００８１号、および特願２００１－６４６２７号などに記載の化合物を用いることができる。また、重合性棒状液晶化合物として好ましくは、下記一般式（１）にて表される重合性棒状液晶化合物である。 The rod-like liquid crystal compound is more preferably fixed in orientation by polymerization, and examples of the polymerizable rod-like liquid crystal compound include Makromol. Chem. 190, 2255 (1989), Advanced Materials, 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648, 5,770,107, WO 95/22586, 95/24455, 97/97 No. 0600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and Japanese Patent Application No. 2001-64627 These compounds can be used. The polymerizable rod-like liquid crystal compound is preferably a polymerizable rod-like liquid crystal compound represented by the following general formula (1).
一般式（１）　Ｑ1－Ｌ1－Ｃｙ1－Ｌ2－（Ｃｙ2－Ｌ3）ｎ－Ｃｙ3－Ｌ4－Ｑ2
（一般式（１）中、Ｑ1およびＱ2はそれぞれ独立に重合性基であり、Ｌ1およびＬ4はそれぞれ独立に二価の連結基であり、Ｌ2およびＬ3はそれぞれ独立に単結合または二価の連結基であり、Ｃｙ1、Ｃｙ2およびＣｙ3は二価の環状基であり、ｎは０、１、２または３である。） General formula (1) Q 1 -L 1 -Cy 1 -L 2- (Cy 2 -L 3 ) n-Cy 3 -L 4 -Q 2
(In General Formula (1), Q 1 and Q 2 are each independently a polymerizable group, L 1 and L 4 are each independently a divalent linking group, and L 2 and L 3 are each independently a single group. A bond or a divalent linking group, Cy 1 , Cy 2 and Cy 3 are divalent cyclic groups, and n is 0, 1, 2 or 3.)
　以下にさらに一般式（１）で表される重合性棒状液晶化合物について説明する。
　一般式（１）中、Ｑ1およびＱ2はそれぞれ独立に重合性基である。重合性基の重合反応は、付加重合（開環重合を含む）または縮合重合であることが好ましい。言い換えると、重合性基は、付加重合反応または縮合重合反応が可能な官能基であることが好ましい。以下に重合性基の例を示す。 Hereinafter, the polymerizable rod-like liquid crystal compound represented by the general formula (1) will be described.
In general formula (1), Q 1 and Q 2 are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記のうち、好ましい重合性基としては、アクリル基、メタクリル基があげられる。特に一般式（１）におけるＱ1およびＱ2の双方がアクリル基またはメタクリル基であることが好ましい。 Among the above, preferred polymerizable groups include acryl groups and methacryl groups. In particular, it is preferable that both Q 1 and Q 2 in the general formula (1) are an acryl group or a methacryl group.
　一般式（１）中、Ｌ1およびＬ4はそれぞれ独立に二価の連結基である。Ｌ1およびＬ4はそれぞれ独立に、－Ｏ－、－Ｓ－、－ＣＯ－、－ＮＲ－、－Ｃ＝Ｎ－、二価の鎖状基、二価の環状基およびそれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。上記Ｒは炭素原子数が１から７のアルキル基または水素原子である。Ｒは、炭素原子数１から４のアルキル基または水素原子であることが好ましく、メチル基、エチル基または水素原子であることがさらに好ましく、水素原子であることがもっとも好ましい。 In general formula (1), L 1 and L 4 are each independently a divalent linking group. L 1 and L 4 each independently comprises —O—, —S—, —CO—, —NR—, —C═N—, a divalent chain group, a divalent cyclic group, and combinations thereof. A divalent linking group selected from the group is preferred. R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. R is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom.
　組み合わせからなる二価の連結基の例を以下に示す。ここで、左側がＱ（Ｑ1またはＱ2）に、右側がＣｙ（Ｃｙ1またはＣｙ3）に結合する。 The example of the bivalent coupling group which consists of a combination is shown below. Here, the left side is coupled to Q (Q 1 or Q 2 ), and the right side is coupled to Cy (Cy 1 or Cy 3 ).
Ｌ－１：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－
Ｌ－２：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－
Ｌ－３：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－
Ｌ－４：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－二価の環状基－
Ｌ－５：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－二価の環状基－ＣＯ－Ｏ－
Ｌ－６：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－二価の環状基－Ｏ－ＣＯ－
Ｌ－７：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－二価の環状基－二価の鎖状基－
Ｌ－８：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－二価の環状基－二価の鎖状基－ＣＯ－Ｏ－
Ｌ－９：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－二価の環状基－二価の鎖状基－Ｏ－ＣＯ－
Ｌ－１０：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－二価の環状基－
Ｌ－１１：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－二価の環状基－ＣＯ－Ｏ－
Ｌ－１２：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－二価の環状基－Ｏ－ＣＯ－
Ｌ－１３：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－二価の環状基－二価の鎖状基－
Ｌ－１４：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－二価の環状基－二価の鎖状基－ＣＯ－Ｏ－
Ｌ－１５：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－二価の環状基－二価の鎖状基－Ｏ－ＣＯ－
Ｌ－１６：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－二価の環状基－
Ｌ－１７：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－二価の環状基－ＣＯ－Ｏ－
Ｌ－１８：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－二価の環状基－Ｏ－ＣＯ－
Ｌ－１９：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－二価の環状基－二価の鎖状基－
Ｌ－２０：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－二価の環状基－二価の鎖状基－ＣＯ－Ｏ－
Ｌ－２１：－ＣＯ－Ｏ－二価の鎖状基－Ｏ－ＣＯ－Ｏ－二価の環状基－二価の鎖状基－Ｏ－ＣＯ－ L-1: —CO—O—divalent chain group —O—
L-2: —CO—O—divalent chain group —O—CO—
L-3: —CO—O—divalent chain group —O—CO—O—
L-4: —CO—O—divalent chain group—O—divalent cyclic group—
L-5: —CO—O—divalent chain group —O—divalent cyclic group —CO—O—
L-6: —CO—O—divalent chain group —O—divalent cyclic group —O—CO—
L-7: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group—
L-8: —CO—O—divalent chain group—O—divalent cyclic group—divalent chain group —CO—O—
L-9: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group —O—CO—
L-10: —CO—O—divalent chain group—O—CO—divalent cyclic group—
L-11: —CO—O—divalent chain group —O—CO—divalent cyclic group —CO—O—
L-12: —CO—O—divalent chain group —O—CO—divalent cyclic group —O—CO—
L-13: —CO—O—Divalent chain group—O—CO—Divalent cyclic group—Divalent chain group—
L-14: —CO—O—divalent chain group—O—CO—divalent cyclic group—divalent chain group—CO—O—
L-15: —CO—O—Divalent chain group—O—CO—Divalent cyclic group—Divalent chain group—O—CO—
L-16: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—
L-17: —CO—O—divalent chain group —O—CO—O—divalent cyclic group —CO—O—
L-18: —CO—O—divalent chain group —O—CO—O—divalent cyclic group —O—CO—
L-19: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—divalent chain group—
L-20: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—divalent chain group—CO—O—
L-21: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—divalent chain group—O—CO—
　二価の鎖状基は、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基を意味する。アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基が好ましく、アルキレン基およびアルケニレン基がさらに好ましい。
　アルキレン基は、分岐を有していてもよい。アルキレン基の炭素数は１乃至１２であることが好ましく、２乃至１０であることがさらに好ましく、２乃至８であることがもっとも好ましい。
　置換アルキレン基のアルキレン部分は、上記アルキレン基と同様である。置換基の例としてはハロゲン原子が含まれる。
　アルケニレン基は、分岐を有していてもよい。アルケニレン基の炭素数は２乃至１２であることが好ましく、２乃至１０であることがさらに好ましく、２乃至８であることがもっとも好ましい。
　置換アルキレン基のアルキレン部分は、上記アルキレン基と同様である。置換基の例としてはハロゲン原子が含まれる。
　アルキニレン基は、分岐を有していてもよい。アルキニレン基の炭素数は２乃至１２であることが好ましく、２乃至１０であることがさらに好ましく、２乃至８であることがもっとも好ましい。
　置換アルキニレン基のアルキニレン部分は、上記アルキニレン基と同様である。置換基の例としてはハロゲン原子が含まれる。
　二価の鎖状基の具体例としては、エチレン、トリメチレン、プロピレン、テトラメチレン、２－メチル－テトラメチレン、ペンタメチレン、ヘキサメチレン、オクタメチレン、２－ブテニレン、２－ブチニレンなどがあげられる。
　二価の環状基の定義および例は、後述するＣｙ1、Ｃｙ2およびＣｙ3の定義および例と同様である。 The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred.
The alkylene group may have a branch. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkenylene group may have a branch. The alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkynylene group may have a branch. The alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent include a halogen atom.
Specific examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.
The definition and examples of the divalent cyclic group are the same as those of Cy 1 , Cy 2 and Cy 3 described later.
　一般式（１）中、Ｌ2またはＬ3はそれぞれ独立に単結合または二価の連結基である。Ｌ2およびＬ3はそれぞれ独立に、－Ｏ－、－Ｓ－、－ＣＯ－、－ＮＲ－、－Ｃ＝Ｎ－、二価の鎖状基、二価の環状基およびそれらの組み合わせからなる群より選ばれる二価の連結基または単結合であることが好ましい。上記Ｒは炭素原子数が１から７のアルキル基または水素原子であり、炭素原子数１から４のアルキル基または水素原子であることが好ましく、メチル基、エチル基または水素原子であることがさらに好ましく、水素原子であることがもっとも好ましい。二価の鎖状基、および二価の環状基についてはＬ1およびＬ4の定義と同義である。
　Ｌ2またはＬ3として好ましい二価の連結基としては、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯ－、－ＯＣＯＮＲ－、－ＣＯＳ－、－ＳＣＯ－、－ＣＯＮＲ－、－ＮＲＣＯ－、－ＣＨ2ＣＨ2－、－Ｃ＝Ｃ－ＣＯＯ－、－Ｃ＝Ｎ－、－Ｃ＝Ｎ－Ｎ＝Ｃ－、等が挙げられる。 In the general formula (1), L 2 and L 3 are each independently a single bond or a divalent linking group. L 2 and L 3 each independently comprises —O—, —S—, —CO—, —NR—, —C═N—, a divalent chain group, a divalent cyclic group, and combinations thereof. It is preferably a divalent linking group or a single bond selected from the group. R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom. The divalent chain group and the divalent cyclic group have the same definitions as L 1 and L 4 .
Preferred divalent linking groups as L 2 or L 3 include —COO—, —OCO—, —OCOO—, —OCONR—, —COS—, —SCO—, —CONR—, —NRCO—, —CH 2. CH 2 —, —C═C—COO—, —C═N—, —C═N—N═C—, and the like.
　一般式（１）において、ｎは０、１、２または３である。ｎが２または３の場合、二つのＬ3は同じであっても異なっていてもよく、二つのＣｙ2も同じであっても異なっていてもよい。ｎは１または２であることが好ましく、１であることがさらに好ましい。 In the general formula (1), n is 0, 1, 2, or 3. When n is 2 or 3, two L 3 may be the same or different, and two Cy 2 may be the same or different. n is preferably 1 or 2, and more preferably 1.
　一般式（１）において、Ｃｙ1、Ｃｙ2およびＣｙ3は、それぞれ独立に、二価の環状基である。
　環状基に含まれる環は、５員環、６員環、または７員環であることが好ましく、５員環または６員環であることがさらに好ましく、６員環であることが最も好ましい。
　環状基に含まれる環は、縮合環であってもよい。ただし、縮合環よりも単環であることがより好ましい。
　環状基に含まれる環は、芳香族環、脂肪族環、および複素環のいずれでもよい。芳香族環の例には、ベンゼン環およびナフタレン環が含まれる。脂肪族環の例には、シクロヘキサン環が含まれる。複素環の例には、ピリジン環およびピリミジン環が含まれる。
　ベンゼン環を有する環状基としては、１、４－フェニレンが好ましい。ナフタレン環を有する環状基としては、ナフタレン－１、５－ジイルおよびナフタレン－２、６－ジイルが好ましい。シクロヘキサン環を有する環状基としては１、４－シクロへキシレンであることが好ましい。ピリジン環を有する環状基としてはピリジン－２、５－ジイルが好ましい。ピリミジン環を有する環状基としては、ピリミジン－２、５－ジイルが好ましい。
　環状基は、置換基を有していてもよい。置換基の例には、ハロゲン原子、シアノ基、ニトロ基、炭素原子数が１乃至５のアルキル基、炭素原子数が１乃至５のハロゲン置換アルキル基、炭素原子数が１乃至５のアルコキシ基、炭素原子数が１乃至５のアルキルチオ基、炭素原子数が２乃至６のアシルオキシ基、炭素原子数が２乃至６のアルコキシカルボニル基、カルバモイル基、炭素原子数が２乃至６のアルキル置換カルバモイル基および炭素原子数が２乃至６のアシルアミノ基が含まれる。 In the general formula (1), Cy 1 , Cy 2 and Cy 3 are each independently a divalent cyclic group.
The ring contained in the cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.
The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
As the cyclic group having a benzene ring, 1,4-phenylene is preferable. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.
The cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. An alkylthio group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms And an acylamino group having 2 to 6 carbon atoms.
　以下に、一般式（１）で表される重合性棒状液晶化合物の例を示すが、重合性棒状液晶化合物の例はこれらに限定されるものではない。 Examples of the polymerizable rod-like liquid crystal compound represented by the general formula (1) are shown below, but examples of the polymerizable rod-like liquid crystal compound are not limited to these.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　また、棒状液晶化合物としては、一般式（１）で表される重合性棒状液晶化合物に加え、少なくとも一種の下記一般式（２）で表される化合物を併用することが好ましい。 In addition to the polymerizable rod-like liquid crystal compound represented by the general formula (1), it is preferable to use at least one compound represented by the following general formula (2) as the rod-like liquid crystal compound.
一般式（２）
　Ｍ1－（Ｌ1）ｐ－Ｃｙ1－Ｌ2－（Ｃｙ2－Ｌ3）ｎ－Ｃｙ3－（Ｌ4）ｑ－Ｍ2
（一般式（２）中、Ｍ1およびＭ2はそれぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、ヘテロ環基、シアノ基、ハロゲン、－ＳＣＮ、－ＣＦ3、ニトロ基、または、Ｑ1を表すが、Ｍ1およびＭ2の少なくとも一つは、Ｑ1以外の基を表す。
　ただし、Ｑ1、Ｌ1、Ｌ2、Ｌ3、Ｌ4、Ｃｙ1、Ｃｙ2、Ｃｙ3およびｎは一般式（１）で表される基と同義である。また、ｐおよびｑは０、または１である。） General formula (2)
M 1- (L 1 ) p-Cy 1 -L 2- (Cy 2 -L 3 ) n-Cy 3- (L 4 ) q-M 2
(In the general formula (2), M 1 and M 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, a cyano group, a halogen, —SCN, — CF 3 , a nitro group, or Q 1 is represented, but at least one of M 1 and M 2 represents a group other than Q 1 .
However, Q 1, L 1, L 2, L 3, L 4, Cy 1, Cy 2, Cy 3 and n have the same meanings as the group represented by the general formula (1). P and q are 0 or 1. )
　Ｍ1およびＭ2がＱ1を表さない場合、Ｍ1およびＭ2は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、シアノ基であることが好ましく、より好ましくは、炭素数１～４のアルキル基、もしくは、フェニル基であり、ｐおよびｑは０であることが好ましい。 When M 1 and M 2 do not represent Q 1 , M 1 and M 2 are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a cyano group, more preferably , An alkyl group having 1 to 4 carbon atoms, or a phenyl group, and p and q are preferably 0.
　また、一般式（１）で表される重合性液晶化合物と、一般式（２）で表される化合物の混合物中における、一般式（２）で表される化合物の好ましい混合比率（質量比）としては、０．１％～４０％であり、より好ましくは、１％～３０％であり、更に好ましくは、５％～２０％である。 Moreover, the preferable mixing ratio (mass ratio) of the compound represented by the general formula (2) in the mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the compound represented by the general formula (2). Is 0.1% to 40%, more preferably 1% to 30%, and still more preferably 5% to 20%.
　以下に、一般式（２）で表される化合物の好ましい例を示すが、本発明はこれらに限定されるものではない。 Hereinafter, preferred examples of the compound represented by the general formula (2) are shown, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　円盤状液晶化合物は、様々な文献（Ｃ．Ｄｅｓｔｒａｄｅ　ｅｔ　ａｌ．，Ｍｏｌ．Ｃｒｙｓｔ．Ｌｉｑ．Ｃｒｙｓｔ．，ｖｏｌ．７１，ｐａｇｅ　１１１（１９８１）；日本化学会編、季刊化学総説、Ｎｏ．２２、液晶の化学、第５章、第１０章第２節（１９９４）；Ｂ．Ｋｏｈｎｅ　ｅｔ　ａｌ．，Ａｎｇｅｗ．Ｃｈｅｍ．Ｓｏｃ．Ｃｈｅｍ．Ｃｏｍｍ．，ｐａｇｅ　１７９４（１９８５）；Ｊ．Ｚｈａｎｇ　ｅｔ　ａｌ．，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，ｖｏｌ．１１６，ｐａｇｅ　２６５５（１９９４））に記載されている。円盤状液晶化合物の重合については、特開平８－２７２８４公報に記載がある。円盤状配向層液晶化合物を重合により固定するためには、円盤状液晶化合物の円盤状コアに、置換基として重合性基を結合させる必要がある。ただし、円盤状コアに重合性基を直結させると、重合反応において配向状態を保つことが困難になる。そこで、円盤状コアと重合性基との間に、連結基を導入する。即ち、光硬化型円盤状液晶化合物は、下記式（３）で表わされる化合物であることが好ましい。 The discotic liquid crystal compounds are disclosed in various literatures (C. Destrade et al., Mol. Cryst. Liq. Cryst., Vol. 71, page 111 (1981); edited by The Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal). Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985): J. Zhang et al., J. Chem. Am. Chem. Soc., Vol. 116, page 2655 (1994)). The polymerization of the discotic liquid crystal compound is described in JP-A-8-27284. In order to fix the discotic alignment layer liquid crystal compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystal compound. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. That is, the photocurable discotic liquid crystal compound is preferably a compound represented by the following formula (3).
一般式（３）
　Ｄ（－Ｌ－Ｐ）ｎ
（一般式中、Ｄは円盤状コアであり、Ｌは二価の連結基であり、Ｐは重合性基であり、ｎは４～１２の整数である。）
　式（３）中の円盤状コア（Ｄ）、二価の連結基（Ｌ）および重合性基（Ｐ）の好ましい具体例は、それぞれ、特開２００１－４８３７号公報に記載の（Ｄ１）～（Ｄ１５）、（Ｌ１）～（Ｌ２５）、（Ｐ１）～（Ｐ１８）であり、同公報に記載の内容を好ましく用いることができる。
　また、円盤状液晶化合物としては、特開２００７－２２２０号公報に記載の一般式（ＤＩ）で表される化合物を用いることも好ましい。 General formula (3)
D (-LP) n
(In the general formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.)
Preferred specific examples of the discotic core (D), the divalent linking group (L), and the polymerizable group (P) in the formula (3) are (D1) to (D1) described in JP-A-2001-4837, respectively. (D15), (L1) to (L25), (P1) to (P18), and the contents described in the publication can be preferably used.
As the discotic liquid crystal compound, it is also preferable to use a compound represented by the general formula (DI) described in JP-A-2007-2220.
　液晶化合物は重合性組成物の固形分質量（溶媒を除いた質量）に対し、８０質量％以上、９０質量％以上、または、９５質量％以上、また、９９．９９質量％以下、９９．９８質量％以下、９９．９７質量％以下で含まれていればよい。特に、アクリル基、またはメタクリル基を含む化合物が、７０質量％以上、８０質量％以上、９０質量％以上、または、９５質量％以上、また、９９．９９質量％以下、９９．９８質量％以下、９９．９７質量％以下で含まれていることが好ましい。 The liquid crystal compound is 80% by mass or more, 90% by mass or more, or 95% by mass or more, and 99.99% by mass or less, 99.98% with respect to the solid content mass (the mass excluding the solvent) of the polymerizable composition. It should just be contained in the mass% or less and 99.97 mass% or less. In particular, the compound containing an acrylic group or a methacryl group is 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, and 99.99% by mass or less, 99.98% by mass or less. 99.97% by mass or less.
　液晶化合物は、水平配向、垂直配向、傾斜配向、およびねじれ配向のいずれの配向状態で固定されていてもよい。尚、本明細書において「水平配向」とは、棒状液晶の場合、分子長軸と透明支持体の水平面が平行であることをいい、円盤状液晶の場合、円盤状液晶化合物のコアの円盤面と透明支持体の水平面が平行であることをいうが、厳密に平行であることを要求するものではなく、本明細書では、水平面とのなす傾斜角が１０度未満の配向を意味するものとする。本発明で用いられる光学異方性層としては、棒状液晶化合物を水平配向させた状態で固定化されたものを含むことが好ましい。 The liquid crystal compound may be fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, and twist alignment. In the present specification, “horizontal alignment” means that in the case of a rod-like liquid crystal, the molecular long axis and the horizontal plane of the transparent support are parallel, and in the case of a disc-like liquid crystal, the disc surface of the core of the disc-like liquid crystal compound. And the horizontal plane of the transparent support is parallel, but it is not required to be strictly parallel, and in this specification, an inclination angle with the horizontal plane is less than 10 degrees. To do. The optically anisotropic layer used in the present invention preferably contains a rod-shaped liquid crystal compound fixed in a horizontally aligned state.
[配向固定化]
　液晶化合物の重合反応は、光重合反応であればよい。光重合反応としては、ラジカル重合、カチオン重合のいずれでもよいが、ラジカル重合が好ましい。ラジカル光重合開始剤の例には、α－カルボニル化合物（米国特許２３６７６６１号、同２３６７６７０号の各明細書記載）、アシロインエーテル（米国特許２４４８８２８号明細書記載）、α－炭化水素置換芳香族アシロイン化合物（米国特許２７２２５１２号明細書記載）、多核キノン化合物（米国特許３０４６１２７号、同２９５１７５８号の各明細書記載）、トリアリールイミダゾールダイマーとｐ－アミノフェニルケトンとの組み合わせ（米国特許３５４９３６７号明細書記載）、アクリジンおよびフェナジン化合物（特開昭６０－１０５６６７号公報、米国特許４２３９８５０号明細書記載）およびオキサジアゾール化合物（米国特許４２１２９７０号明細書記載）が含まれる。カチオン光重合開始剤の例には、有機スルフォニウム塩系、ヨードニウム塩系、フォスフォニウム塩系等を例示することができ、有機スルフォニウム塩系、が好ましく、トリフェニルスルフォニウム塩が特に好ましい。これら化合物の対イオンとしては、ヘキサフルオロアンチモネート、ヘキサフルオロフォスフェートなどが好ましく用いられる。 [Fixed orientation]
The polymerization reaction of the liquid crystal compound may be a photopolymerization reaction. The photopolymerization reaction may be either radical polymerization or cationic polymerization, but radical polymerization is preferred. Examples of radical photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon-substituted aromatics. An acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970). Examples of the cationic photopolymerization initiator include organic sulfonium salt systems, iodonium salt systems, phosphonium salt systems, and the like. Organic sulfonium salt systems are preferable, and triphenylsulfonium salts are particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.
　光重合開始剤の使用量は、塗布液の固形分の０．０１～２０質量％であることが好ましく、０．５～５質量％であることがさらに好ましい。液晶化合物の重合のための光照射は、紫外線を用いることが好ましい。照射エネルギーは、１０ｍＪ／ｃｍ2～１０Ｊ／ｃｍ2であることが好ましく、２５～１０００ｍＪ／ｃｍ2であることがさらに好ましい。照度は１０～２０００ｍＷ／ｃｍ2であることが好ましく、２０～１５００ｍＷ／ｃｍ2であることがより好ましく、４０～１０００ｍＷ／ｃｍ2であることがさらに好ましい。照射波長としては２５０～４５０ｎｍにピークを有することが好ましく、３００～４１０ｎｍにピークを有することがさらに好ましい。光重合反応を促進するため、窒素などの不活性ガス雰囲気下あるいは加熱条件下で光照射を実施してもよい。 The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. Light irradiation for the polymerization of the liquid crystal compound is preferably performed using ultraviolet rays. The irradiation energy is preferably 10 mJ / cm 2 to 10 J / cm 2 , and more preferably 25 to 1000 mJ / cm 2 . The illuminance is preferably 10 to 2000 mW / cm 2 , more preferably 20 to 1500 mW / cm 2 , and still more preferably 40 to 1000 mW / cm 2 . The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In order to accelerate the photopolymerization reaction, light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions.
［水平配向剤］
　液晶化合物を含む重合性組成物中に、特開２００９－６９７９３号公報の段落「００９８」～「０１０５」に記載の、一般式（１）～（３）で表される化合物および一般式（４）のモノマーを用いた含フッ素ホモポリマーまたはコポリマーの少なくとも一種を含有させることで、液晶化合物の分子を実質的に水平配向させることができる。液晶化合物を水平配向させる場合、その傾斜角は０～５度が好ましく、０～３度がより好ましく、０～２度がさらに好ましく、０～１度が最も好ましい。 [Horizontal alignment agent]
In the polymerizable composition containing a liquid crystal compound, the compounds represented by the general formulas (1) to (3) and the general formula (4) described in paragraphs “0098” to “0105” of JP2009-69793A are described. The molecule of the liquid crystal compound can be substantially horizontally aligned by containing at least one of a fluorine-containing homopolymer or copolymer using the monomer (1). When the liquid crystal compound is horizontally aligned, the inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.
　水平配向剤の添加量としては、液晶化合物の質量の０．０１～２０質量％が好ましく、０．０１～１０質量％がより好ましく、０．０２～１質量％が特に好ましい。なお、特開２００９－６９７９３号公報の段落「００９８」～「０１０５」に記載の一般式（１）～（４）にて表される化合物は、単独で用いてもよいし、二種以上を併用してもよい。 The addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass, based on the mass of the liquid crystal compound. The compounds represented by the general formulas (1) to (4) described in paragraphs “0098” to “0105” of JP-A-2009-69793 may be used alone or in combination of two or more. You may use together.
［その他の添加剤］
　液晶化合物を含む重合性組成物は、特開２００６－１１３５００号公報に記載の式（Ｉ）で表されるピリジニウム化合物を含んでいてもよい。ピリジニウム化合物は配向層界面側垂直配向剤として機能することができ、例えば、ディスコティック液晶性化合物の分子を配向層近傍で実質的に垂直に配向させることができる。液晶化合物を含む重合性組成物は、特開２０１３－０５４２０１号公報に記載の一般式（Ｉ）で表されるボロン酸化合物を含んでいてもよい。
　液晶化合物を含む重合性組成物はそのほか必要な添加剤を含んでいてもよいが、いわゆるカイラル剤を含んでいないことが好ましい。 [Other additives]
The polymerizable composition containing a liquid crystal compound may contain a pyridinium compound represented by the formula (I) described in JP-A-2006-113500. The pyridinium compound can function as an alignment layer interface-side vertical alignment agent. For example, the molecules of the discotic liquid crystalline compound can be aligned substantially vertically in the vicinity of the alignment layer. The polymerizable composition containing a liquid crystal compound may contain a boronic acid compound represented by the general formula (I) described in JP2013-05201A.
The polymerizable composition containing a liquid crystal compound may contain other necessary additives, but preferably does not contain a so-called chiral agent.
[配向層]
　光学異方性層は、配向層の表面に塗布された重合性組成物の層から形成されたものであってもよい。配向層は、仮支持体（延伸フィルム）もしくは仮支持体上に塗設された下塗層の表面に設けられる。配向層は、その上に設けられる重合性組成物中の液晶化合物の配向を規定するように機能する。配向層は、光学異方性層に配向性を付与できるものであれば、どのような層でもよい。配向層の好ましい例としては、フェノール樹脂、エポキシ樹脂、フッ素樹脂、ポリエチレン樹脂、ポリプロピレン樹脂などが挙げられる。また、例えば、水酸基、アミノ基、カルボキシル基、スルホン酸基、リン酸基など、親水性基を含む有機材料が好ましい。具体的には、アクリル樹脂、ポリビニルアルコール樹脂、ポリエステル樹脂、アミノ樹脂等を使用することができる。さらに、有機化合物（好ましくはポリマー）のラビング処理された層、アゾベンゼンポリマーやポリビニルシンナメートに代表される偏光照射により液晶の配向性を発現する光配向層、無機化合物の斜方蒸着層、およびマイクログルーブを有する層、さらにω－トリコサン酸、ジオクタデシルメチルアンモニウムクロライドおよびステアリル酸メチル等のラングミュア・ブロジェット法（ＬＢ膜）により形成される累積膜、あるいは電場あるいは磁場の付与により誘電体を配向させた層を挙げることができる。配向層としてはラビングの態様ではポリビニルアルコールを含むことが好ましく、配向層の上または下の少なくともいずれか１層と架橋できることが特に好ましい。配向方向を制御する方法としては、光配向層およびマイクログルーブが好ましい。光配向層としては、ポリビニルシンナメートのように二量化によって配向性を発現するものが特に好ましく、マイクログルーブとしてはあらかじめ機械加工またはレーザ加工により作製したマスターロールのエンボス処理が特に好ましい。 [Alignment layer]
The optically anisotropic layer may be formed from a layer of a polymerizable composition applied to the surface of the alignment layer. The alignment layer is provided on the surface of a temporary support (stretched film) or an undercoat layer coated on the temporary support. The alignment layer functions to define the alignment of the liquid crystal compound in the polymerizable composition provided thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer. Preferable examples of the alignment layer include phenol resin, epoxy resin, fluororesin, polyethylene resin, and polypropylene resin. Further, for example, an organic material containing a hydrophilic group such as a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group is preferable. Specifically, an acrylic resin, a polyvinyl alcohol resin, a polyester resin, an amino resin, or the like can be used. Furthermore, a layer subjected to a rubbing treatment of an organic compound (preferably a polymer), a photo-alignment layer that exhibits liquid crystal orientation by polarized irradiation represented by azobenzene polymer or polyvinyl cinnamate, an oblique deposition layer of an inorganic compound, and a micro A layer having a groove, a cumulative film formed by Langmuir-Blodgett method (LB film) such as ω-tricosanoic acid, dioctadecylmethylammonium chloride and methyl stearylate, or a dielectric by orienting an electric or magnetic field Can be mentioned. In the rubbing mode, the alignment layer preferably contains polyvinyl alcohol, and it is particularly preferable that the alignment layer can be cross-linked with at least one of the upper and lower alignment layers. As a method for controlling the orientation direction, a photo-alignment layer and a microgroove are preferable. The photo-alignment layer is particularly preferably a material that exhibits orientation by dimerization, such as polyvinyl cinnamate, and the microgroove is particularly preferably an embossing treatment of a master roll prepared in advance by machining or laser processing.
　配向層などの光学異方性層の下層などの層に施されるラビング処理は、一般にはポリマーを主成分とする膜の表面を、紙や布で一定方向に擦ることにより実施することができる。ラビング処理の一般的な方法については、例えば、「液晶便覧」（丸善社発行、平成１２年１０月３０日）に記載されている。 The rubbing treatment applied to the layer such as the lower layer of the optically anisotropic layer such as the alignment layer can be generally performed by rubbing the surface of the film mainly composed of a polymer with paper or cloth in a certain direction. . A general method of rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).
　ラビング密度を変える方法としては、「液晶便覧」（丸善社発行）に記載されている方法を用いることができる。ラビング密度（Ｌ）は、下記式（Ａ）で定量化されている。
　式（Ａ）　Ｌ＝Ｎｌ（１＋２πｒｎ／６０ｖ）
　式（Ａ）中、Ｎはラビング回数、ｌはラビングローラーの接触長、ｒはローラーの半径、ｎはローラーの回転数（ｒｐｍ）、ｖはステージ移動速度（秒速）である。 As a method for changing the rubbing density, a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used. The rubbing density (L) is quantified by the following formula (A).
Formula (A) L = Nl (1 + 2πrn / 60v)
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed).
　ラビング密度を高くするためには、ラビング回数を増やす、ラビングローラーの接触長を長く、ローラーの半径を大きく、ローラーの回転数を大きく、ステージ移動速度を遅くすればよく、一方、ラビング密度を低くするためには、この逆にすればよい。
　また、ラビング処理の際の条件としては、特許４０５２５５８号の記載を参照することもできる。 In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can reverse this.
In addition, the description in Japanese Patent No. 4052558 can also be referred to as conditions for the rubbing process.
 [アクリルポリマー層]
　転写材料はアクリルポリマー層を含んでいてもよい。また、本発明の製造方法により製造される偏光板はアクリルポリマー層を含んでいてもよい。
　アクリルポリマー層形成用の材料は一般にシクロオレフィンポリマー含有層形成用の材料より安価であるが、アクリルポリマー層を偏光子を含むフィルムに設けるための転写材料として、上記の仮支持体の表面に直接アクリルポリマー層を設けた構成の転写材料を本発明者らが作製しようとしても、アクリルポリマー層を欠損なく剥離することが困難であった。しかし、仮支持体上にシクロオレフィンポリマー含有層を有する転写材料を用い、シクロオレフィンポリマー含有層上にアクリルポリマー層を設けることにより、仮支持体からの良好な剥離性を有するとともに、より安価な構成で必要な膜厚を有する、透明かつ低複屈折性の保護フィルムを形成することができる。 [Acrylic polymer layer]
The transfer material may include an acrylic polymer layer. Moreover, the polarizing plate manufactured by the manufacturing method of this invention may contain the acrylic polymer layer.
The material for forming the acrylic polymer layer is generally less expensive than the material for forming the cycloolefin polymer-containing layer, but as a transfer material for providing the acrylic polymer layer on the film containing the polarizer, it is directly applied to the surface of the temporary support. Even if the present inventors tried to produce a transfer material having a configuration provided with an acrylic polymer layer, it was difficult to peel the acrylic polymer layer without any defects. However, by using a transfer material having a cycloolefin polymer-containing layer on the temporary support, and providing an acrylic polymer layer on the cycloolefin polymer-containing layer, it has good peelability from the temporary support and is less expensive. A transparent and low birefringent protective film having a film thickness required for the structure can be formed.
　転写材料はアクリルポリマー層とともに光学異方性層を含んでいてもよい。このとき、アクリルポリマー層および光学異方性層の層順は特に限定されない。シクロオレフィンポリマー含有層、アクリルポリマー層、および光学異方性層をこの順で含み、アクリルポリマー層が光学異方性層形成のための配向層を兼ねていてもよい。 The transfer material may include an optically anisotropic layer together with the acrylic polymer layer. At this time, the layer order of the acrylic polymer layer and the optically anisotropic layer is not particularly limited. A cycloolefin polymer-containing layer, an acrylic polymer layer, and an optically anisotropic layer may be included in this order, and the acrylic polymer layer may also serve as an alignment layer for forming the optically anisotropic layer.
　アクリルポリマー層としては、シクロオレフィンポリマー含有層または光学異方性層などの下層の表面に、（メタ）アクリレートモノマーを含む重合性組成物を塗布し、この塗布層を硬化して形成される層であってもよく、アクリルポリマー含有組成物を塗布して、この塗布層を乾燥させて形成される層であってもよく、別途作製したアクリルポリマーフィルムを接着等により設けた層であってもよい。 As the acrylic polymer layer, a layer formed by applying a polymerizable composition containing a (meth) acrylate monomer to the surface of a lower layer such as a cycloolefin polymer-containing layer or an optically anisotropic layer, and curing the applied layer. It may be a layer formed by applying an acrylic polymer-containing composition and drying this coating layer, or may be a layer in which a separately prepared acrylic polymer film is provided by adhesion or the like. Good.
　アクリルポリマー層としては低複屈折性で透明であるものが好ましい。光学的に等方性であるものを用いればよい。光学的に等方性であるとは、面内レターデーション（Ｒｅ（５５０））の絶対値が１０ｎｍ以下、かつ、厚み方向レターデーション（Ｒｔｈ）の絶対値が１０ｎｍ以下であることを意味する。 The acrylic polymer layer is preferably a transparent material having low birefringence. What is optically isotropic may be used. Optically isotropic means that the in-plane retardation (Re (550)) has an absolute value of 10 nm or less and the thickness direction retardation (Rth) has an absolute value of 10 nm or less.
　アクリルポリマー層を形成するための（メタ）アクリレートを含む重合性組成物中の（メタ）アクリレートとしては、アクリロイル基またはメタアクリロイル基を含む化合物であれば特に限定されない。化合物中のアクリロイル基またはメタアクリロイル基は１つであっても、２つ以上（例えば、２つ、３つ、４つなど）であってもよい。（メタ）アクリレートの分子量は５０００以下程度であればよく、３０００以下が好ましく、２０００以下がより好ましく、１０００以下が特に好ましい。例えば、（メタ）アクリレートとしては、（メタ）アクリル酸、その各種エステル（メチル（メタ）アクリレート等）が挙げられる。
　アクリルポリマー層を形成するための（メタ）アクリレートを含む重合性組成物中には（メタ）アクリレート以外の重合性化合物が含まれていてもよい。 The (meth) acrylate in the polymerizable composition containing (meth) acrylate for forming the acrylic polymer layer is not particularly limited as long as it is a compound containing an acryloyl group or a methacryloyl group. The compound may have one acryloyl group or methacryloyl group, or two or more (for example, 2, 3, 4, etc.). The molecular weight of the (meth) acrylate may be about 5000 or less, preferably 3000 or less, more preferably 2000 or less, and particularly preferably 1000 or less. For example, (meth) acrylate includes (meth) acrylic acid and various esters thereof (such as methyl (meth) acrylate).
In the polymerizable composition containing (meth) acrylate for forming the acrylic polymer layer, a polymerizable compound other than (meth) acrylate may be contained.
　アクリルポリマーは、例えば、ポリメチル（メタ）アクリレート、（メタ）アクリル酸とその各種エステルの共重合体、スチレンと（メタ）アクリル酸あるいは各種（メタ）アクリル酸エステルの共重合体、ビニルトルエンと（メタ）アクリル酸あるいは各種（メタ）アクリル酸エステルの共重合体等を挙げることができる。好ましい例としてはメチル（メタ）アクリレートと（メタ）アクリル酸との共重合体、アリル（メタ）アクリレートと（メタ）アクリル酸の共重合体、ベンジル（メタ）アクリレートと（メタ）アクリル酸と他のモノマーとの多元共重合体などを挙げることができる。これらのポリマーは単独で用いてもよく、複数種を組み合わせて使用してもよい。 Acrylic polymers include, for example, polymethyl (meth) acrylate, copolymers of (meth) acrylic acid and various esters thereof, copolymers of styrene and (meth) acrylic acid or various (meth) acrylic esters, vinyltoluene and ( Mention may be made of (meth) acrylic acid or copolymers of various (meth) acrylic acid esters. Preferred examples include copolymers of methyl (meth) acrylate and (meth) acrylic acid, copolymers of allyl (meth) acrylate and (meth) acrylic acid, benzyl (meth) acrylate and (meth) acrylic acid, and others. And multi-component copolymers with other monomers. These polymers may be used alone or in combination of two or more.
　アクリルポリマー層は（メタ）アクリレートおよびそのほかのモノマーを熱重合したものであっても光重合したものであってもよいが、光重合したものが特に好ましい。光重合反応は、液晶化合物を含む重合性組成物から形成される層に、（メタ）アクリレートを含む重合性組成物が直接塗布され、その塗布層において行われていればよい。光重合反応のための光照射は上述の液晶化合物の重合のための光照射と同様の条件で行われればよく、液晶化合物の重合のための光照射が、（メタ）アクリレートを同時に重合させていてもよい。 The acrylic polymer layer may be either one obtained by thermal polymerization of (meth) acrylate and other monomers, or one obtained by photopolymerization, but one obtained by photopolymerization is particularly preferred. The photopolymerization reaction should just be performed in the coating layer in which the polymeric composition containing (meth) acrylate is directly apply | coated to the layer formed from the polymeric composition containing a liquid crystal compound. The light irradiation for the photopolymerization reaction may be performed under the same conditions as the light irradiation for the polymerization of the liquid crystal compound described above, and the light irradiation for the polymerization of the liquid crystal compound simultaneously polymerizes the (meth) acrylate. May be.
　重合開始剤としては熱重合開始剤、光重合開始剤が、手法に合わせて適宜用いられる。
　光重合開始剤としては米国特許第２３６７６６０号明細書に開示されているビシナルポリケタルドニル化合物、米国特許第２４４８８２８号明細書に記載されているアシロインエーテル化合物、米国特許第２７２２５１２号明細書に記載のα－炭化水素で置換された芳香族アシロイン化合物、米国特許第３０４６１２７号明細書および同第２９５１７５８号明細書に記載の多核キノン化合物、米国特許第３５４９３６７号明細書に記載のトリアリールイミダゾール２量体とｐ－アミノケトンの組み合わせ、特公昭５１－４８５１６号公報に記載のベンゾチアゾール化合物とトリハロメチル－ｓ－トリアジン化合物、米国特許第４２３９８５０号明細書に記載されているトリハロメチル－トリアジン化合物、米国特許第４２１２９７６号明細書に記載されているトリハロメチルオキサジアゾール化合物等を挙げることができる。特に、トリハロメチル－ｓ－トリアジン、トリハロメチルオキサジアゾールおよびトリアリールイミダゾール２量体が好ましい。また、この他、特開平１１－１３３６００号公報に記載の「重合開始剤Ｃ」も好適なものとしてあげることができる。
　また重合開始剤の量は、アクリルポリマー層形成のための重合性組成物の固形分の０．０１～２０質量％であることが好ましく、０．２～１０質量％であることがさらに好ましい。 As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator is appropriately used according to the method.
As photopolymerization initiators, vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, US Pat. No. 2,722,512 An aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. Nos. 3,046,127 and 2,951,758, and a triarylimidazole described in US Pat. No. 3,549,367 A combination of a dimer and p-aminoketone, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, a trihalomethyl-triazine compound described in US Pat. No. 4,239,850, US Pat. No. 4,221,976 And the like trihalomethyl oxadiazole compounds described. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable. In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
The amount of the polymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.2 to 10% by mass, based on the solid content of the polymerizable composition for forming the acrylic polymer layer.
　アクリルポリマー層にハードコート性を持たせるために、アクリルポリマー層中のポリマーとしてＴｇの高いポリマーを用いてもよい。そのＴｇは５０℃以上が好ましく、８０℃以上であればより好ましく、１００℃以上であればさらに好ましい。ポリマーのＴｇを上げるために、水酸基、カルボン酸基、アミノ基といった極性基を導入するとよい。高Ｔｇポリマーの一例として、ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート等のアルキル（メタ）アクリレートの反応物、アルキル（メタ）アクリレートと（メタ）アクリル酸との共重合体、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレートの反応物、アルキル（メタ）アクリレートと、水酸基含有（メタ）アクリレートと無水コハク酸、無水フタル酸等の酸無水物との反応物であるハーフエステルの共重合体等が挙げられる。 In order to give the acrylic polymer layer a hard coat property, a polymer having a high Tg may be used as the polymer in the acrylic polymer layer. The Tg is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher. In order to increase the Tg of the polymer, a polar group such as a hydroxyl group, a carboxylic acid group, or an amino group may be introduced. Examples of high Tg polymers include poly (methyl) acrylate, alkyl (meth) acrylate reactants such as polyethyl (meth) acrylate, copolymers of alkyl (meth) acrylate and (meth) acrylic acid, 2-hydroxyethyl Reaction products of hydroxyl group-containing (meth) acrylates such as (meth) acrylate and 2-hydroxypropyl (meth) acrylate, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates and succinic anhydride, acid anhydrides such as phthalic anhydride And a copolymer of a half ester which is a reaction product with the product.
　また、ハードコート性を付与するために、少なくとも１種類の二官能以上の重合性モノマーおよび重合性ポリマーを含む層を光照射または熱により重合した層を用いてもよい。反応性基としては、（メタ）アクリル基のほか、ビニル基、アリル基、エポキシ基、オキセタニル基、ビニルエーテル基等が挙げられる。重合性ポリマーの一例として、グリシジル（メタ）アクリレート、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、グリセロール１，３－ジ（メタ）アクリレート等の重合性基含有アクリレートの反応物、重合性基含有アクリレートと（メタ）アクリル酸との共重合体、および重合性基含有アクリレートと他のモノマーとの多元共重合体が挙げられる。 Further, in order to impart hard coat properties, a layer obtained by polymerizing a layer containing at least one bifunctional or higher polymerizable monomer and a polymerizable polymer by light irradiation or heat may be used. Examples of reactive groups include (meth) acryl groups, vinyl groups, allyl groups, epoxy groups, oxetanyl groups, vinyl ether groups, and the like. Examples of polymerizable polymers include glycidyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol 1,3-di (meth) acrylate-containing acrylate reactants, polymerizability Examples thereof include a copolymer of a group-containing acrylate and (meth) acrylic acid, and a multi-component copolymer of a polymerizable group-containing acrylate and another monomer.
　アクリルポリマー層の膜厚は、６０μｍ以下、５０μｍ以下、４０μｍ以下、３０μｍ以下、２５μｍ以下、または１５μｍ以下、また、２μｍ以上、３μｍ以上、３．５μｍ以上、４μｍ以上、４．５μｍ以上、または５μｍ以上であることが好ましい。 The thickness of the acrylic polymer layer is 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, or 15 μm or less, or 2 μm or more, 3 μm or more, 3.5 μm or more, 4 μm or more, 4.5 μm or more, or 5 μm. The above is preferable.
［その他の層］
　転写材料は、上記の層のほか、低透湿層、保護層、帯電防止層、ハードコート層、接着層等の他の機能性層を含んでいてもよい。 [Other layers]
In addition to the above layers, the transfer material may contain other functional layers such as a low moisture permeability layer, a protective layer, an antistatic layer, a hard coat layer, and an adhesive layer.
［偏光板の作製方法］
　本発明の偏光板の作製方法においては、上述の転写材料の仮支持体を剥離し、仮支持体の剥離後の層または積層体を偏光子を含むフィルムに積層してもよいし、上述の転写材料を偏光子を含むフィルムに積層し、その後、仮支持体を剥離してもよい。仮支持体を剥離してから積層する場合は、シクロオレフィンポリマー含有層が偏光子を含むフィルム側の面にあってもよいし、シクロオレフィンポリマー含有層以外の層の面が偏光子を含むフィルム側の面にあってもよい。積層後に仮支持体を剥離する場合は、仮支持体からみてシクロオレフィンポリマー含有層側の面が偏光子を含むフィルム側の面になるように積層する。積層は接着層を介して行えばよい。接着層は接着剤または粘着剤を含む層であればよい。すなわち、転写材料と偏光子を含むフィルムとは接着剤または粘着剤により接着または粘着させられていればよい。接着剤としては特に限定はないが、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の硬化性接着剤、特開２００８－１７４６６７号公報記載の３６０～４５０ｎｍの波長におけるモル吸光係数が４００以上である光重合開始剤と紫外線硬化性化合物とを必須成分とする活性エネルギー線硬化型接着剤、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（ａ）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、（ｂ）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、（ｃ）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あげられる。 [Production Method of Polarizing Plate]
In the method for producing a polarizing plate of the present invention, the temporary support of the transfer material described above may be peeled off, and the layer or laminate after peeling off the temporary support may be laminated on a film containing a polarizer. The transfer material may be laminated on a film containing a polarizer, and then the temporary support may be peeled off. When the temporary support is peeled off and then laminated, the cycloolefin polymer-containing layer may be on the film-side surface containing the polarizer, or the surface of the layer other than the cycloolefin polymer-containing layer may contain the polarizer. It may be on the side surface. When the temporary support is peeled after the lamination, the layers are laminated so that the surface on the cycloolefin polymer-containing layer side is the film side surface containing the polarizer as viewed from the temporary support. Lamination may be performed via an adhesive layer. The adhesive layer may be a layer containing an adhesive or a pressure-sensitive adhesive. That is, the transfer material and the film containing the polarizer need only be adhered or adhered to each other by an adhesive or an adhesive. The adhesive is not particularly limited, but is an epoxy compound curable adhesive that does not contain an aromatic ring in the molecule, as disclosed in JP-A No. 2004-245925, and is disclosed in JP-A-2008-174667. An active energy ray-curable adhesive comprising a photopolymerization initiator having a molar extinction coefficient of 400 or more at a wavelength of 450 nm and an ultraviolet curable compound as essential components, and a (meth) acrylic compound described in JP-A-2008-174667 (A) a (meth) acrylic compound having 2 or more (meth) acryloyl groups in the molecule and (b) a hydroxyl group in the molecule, and having only a polymerizable double bond (Meth) acrylic compound and (c) phenolethylene oxide modified acrylate or nonylphenol ethylene oxide modified acrylic Such as an active energy ray-curable adhesive containing a chromatography bets and the like.
［偏光子を含むフィルム］
　偏光子を含むフィルムは、偏光子のみからなっていてもよく、偏光子の他、保護フィルムなどの他の層を含んでいてもよい。偏光子を含むフィルムは、偏光子を最表面に含んでいてもよく、偏光子の両側の面に他の層があってもよい。最表面にある偏光子の面で転写材料（または転写材料から仮支持体が剥離された積層体）に接着されていてもよく、他の層の面で接着されていてもよい。 [Film including polarizer]
The film containing a polarizer may consist of only a polarizer, and may contain other layers, such as a protective film, other than a polarizer. The film containing a polarizer may contain the polarizer on the outermost surface, and may have other layers on both sides of the polarizer. The surface of the polarizer on the outermost surface may be adhered to the transfer material (or the laminate in which the temporary support is peeled off from the transfer material), or may be adhered to the surface of another 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５０μｍ以下であればよく、３０μｍ以下が好ましく、２０μｍ以下がより好ましい。 [Polarizer]
Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol 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 a polarizer composed of polyvinyl alcohol (PVA) and a dichroic molecule, reference can be made to, for example, the description in JP-A-2009-237376. The film thickness of a polarizer should just be 50 micrometers or less, 30 micrometers or less are preferable and 20 micrometers or less are more preferable.
［保護フィルム（保護層）］
　偏光板は保護フィルムを含んでいてもよい。例えば、上記の転写材料によりシクロオレフィンポリマー層またはこの層を含む積層体を設けられる偏光子の面の反対側の面には、保護フィルムが配されていてもよい。保護フィルムとしては、セルロースアシレ―ト系ポリマーフィルム、アクリル系ポリマーフィルム、またはシクロオレフィン系ポリマーフィルムを用いることができる。セルロースアシレ―ト系ポリマーに関しては特開２０１１－２３７４７４号公報のセルロースアシレ―ト系樹脂に関する記載を参照できる。シクロオレフィン系ポリマーフィルムとしては、上記のシクロオレフィンポリマー含有層として記載したものと同様の材料より形成されたものを用いればよく、また、特開２００９－１７５２２２号および特開２００９－２３７３７６号公報の記載も参照できる。　保護フィルムの膜厚は、３０μｍ以下であればよく、２０μｍ以下が好ましく、１０μｍ以下がより好ましい。 [Protective film (protective layer)]
The polarizing plate may contain a protective film. For example, a protective film may be disposed on the surface opposite to the surface of the polarizer on which the cycloolefin polymer layer or the laminate including this layer is provided by the transfer material. As the protective film, a cellulose acylate polymer film, an acrylic polymer film, or a cycloolefin polymer film can be used. Regarding the cellulose acylate polymer, reference can be made to the description of the cellulose acylate resin in JP2011-237474A. As the cycloolefin-based polymer film, a film formed from the same material as that described for the cycloolefin polymer-containing layer may be used, and JP 2009-175222 A and JP 2009-237376 A may be used. Reference can also be made to the description. The film thickness of a protective film should just be 30 micrometers or less, 20 micrometers or less are preferable and 10 micrometers or less are more preferable.
［ハードコート層］
　偏光板はハードコート層を含んでいてもよい。ハードコート層は最外層として含まれていればよく、偏光子からみて、光学異方性層側の最外層に含まれていることが好ましい。
　本明細書において、ハードコート層とは、形成されることで透明支持体の鉛筆硬度が上昇する層をいう。実用的には、ハードコート層積層後の鉛筆硬度（ＪＩＳ Ｋ５４００）はＨ以上が好ましく、更に好ましくは２Ｈ以上であり、最も好ましくは３Ｈ以上である。ハードコート層の厚みは、０．４～３５μｍが好ましく、更に好ましくは１～３０μｍであり、最も好ましくは１．５～２０μｍである。
　具体的な組成については特開２０１２－１０３６８９号公報の記載を参照することができる。 [Hard coat layer]
The polarizing plate may include a hard coat layer. The hard coat layer may be included as the outermost layer, and is preferably included in the outermost layer on the optically anisotropic layer side as viewed from the polarizer.
In this specification, the hard coat layer refers to a layer that, when formed, increases the pencil hardness of the transparent support. Practically, the pencil hardness (JIS K5400) after laminating the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. The thickness of the hard coat layer is preferably 0.4 to 35 μm, more preferably 1 to 30 μm, and most preferably 1.5 to 20 μm.
For the specific composition, reference can be made to the description in JP 2012-103689 A.
　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、試薬、物質量とその割合、操作等は本発明の趣旨から逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下の実施例に限定されるものではない。
　下記実施例において、シクロオレフィンポリマー含有層、アクリルポリマー層、光学異方性層等の形成の際の塗布液の塗布には図２に示す工程を用い、塗布装置としてはエクストルージョン型のコータを用いた。塗布工程の後、フィルムはそのまま乾燥工程に付した。乾燥装置としてはスリットノズルによる対流乾燥方式を用い、乾燥時間はフィルム１２（図２）の搬送速度を制御することで調整した。 The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following examples.
In the following examples, the process shown in FIG. 2 is used for coating of the coating liquid when forming the cycloolefin polymer-containing layer, the acrylic polymer layer, the optically anisotropic layer, etc., and an extrusion type coater is used as the coating apparatus. Using. After the coating process, the film was directly subjected to the drying process. A convection drying method using a slit nozzle was used as a drying device, and the drying time was adjusted by controlling the conveyance speed of the film 12 (FIG. 2).
＜仮支持体1（セルロースアセテートフィルム）の作製＞
　下記の組成物をミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、セルロースアセテート溶液を調製した。

　セルロースアセテート溶液の組成
――――――――――――――――――――――――――――――――――
酢化度６０．７～６１．１％のセルロースアセテート　　　　１００質量部
トリフェニルホスフェート（可塑剤）　　　　　　　　　　　７．８質量部
ビフェニルジフェニルホスフェート（可塑剤）　　　　　　　３．９質量部
メチレンクロライド（第１溶媒）　　　　　　　　　　　　　３３６質量部
メタノール（第２溶媒）　　　　　　　　　　　　　　　　　　２９質量部
１－ブタノール（第３溶媒）　　　　　　　　　　　　　　　　１１質量部
―――――――――――――――――――――――――――――――――― <Preparation of temporary support 1 (cellulose acetate film)>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

Composition of cellulose acetate solution ――――――――――――――――――――――――――――――――――
Cellulose acetate having an acetylation degree of 60.7 to 61.1% 100 parts by mass of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass of methylene chloride (first solvent) 336 parts by mass Methanol (second solvent) 29 parts by mass 1-butanol (third solvent) 11 parts by mass ――――――――――――――――――――――――――――― ―――――
　別のミキシングタンクに、下記の添加剤（Ａ）１６質量部、メチレンクロライド９２質量部及びメタノール８質量部を投入し、加熱しながら攪拌して、添加剤（Ａ）溶液を調製した。セルロースアセテート溶液４７４質量部に添加剤（Ａ）２５質量部を混合し、充分に攪拌してドープを調製した。添加剤（Ａ）の添加量は、セルロースアセテート１００質量部に対して、６．０質量部であった。 In another mixing tank, 16 parts by mass of the following additive (A), 92 parts by mass of methylene chloride and 8 parts by mass of methanol were added and stirred while heating to prepare an additive (A) solution. The dope was prepared by mixing 474 parts by mass of the cellulose acetate solution with 25 parts by mass of the additive (A) and stirring sufficiently. The addition amount of the additive (A) was 6.0 parts by mass with respect to 100 parts by mass of cellulose acetate.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　得られたドープを、バンド延伸機を用いて流延した。バンド上での膜面温度が４０℃となってから、７０℃の温風で１分乾燥し、バンドからフィルムを１４０℃の乾燥風で１０分乾燥し、残留溶剤量が０．３質量％のセルロースアセテートフィルム（仮支持体1）を作製した。
　得られた長尺状の仮支持体1の幅は１４９０ｍｍであり、厚さは８０μｍであった。また、面内レターデーション（Ｒｅ）は８ｎｍ、厚み方向のレターデーション（Ｒｔｈ）は７８ｎｍであった。 The obtained dope was cast using a band stretching machine. After the film surface temperature on the band reaches 40 ° C., the film is dried with warm air of 70 ° C. for 1 minute, and the film from the band is dried with 140 ° C. drying air for 10 minutes, and the residual solvent amount is 0.3% by mass. A cellulose acetate film (temporary support 1) was prepared.
The obtained long temporary support 1 had a width of 1490 mm and a thickness of 80 μm. The in-plane retardation (Re) was 8 nm and the thickness direction retardation (Rth) was 78 nm.
＜フィルムＴ１（仮支持体／シクロオレフィンポリマー含有層）の作製＞
（シクロオレフィンポリマー含有層の形成）
上記で作製した仮支持体1上に、下記組成のシクロオレフィンポリマー塗布液７０ｃｃ/ｍ2を連続的に塗布した。仮支持体1の搬送速度は３０ｍ/分とし、８０℃の温風で６０秒乾燥させた。乾燥後の膜厚は７μｍであった。

シクロオレフィンポリマー含有層形成用塗布液１の組成
――――――――――――――――――――――――――――――――――
シクロオレフィンポリマー１（アペル、三井化学製）　　　　　１０質量部
シクロヘキサン　　　　　　　　　　　　　　　　　　　　　１００質量部
―――――――――――――――――――――――――――――――――― <Preparation of film T1 (temporary support / cycloolefin polymer-containing layer)>
(Formation of cycloolefin polymer-containing layer)
On the temporary support 1 produced as described above, a cycloolefin polymer coating solution of 70 cc / m 2 having the following composition was continuously applied. The transport speed of the temporary support 1 was 30 m / min, and it was dried with warm air at 80 ° C. for 60 seconds. The film thickness after drying was 7 μm.

Composition of coating solution 1 for forming a layer containing cycloolefin polymer ――――――――――――――――――――――――――――――――――
Cycloolefin polymer 1 (Appel, manufactured by Mitsui Chemicals) 10 parts by mass Cyclohexane 100 parts by mass ――――――――――――――――――――――――――――――― -
＜フィルムＴ２（仮支持体／シクロオレフィンポリマー含有層）の作製＞
（シクロオレフィンポリマー含有層の形成）
　仮支持体1上に、上記のシクロオレフィンポリマー含有層形成用塗布液１の２０ｃｃ/ｍ2を連続的に塗布した。仮支持体1の搬送速度は３０ｍ/分とし、８０℃の温風で６０秒乾燥させた。乾燥後の膜厚は２μｍであった。 <Production of film T2 (temporary support / cycloolefin polymer-containing layer)>
(Formation of cycloolefin polymer-containing layer)
On the temporary support 1, 20 cc / m 2 of the above cycloolefin polymer-containing layer forming coating solution 1 was continuously applied. The transport speed of the temporary support 1 was 30 m / min, and it was dried with warm air at 80 ° C. for 60 seconds. The film thickness after drying was 2 μm.
＜フィルムＴ３（仮支持体／シクロオレフィンポリマー含有層）の作製＞
（シクロオレフィンポリマー含有層の形成）
　仮支持体1上に、下記組成のシクロオレフィンポリマー塗布液７０ｃｃ/ｍ2を連続的に塗布した。仮支持体1の搬送速度は３０ｍ/分とし、８０℃の温風で６０秒乾燥した。乾燥装置としてはスリットノズルによる対流乾燥方式を用い、乾燥時間はフィルム１２（図２）の搬送速度を制御することで調整した。乾燥後の膜厚は７μｍであった。 <Production of film T3 (temporary support / cycloolefin polymer-containing layer)>
(Formation of cycloolefin polymer-containing layer)
On the temporary support 1, a cycloolefin polymer coating solution 70 cc / m 2 having the following composition was continuously coated. The conveyance speed of the temporary support 1 was 30 m / min, and it was dried with warm air at 80 ° C. for 60 seconds. A convection drying method using a slit nozzle was used as a drying device, and the drying time was adjusted by controlling the conveyance speed of the film 12 (FIG. 2). The film thickness after drying was 7 μm.
シクロオレフィンポリマー含有層形成用塗布液２の組成
――――――――――――――――――――――――――――――――――
シクロオレフィンポリマー２（アートン、JＳＲ製）　　　 　　１０質量部
シクロヘキサン　　　　　　　　　　　　　　　　　　　　　１００質量部
―――――――――――――――――――――――――――――――――― Composition of coating solution 2 for forming a layer containing cycloolefin polymer ――――――――――――――――――――――――――――――――――
Cycloolefin polymer 2 (Arton, manufactured by JSR) 10 parts by mass Cyclohexane 100 parts by mass ――――――――――――――――――――――――――――――――― -
＜フィルムＴ４（仮支持体／シクロオレフィンポリマー含有層/アクリルポリマー層）の作製＞
（アクリルポリマー層の形成）
　上記フィルムＴ１のシクロオレフィンポリマー含有層側表面に、下記組成のアクリル層形成用塗布液８．８ｃｃ/ｍ2を連続的に塗布した。フィルムＴ１の搬送速度は３０ｍ/分とし、４０℃の温風で６０秒乾燥した。更に窒素パージ下酸素濃度約０．１％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４００ｍＷ／ｃｍ2、照射量３００ｍＪ／ｃｍ2の紫外線を照射して塗布層を硬化させて、膜厚は２．６μｍのアクリルポリマー層を形成した。 <Preparation of film T4 (temporary support / cycloolefin polymer-containing layer / acrylic polymer layer)>
(Formation of acrylic polymer layer)
On the surface of the film T1 on the side of the cycloolefin polymer-containing layer, 8.8 cc / m 2 of an acrylic layer forming coating solution having the following composition was continuously applied. The transport speed of the film T1 was 30 m / min, and it was dried for 60 seconds with warm air at 40 ° C. Furthermore, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm 2 and an irradiation amount of 300 mJ / cm 2 were irradiated. The coating layer was cured to form an acrylic polymer layer having a film thickness of 2.6 μm.
アクリルポリマー層形成用塗布液１の組成
――――――――――――――――――――――――――――――――――
アクリレート（ＰＥＴ－３０、日本化薬製）　　　　　　　　　２０質量部
重合開始剤（イルガキュア１２７、チバ・スペシャルティ・ケミカルズ製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．３質量部
レベリング剤　ＦＰ１　　　　　　　　　　　　　　　　　　０．２質量部
溶剤　　　　　酢酸メチル　　　　　　　　　　　　　　　　　７２質量部
―――――――――――――――――――――――――――――――――― Composition of Coating Solution 1 for Acrylic Polymer Layer Formation ――――――――――――――――――――――――――――――――――
Acrylate (PET-30, Nippon Kayaku) 20 parts by mass polymerization initiator (Irgacure 127, Ciba Specialty Chemicals)
0.3 parts by weight leveling agent FP1 0.2 parts by weight Solvent methyl acetate 72 parts by weight ――――――――――――――――――――――――――――――― ―――
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
＜仮支持体／シクロオレフィンポリマー含有層/アクリルポリマー層/光学異方性層/ 付フィルムＴ５の作製＞
（光学異方性層１の形成）
　上記フィルムＴ４のアクリルポリマー層側表面に下記組成の塗布液５．６ｃｃ/ｍ2を連続的に塗布した。フィルムＴ４の搬送速度を３０ｍ/分とし、塗布液の溶媒の乾燥および棒状液晶化合物の配向熟成のために、６０℃の温風で６０秒間加熱した。その後、酸素濃度３００ｐｐｍ雰囲気中で高圧水銀灯により３００ｍＪ／ｃｍ2の積算光量の紫外線照射を行い、液晶化合物の配向を固定化した。上記光学異方性層の厚みは１．９μｍであった。棒状液晶化合物の長軸のフィルム面に対する平均傾斜角は９０°であり、液晶化合物がフィルム面に対して、垂直に配向していることを確認した。 <Temporary support / Cycloolefin polymer-containing layer / Acrylic polymer layer / Optically anisotropic layer / Production of attached film T5>
(Formation of optically anisotropic layer 1)
A coating liquid 5.6 cc / m 2 having the following composition was continuously applied to the surface of the film T4 on the acrylic polymer layer side. The conveyance speed of the film T4 was set to 30 m / min, and heating was performed with warm air of 60 ° C. for 60 seconds in order to dry the solvent of the coating solution and to mature the alignment of the rod-like liquid crystal compound. Thereafter, ultraviolet rays were irradiated with an integrated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp in an atmosphere with an oxygen concentration of 300 ppm to fix the orientation of the liquid crystal compound. The thickness of the optically anisotropic layer was 1.9 μm. The average inclination angle of the long axis of the rod-like liquid crystal compound with respect to the film surface was 90 °, and it was confirmed that the liquid crystal compound was aligned perpendicular to the film surface.
光学異方性層１の塗布液の組成
――――――――――――――――――――――――――――――――――
重合性液晶化合物（ＬＣ－１－１）　　　　　　　　　　　　　８０質量部
重合性液晶化合物（ＬＣ－２）　　　　　　　　　　　　　　　２０質量部
光重合開始剤（イルガキュア９０７、チバ・ジャパン社製）　　　３質量部
配向制御剤　ＦＰ２　　　　　　　　　　　　　　　　　　　　　１質量部
配向補助剤　ＦＰ３　　　　　　　　　　　　　　　　　　　０．４質量部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　１９３質量部
シクロヘキサノン　　　　　　　　　　　　　　　　　　　　　５０質量部
―――――――――――――――――――――――――――――――――― Composition of coating solution for optically anisotropic layer 1 ――――――――――――――――――――――――――――――――――
Polymerizable liquid crystal compound (LC-1-1) 80 parts by mass Polymerizable liquid crystal compound (LC-2) 20 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass orientation controller FP2 1 part by mass Alignment aid FP3 0.4 parts by mass Methyl ethyl ketone 193 parts by mass Cyclohexanone 50 parts by mass ――――――――――――――――――――――――――――――――― -
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
＜仮支持体／シクロオレフィンポリマー含有層/光学異方性層/アクリルポリマー層/ 付フィルムＴ６の作製＞
（光学異方性層２の形成）
　　上記フィルムＴ１のシクロオレフィンポリマー含有層側表面に、連続的にラビング処理を施した。このとき、長尺状のフィルムの長手方向と搬送方向は平行であり、フィルム長手方向とラビングローラーの回転軸とのなす角度が１５°（時計回り）とした（フィルム長手方向を９０°とすると、ラビングローラーの回転軸は７５°）。
　上記光学異方性層１の塗布液を下記光学異方性層２の塗布液に変更すること以外は光学異方性層１と同様に作製した。上記光学異方性層の厚みは１．９μｍであった。棒状液晶化合物の長軸のフィルム面に対する平均傾斜角は０°であり、液晶化合物がフィルム面に対して、水平に配向していることを確認した。 <Temporary Support / Cycloolefin Polymer-Containing Layer / Optically Anisotropic Layer / Acrylic Polymer Layer / Fabrication of Attached Film T6>
(Formation of optically anisotropic layer 2)
The surface of the film T1 on the cycloolefin polymer-containing layer side was continuously rubbed. At this time, the longitudinal direction of the long film and the transport direction are parallel, and the angle formed by the film longitudinal direction and the rotation axis of the rubbing roller is 15 ° (clockwise) (when the film longitudinal direction is 90 °). The rotation axis of the rubbing roller is 75 °).
The optically anisotropic layer 1 was prepared in the same manner as the optically anisotropic layer 1 except that the coating liquid for the optically anisotropic layer 1 was changed to the coating liquid for the optically anisotropic layer 2 described below. The thickness of the optically anisotropic layer was 1.9 μm. The average inclination angle of the long axis of the rod-like liquid crystal compound with respect to the film surface was 0 °, and it was confirmed that the liquid crystal compound was aligned horizontally with respect to the film surface.
光学異方性層２の塗布液の組成
――――――――――――――――――――――――――――――――――
重合性液晶化合物（ＬＣ－１－１）　　　　　　　　　　　　　８０質量部
重合性液晶化合物（ＬＣ－２）　　　　　　　　　　　　　　　２０質量部
光重合開始剤（イルガキュア９０７、チバ・ジャパン社製）  　　３質量部
ポリマー（Ａ）　　　　　　　　　　　　　　　　　　　　　０．６質量部
フッ素系ポリマー（ＦＰ１）　　　　　　　　　　　　　　　０．３質量部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　１８３質量部
シクロヘキサノン　　　　　　　　　　　　　　　　　　　　　４０質量部
―――――――――――――――――――――――――――――――――― Composition of coating solution for optically anisotropic layer 2 ――――――――――――――――――――――――――――――――――
Polymerizable liquid crystal compound (LC-1-1) 80 parts by mass Polymerizable liquid crystal compound (LC-2) 20 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass polymer (A) 0.6 Part by mass Fluoropolymer (FP1) 0.3 part by mass Methyl ethyl ketone 183 parts by mass Cyclohexanone 40 parts by mass ――――――――――――――――――――――――――――― ―――――
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（アクリルポリマー層の形成）
　上記光学異方性層２表面に、上記のアクリルポリマー層形成用塗布液８．８ｃｃ/ｍ2を連続的に塗布した。フィルムの搬送速度を３０ｍ/分とし、４０℃の温風で６０秒乾燥した。更に窒素パージ下酸素濃度約０．１％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４００ｍＷ／ｃｍ2、照射量３００ｍＪ／ｃｍ2の紫外線を照射して塗布層を硬化させて、膜厚は２．６μｍのアクリルポリマー層を形成した。 (Formation of acrylic polymer layer)
The acrylic polymer layer forming coating solution 8.8 cc / m 2 was continuously applied to the surface of the optically anisotropic layer 2. The film was conveyed at a speed of 30 m / min and dried with warm air at 40 ° C. for 60 seconds. Furthermore, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm 2 and an irradiation amount of 300 mJ / cm 2 were irradiated. The coating layer was cured to form an acrylic polymer layer having a film thickness of 2.6 μm.
＜偏光板１～６の作製＞
（偏光子の作製）
　厚さ８０μｍのロール状ポリビニルアルコールフィルムをヨウ素水溶液中で連続して５倍に延伸し、乾燥して厚さ２０μｍの偏光膜（偏光子）を得た。
(フィルムＴ１の偏光子への貼り付け)
フィルムＴ１のシクロオレフィンポリマー含有層側にコロナ処理を行い、コロナ処理面においてＰＶＡ（（株）クラレ製、ＰＶＡ－１１７Ｈ）３％水溶液を接着剤を用いて上記偏光膜の片側と貼り合わせた。貼り合わせた後、仮支持体1をシクロオレフィンポリマー含有層との界面で剥離して、偏光板１を得た。仮支持体1は容易に剥がすことができた。偏光板１の厚みは２７μｍであった。 <Preparation of polarizing plates 1 to 6>
(Production of polarizer)
A roll-like polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film (polarizer) having a thickness of 20 μm.
(Attaching film T1 to polarizer)
The cycloolefin polymer-containing layer side of the film T1 was subjected to corona treatment, and on the corona treatment surface, a 3% aqueous solution of PVA (manufactured by Kuraray Co., Ltd., PVA-117H) was bonded to one side of the polarizing film. After the lamination, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer, whereby the polarizing plate 1 was obtained. The temporary support 1 could be easily peeled off. The thickness of the polarizing plate 1 was 27 μm.
(フィルムＴ２の偏光子への貼り付け)
　フィルムＴ１をフィルムＴ２に置き換える以外は偏光板１と同様に偏光板２を作製した。偏光子に貼り合わせた後、仮支持体1をシクロオレフィンポリマー含有層との界面で剥離し（容易に剥がすことができた。）、偏光板２を得た。偏光板２の厚みは２２μｍであった。 (Attaching film T2 to polarizer)
A polarizing plate 2 was produced in the same manner as the polarizing plate 1 except that the film T1 was replaced with the film T2. After bonding to the polarizer, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 2. The thickness of the polarizing plate 2 was 22 μm.
(フィルムＴ３の偏光子への貼り付け)
　フィルムＴ１をフィルムＴ３に置き換える以外は偏光板１と同様に偏光板３を作製した。偏光子に貼り合わせた後、仮支持体1をシクロオレフィンポリマー含有層との界面で剥離し（容易に剥がすことができた。）、偏光板３を得た。偏光板３の厚みは２７μｍであった。 (Attaching film T3 to polarizer)
A polarizing plate 3 was produced in the same manner as the polarizing plate 1 except that the film T1 was replaced with the film T3. After bonding to the polarizer, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be peeled off easily) to obtain the polarizing plate 3. The thickness of the polarizing plate 3 was 27 μm.
(フィルムＴ４の偏光子への貼り付け)
　市販のアクリル接着剤（東亞合成株式会社製　ＵＶ-3300）を用いてフィルムＴ２のアクリルポリマー層の面と上記偏光膜の片側と貼り合わせた。貼り合わせた後、仮支持体1をシクロオレフィンポリマー含有層との界面で剥離し（容易に剥がすことができた。）、偏光板４を得た。偏光板４の厚みは２９．６μｍであった。 (Attaching film T4 to polarizer)
A commercially available acrylic adhesive (UV-3300, manufactured by Toagosei Co., Ltd.) was used to attach the surface of the acrylic polymer layer of the film T2 to one side of the polarizing film. After the lamination, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 4. The thickness of the polarizing plate 4 was 29.6 μm.
(フィルムＴ５の偏光子への貼り付け)
　ＰＶＡ（（株）クラレ製、ＰＶＡ－１１７Ｈ）３％水溶液を接着剤を用いてフィルムＴ３の液晶面と上記偏光膜の片側と貼り合わせた。貼り合わせた後、仮支持体1をシクロオレフィンポリマー含有層との界面で剥離し（容易に剥がすことができた。）、偏光板５を得た。偏光板５の厚みは３１．５μｍであった。 (Attaching film T5 to polarizer)
A 3% aqueous solution of PVA (manufactured by Kuraray Co., Ltd., PVA-117H) was bonded to the liquid crystal surface of the film T3 and one side of the polarizing film using an adhesive. After the lamination, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 5. The thickness of the polarizing plate 5 was 31.5 μm.
(フィルムＴ６の偏光子への貼り付け)
　市販のアクリル接着剤（東亞合成株式会社製　ＵＶ-3300）を用いてフィルムＴ４のアクリルポリマー層の面と上記偏光膜の片側と貼り合わせた。貼り合わせた後、仮支持体1をシクロオレフィンポリマー含有層との界面で剥離し（容易に剥がすことができた。）、偏光板６を得た。偏光板６の厚みは３１．５μｍであった。 (Attaching film T6 to polarizer)
A commercially available acrylic adhesive (UV-3300, manufactured by Toagosei Co., Ltd.) was used to bond the surface of the acrylic polymer layer of the film T4 to one side of the polarizing film. After the lamination, the temporary support 1 was peeled off at the interface with the cycloolefin polymer-containing layer (it could be easily peeled off) to obtain the polarizing plate 6. The thickness of the polarizing plate 6 was 31.5 μm.
＜偏光板７～１２の作製　仮支持体剥離後に偏光子貼り付け＞
（仮支持体からの剥離）
　上記で得られたフィルムＴ１～Ｔ６を仮支持体1から剥がし、フィルムＴ７～Ｔ１２を得た。
（フィルムＴ７～１２の偏光子への貼り付け）
　フィルムＴ７～Ｔ１２それぞれのシクロオレフィンポリマー含有層以外の層の面が偏光子側の面になるように、偏光子と貼り合わせた。
　フィルムＴ７～Ｔ１２を偏光子と貼り合わせる際は、偏光板１～６のそれぞれと同じ方法で貼り合わせ、偏光子７～１２を得た。偏光板の厚みは偏光板７：２７μｍ、偏光板８：２２μｍ、偏光板９：２７μｍ、偏光板１０：２９．６μｍ、偏光板１１：３１．５μｍ、偏光板１２：３１．５μｍであった。 <Preparation of Polarizing Plates 7 to 12: Affixing the polarizer after peeling the temporary support>
(Peeling from temporary support)
The films T1 to T6 obtained above were peeled from the temporary support 1 to obtain films T7 to T12.
(Attaching films T7-12 to polarizer)
The films T7 to T12 were bonded to the polarizer so that the surfaces of the layers other than the cycloolefin polymer-containing layer were surfaces on the polarizer side.
When the films T7 to T12 were bonded to the polarizer, the polarizers 7 to 12 were obtained by bonding the films T7 to T12 in the same manner as the polarizing plates 1 to 6. The thicknesses of the polarizing plate were as follows: polarizing plate 7: 27 μm, polarizing plate 8: 22 μm, polarizing plate 9: 27 μm, polarizing plate 10: 29.6 μm, polarizing plate 11: 31.5 μm, polarizing plate 12: 31.5 μm.
比較例
＜ＰＥＴ／アクリルポリマー層/光学異方性層/ 付フィルムＴ１３の作製＞
　支持体ＰＥＴ（富士フイルム製　厚み７５μｍ）上にフィルムＴ４の作製の際と同様の方法でに記載の方法でアクリルポリマー層を形成し、さらに、光学異方性層１の形成の際と同様の方法で光学異方性層を形成してフィルムＴ１３を得た。 Comparative Example <Preparation of PET / acrylic polymer layer / optically anisotropic layer / attached film T13>
An acrylic polymer layer is formed on the support PET (Fuji Film, thickness 75 μm) in the same manner as in the production of the film T4, and the same as in the formation of the optically anisotropic layer 1. An optically anisotropic layer was formed by the method to obtain a film T13.
　得られたフィルムＴ１～Ｔ６、Ｔ１３の面状検査を行った。面状検査は光源としてはFLAT PANEL FP-901-2（GUNMA USHIO 製）を用い、偏光板をクロスニコルで配置して目視で検査を行った。フィルムＴ１３は虹ムラが顕著であり検査することができなかったのに対し、フィルムＴ１～Ｔ６は虹ムラなく検査することが可能であった。 The surface inspection of the obtained films T1 to T6 and T13 was performed. For the surface inspection, FLAT PANEL FP-901-2 (manufactured by GUNMA） USHIO) was used as the light source, and the polarizing plate was placed in crossed Nicols and visually inspected. The film T13 showed remarkable rainbow unevenness and could not be inspected, whereas the films T1 to T6 could be inspected without rainbow unevenness.
＜ＴＡＣ／アクリルポリマー層/光学異方性層/ 付フィルムＴ１４の作製＞
　支持体ＴＡＣ（富士フイルム製　フジタック厚み８０μｍ）上にフィルムＴ４の作製の際と同様の方法でアクリルポリマー層を形成し、さらに、光学異方性層１の形成の際と同様の光学異方性層を形成してフィルムＴ１４を得た。フィルムＴ１４はＴＡＣとアクリルポリマー層の界面が密着しており剥離することができなかった。 <Production of TAC / acrylic polymer layer / optically anisotropic layer / attached film T14>
An acrylic polymer layer is formed on the support TAC (Fuji Film Fujitak thickness 80 μm) in the same manner as in the production of the film T4, and the optical anisotropy is the same as in the formation of the optically anisotropic layer 1. A layer was formed to obtain a film T14. In the film T14, the interface between the TAC and the acrylic polymer layer was in close contact and could not be peeled off.
＜シクロオレフィンポリマー樹脂シートＴ１５の作製）
　市販されているシクロオレフィンポリマーフィルム“ＺＥＯＮＯＲ　ＺＦ１４”（日本ゼオン製）を、下記表１に示す延伸温度（Ｔｇは環状オレフィン系樹脂のガラス転移温度）及び延伸倍率により延伸して、環状オレフィン樹脂シートＴ１５を得た。発明者の実験では、これ以上の倍率で延伸した場合、フィルム搬送中にフィルムが破断しフィルムを形成することができなかった。 <Preparation of cycloolefin polymer resin sheet T15)
A commercially available cycloolefin polymer film “ZEONOR ZF14” (manufactured by Nippon Zeon Co., Ltd.) is stretched at the stretching temperature (Tg is the glass transition temperature of the cyclic olefin resin) and the stretching ratio shown in Table 1 below, and the cyclic olefin resin sheet T15 was obtained. In the inventor's experiment, when the film was stretched at a higher magnification, the film was broken during film conveyance, and a film could not be formed.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
１　仮支持体
２　シクロオレフィンポリマー含有層
３　アクリルポリマー層
４　光学異方性層 DESCRIPTION OF SYMBOLS 1 Temporary support body 2 Cycloolefin polymer content layer 3 Acrylic polymer layer 4 Optically anisotropic layer

Claims (14)

  1. 偏光板の製造方法であって、下記（１）～（３）を含む製造方法：
    （１）仮支持体上にシクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成すること、
    （２）前記シクロオレフィンポリマー含有層と偏光子を含むフィルムとを積層すること、
    （３）前記仮支持体を剥離すること。     A method for producing a polarizing plate, comprising the following (1) to (3):
    (1) applying a composition containing a cycloolefin polymer on a temporary support to form a cycloolefin polymer-containing layer;
    (2) laminating the cycloolefin polymer-containing layer and a film containing a polarizer;
    (3) Peeling off the temporary support.
  2. 前記（１）において、仮支持体の表面に直接、シクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成する請求項１に記載の製造方法。 2. The production method according to claim 1, wherein in (1), the cycloolefin polymer-containing layer is formed by directly applying a composition containing a cycloolefin polymer to the surface of the temporary support.
  3. 前記（１）～（３）をこの順で含み、
    前記（２）において、前記仮支持体と前記シクロオレフィンポリマー含有層とを含む転写材料および偏光子を含むフィルムが積層され、
    前記（２）において形成された積層体から前記仮支持体を剥離することを含む請求項１または２に記載の製造方法。     Including (1) to (3) in this order,
    In (2), a film including a transfer material and a polarizer including the temporary support and the cycloolefin polymer-containing layer is laminated,
    The manufacturing method of Claim 1 or 2 including peeling the said temporary support body from the laminated body formed in said (2).
  4. 前記（１）のシクロオレフィンポリマー含有層の形成が前記シクロオレフィンポリマー含有層の膜厚が２０μｍ以下となるように行われる請求項１～３のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 3, wherein the cycloolefin polymer-containing layer (1) is formed so that the thickness of the cycloolefin polymer-containing layer is 20 µm or less.
  5. 前記（１）のシクロオレフィンポリマー含有層の形成が前記シクロオレフィンポリマー含有層の膜厚が１５μｍ以下となるように行われる請求項１～３のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 3, wherein the formation of the cycloolefin polymer-containing layer (1) is performed so that the thickness of the cycloolefin polymer-containing layer is 15 µm or less.
  6. 前記（２）の積層が前記シクロオレフィンポリマー含有層と前記の偏光子を含むフィルムとが接着層を介して直接接着するように行われる請求項１～５のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 5, wherein the lamination of (2) is performed such that the cycloolefin polymer-containing layer and the film containing the polarizer are directly bonded via an adhesive layer. .
  7. 前記積層が前記シクロオレフィンポリマー含有層と前記偏光子とが前記接着層を介して直接接着するように行われる請求項６に記載の製造方法。 The manufacturing method according to claim 6, wherein the stacking is performed so that the cycloolefin polymer-containing layer and the polarizer are directly bonded via the adhesive layer.
  8. 前記（１）の後かつ前記（２）の前に、光学異方性層およびアクリルポリマー層からなる群から選択される1層以上の層を前記シクロオレフィンポリマー含有層上に形成することを含む請求項１～５のいずれか一項に記載の製造方法。 Forming one or more layers selected from the group consisting of an optically anisotropic layer and an acrylic polymer layer on the cycloolefin polymer-containing layer after (1) and before (2) The production method according to any one of claims 1 to 5.
  9. 請求項１～８のいずれか一項に記載の製造方法により得られる偏光板であって、膜厚が２０μｍ以下のシクロオレフィンポリマー含有層と偏光子とを含む偏光板。 A polarizing plate obtained by the production method according to any one of claims 1 to 8, comprising a cycloolefin polymer-containing layer having a film thickness of 20 μm or less and a polarizer.
  10. 偏光子および前記偏光子と接着層を介して直接接着されている膜厚が２０μｍ以下のシクロオレフィンポリマー含有層を含む偏光板。 A polarizing plate comprising a polarizer and a cycloolefin polymer-containing layer having a thickness of 20 μm or less that is directly bonded to the polarizer via an adhesive layer.
  11. 偏光板製造のための転写材料の製造方法であって、
    仮支持体上にシクロオレフィンポリマーを含む組成物を塗布してシクロオレフィンポリマー含有層を形成することを含む製造方法。     A method for producing a transfer material for producing a polarizing plate,
    The manufacturing method including apply | coating the composition containing a cycloolefin polymer on a temporary support body, and forming a cycloolefin polymer content layer.
  12. 前記シクロオレフィンポリマー含有層の形成が前記シクロオレフィンポリマー含有層の膜厚が２０μｍ以下となるように行われる請求項１１に記載の製造方法。 The production method according to claim 11, wherein the cycloolefin polymer-containing layer is formed so that the film thickness of the cycloolefin polymer-containing layer is 20 μm or less.
  13. 前記シクロオレフィンポリマー含有層の形成が前記シクロオレフィンポリマー含有層の膜厚が１５μｍ以下となるように行われる請求項１１または１２に記載の製造方法。 The production method according to claim 11 or 12, wherein the cycloolefin polymer-containing layer is formed so that a film thickness of the cycloolefin polymer-containing layer is 15 µm or less.
  14. 請求項１１～１３のいずれか一項に記載の製造方法により得られる、偏光板製造のための転写材料であって、膜厚が２０μｍ以下のシクロオレフィンポリマー含有層と仮支持体とを含む転写材料。 A transfer material for producing a polarizing plate obtained by the production method according to any one of claims 11 to 13, comprising a cycloolefin polymer-containing layer having a thickness of 20 µm or less and a temporary support. material.
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