JP2016105127A - Alignment layer, laminate, optical film, method for producing optical film, polarizing plate, liquid crystal display device and alignment layer forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alignment layer having excellent peelability from a base material and also excellent liquid crystal aligning properties, and a laminate, an optical film, a method for producing an optical film, a polarizing plate, a liquid crystal display device and an alignment layer forming composition.SOLUTION: An alignment layer comprises a polymer that consists of only a monomer with an SP value of 22.0 or more and a percentage of number of hydroxy groups per molecule based on the monomer molecular weight of 0.4% or more, the polymer obtained by curing the monomer with active energy rays.SELECTED DRAWING: None

Description

  The present invention relates to an alignment film, a laminate, an optical film, a method for producing an optical film, a polarizing plate, a liquid crystal display device, and a composition for forming an alignment film.

  In general, a retardation film is used for a liquid crystal display device. As a method for producing a retardation film, it is known to form a retardation layer on an alignment-treated substrate. In addition, the retardation layer formed on the base material is adhered to the film to be transferred, and then the base material is peeled from the phase difference layer to produce a phase difference film in which the phase difference layer and the film to be transferred are laminated. It is known to do.

  For example, in Patent Document 1, a step of applying a light-transmitting isotropic resin on a substrate to form an isotropic resin layer, and applying a polymerizable liquid crystal or a liquid crystal polymer on the isotropic resin layer An optical element manufacturing method including a step of forming a liquid crystal layer by aligning the substrate and a step of peeling and removing the substrate from the isotropic resin layer is described.

  Patent Document 2 discloses an optical film transfer body provided with a transfer layer to be laminated on a transfer substrate and a substrate that supports the transfer layer, and the orientation in which the transfer layer is formed on the substrate. The first alignment film by the film material layer and the first retardation layer according to the first alignment film, the substrate is a polyethylene terephthalate (PET) film, and the alignment film material layer is trimethylolpropane. An optical film transfer body produced from a mixed composition containing triacrylate, urethane-modified pentaerythritol acrylate oligomer, and butyl acrylate is described.

  Patent Document 3 discloses a retardation film having a support, an intermediate layer, and a retardation layer in which the alignment state of the liquid crystal material is fixed in this order, and the support has an average acyl group substitution degree DS of 2. Containing cellulose acylate satisfying 0 <DS <2.6, and a specific polycondensation ester or a specific sugar ester, the intermediate layer containing a polyvinyl alcohol resin or an acrylic resin having a polar group, and a retardation layer Describes a retardation film containing a liquid crystal compound having homeotropic alignment and having specific optical characteristics.

JP 2007-71932 A JP 2014-71190 A JP 2013-235232 A

  As a method for producing an alignment film for forming a retardation layer, a method of applying an aqueous composition containing polyvinyl alcohol is known. However, the application of the aqueous composition takes time to dry, has low productivity, and has high surface tension. Therefore, if the substrate is not pretreated (corona treatment, saponification treatment, etc.), the wettability is poor and defects appear. It tends to be easy. An alignment film can also be produced by applying a composition containing an organic solvent, but the base material and the coating layer are mixed by dissolution of the base material with the organic solvent, and the peelability of the alignment film from the base material ( In some cases, the transferability is lowered, and the alignment film becomes hydrophobic, so that the liquid crystal alignment becomes poor.

  This invention is made | formed in view of such a situation, It was made into the problem which should be solved to provide the orientation film | membrane with favorable peelability from a base material and favorable liquid crystal orientation. Furthermore, this invention made it the subject which should be solved to provide the laminated body containing the said oriented film, the optical film manufactured using the said oriented film, and the manufacturing method of the said optical film. Furthermore, this invention made it the subject which should be solved to provide the polarizing plate and liquid crystal display device which have the said optical film. Furthermore, this invention made it the problem which should be solved to provide the composition for alignment film formation for manufacturing the said alignment film.

  In order to solve the above-mentioned problems, the present inventors have intensively investigated the results of SP (solubility parameter) value and a monomer satisfying a predetermined condition in terms of the number of hydroxyl groups per monomer molecule with respect to the molecular weight of the monomer using active energy rays. It discovered that it could provide the oriented film which solved the said subject by hardening, and came to complete this invention. That is, according to the present invention, the following inventions are provided.

(1) The monomer constituting the polymer includes only a monomer having an SP value of 22.0 or more and a ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer of 0.4% or more. An alignment film comprising a polymer obtained by curing with active energy rays.
(2) The alignment film according to (1), wherein the SP value of the monomer is 23.0 to 25.0.
(3) The alignment film according to (1) or (2), wherein the ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer is 0.4% or more and 2% or less.
(4) The alignment film according to any one of (1) to (3), wherein the polymerizable group equivalent of the monomer represented by the following formula is 100 to 200.
Polymerizable group equivalent of monomer = molecular weight of monomer / number of polymerizable groups per molecule of monomer (5) Any of (1) to (4), wherein the monomer has 2 to 8 polymerizable groups in one molecule The alignment film described in 1.
(6) The alignment film according to any one of (1) to (5), wherein the monomer has an acryloyl group or a methacryloyl group.
(7) A laminate having a base material, the alignment film according to any one of (1) to (6), and a retardation layer in the order described above.
(8) The laminate according to (7), wherein the substrate is a cellulose acylate film.
(9) The laminate according to (7) or (8), wherein the liquid crystal compound is vertically or horizontally aligned in the retardation layer.
(10) The laminate according to any one of (7) to (9), wherein the retardation layer includes a vertical alignment agent or a horizontal alignment agent.
(11) An optical film obtained by transferring the laminate according to any one of (7) to (10) to a transfer film.
(12) A method for producing an optical film, comprising a step of transferring the laminate according to any one of (7) to (10) onto a film to be transferred.
(13) A polarizing plate having a polarizer and the optical film according to (11).
(14) A liquid crystal display device comprising the polarizing plate according to (13).
(15) As a polymerization monomer, it contains only a monomer having an SP value of 22.0 or more, a ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer of 0.4% or more, and a polymerization initiator and leveling The composition for alignment film formation containing an agent.

  ADVANTAGE OF THE INVENTION According to this invention, the peeling property from a base material is favorable and the composition for alignment film and alignment film formation which liquid crystal orientation is favorable are provided. In the laminate including the alignment film of the present invention, the optical film, the method for producing the optical film, the polarizing plate and the liquid crystal display device, the releasability of the alignment film from the substrate is good and the liquid crystal alignment is good.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Alignment film>
The alignment film of the present invention uses only a monomer having a SP value of 22.0 or more and a ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer of 0.4% or more as a monomer constituting the polymer. And a polymer obtained by curing the monomer with active energy rays. Since the alignment film of the present invention has good peelability from the substrate, productivity can be improved. Further, the alignment film of the present invention can be provided with a layer exhibiting liquid crystal alignment properties as an upper layer by applying a coating solution containing a liquid crystal compound and performing a predetermined treatment. This is because the use of a monomer having an SP value of 22.0 or more and a ratio of the number of hydroxyl groups per molecule of 0.4% or more increases the surface energy of the alignment film surface, and the liquid crystal alignment I think it showed gender.

<< Polymer >>
The polymer in the present invention is obtained by curing an active energy ray of a monomer having an SP value of 22.0 or more and a ratio of the number of hydroxyl groups per monomer molecule to the monomer molecular weight of 0.4% or more. Two or more types of monomers may be mixed and used as long as they satisfy the above conditions. The structure of the monomer constituting the polymer can be determined by analysis such as liquid chromatography, gas chromatography, TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry), FT-IR, and Raman spectroscopy.

  The SP value of the monomer is 22.0 or more, and preferably 23.0 or more. As described above, the use of a monomer having an SP value of 22.0 or more improves the peelability from the substrate. Further, the SP value of the monomer is preferably 27.0 or less, and more preferably 25.0 or less. The SP value of the monomer is particularly preferably 23.0 to 25.0. The SP value refers to the value of the solubility parameter calculated by the Hoy method. The Hoy method is described in POLYMER HANDBOOK FOURTH EDITION.

  The ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer is 0.4% or more, preferably 0.5% or more, more preferably 0.55% or more, and preferably 2% or less, preferably 1% or less. More preferred. The ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer is particularly preferably 0.4 to 2%. The ratio (percentage) of the number of hydroxyl groups per molecule of the monomer to the molecular weight of the monomer can be obtained by multiplying the quotient obtained by dividing the number of hydroxyl groups per molecule of the monomer by the molecular weight of the monomer by 100. Moreover, when using the mixture of a some monomer, it can calculate by calculating | requiring the number of hydroxyl groups per molecule | numerator of each monomer, and adding the value with a mixing ratio. In addition, 1-6 are preferable and, as for the number of hydroxyl groups which one monomer has, 2-4 are more preferable.

The monomer contains a polymerizable group, and the polymerizable group equivalent of the monomer is preferably 100 to 200, and more preferably 150 to 180. Here, the polymerizable group equivalent of the monomer means a quotient obtained by dividing the molecular weight of the monomer by the number of polymerizable groups per molecule of the monomer, and can be represented by the following formula.
Equivalent polymerizable group of monomer = molecular weight of monomer / number of polymerizable groups per monomer molecule The monomer preferably has one or more polymerizable groups in one molecule, and preferably has 1 to 8 polymerizable groups. More preferably, it has 2 to 8 polymerizable groups, more preferably 2 to 4 polymerizable groups.
As the polymerizable group of the monomer, an acryloyl group, a methacryloyl group, an epoxy group, an oxetane group, and the like are preferable, and an acryloyl group is particularly preferable.
The molecular weight of the monomer is preferably 100 to 1000, and more preferably 150 to 700.

As the monomer, a compound represented by the following general formula (1) is preferable.
R (OH) _m (L-X) _n (1)
In general formula (1), R represents a linear or branched alkyl group or a (m + n) -valent group derived from an alkyl chain, provided that
One or more —CH ₂ — in the alkyl chain group may be substituted by —O—. The number of carbon atoms constituting R is not particularly limited, but is preferably 3 to 40, and more preferably 3 to 30. m preferably represents an integer of 1 to 6, more preferably an integer of 2 to 4. L represents a single bond or a divalent linking group, and preferably represents —O—, —OCO—, or —COO—. X represents a polymerizable group, and the preferred range is the same as the polymerizable group possessed by the monomer. n preferably represents an integer of 1 to 8, more preferably an integer of 2 to 8, and still more preferably an integer of 2 to 4.

  As monomers, Blemmer GLM (manufactured by NOF Corporation), glycerol 1,3-diglycerolate diacrylate (manufactured by Sigma Aldrich), NK oligo EA-5321 (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK oligo EA-5323 Commercial products such as (manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be used.

  The amount of the polymer in the alignment film is preferably 80 to 99% by mass, and more preferably 90 to 99% by mass.

<Composition for alignment film formation>
The alignment film of the present invention includes, as a polymerization monomer, only the monomer having the above-described SP value of 22.0 or more and the ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer being 0.4% or more, Furthermore, it can form using the composition for alignment film formation containing a polymerization initiator and a leveling agent.
The amount of the monomer in the alignment film-forming composition is preferably 80 to 99% by mass, more preferably 90 to 99% by mass, based on the total solid content.

<< Polymerization initiator >>
As the polymerization initiator, it is preferable to use a photopolymerization initiator. As the photopolymerization initiator, a photoradical polymerization initiator or a photocationic polymerization initiator is preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  As a commercially available radical photopolymerization initiator, Kayacure (registered trademark) manufactured by Nippon Kayaku Co., Ltd. (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.), BASF Irgacure (registered trademark) (651, 184, 127, 500, 907, 369, 1173, 2959, 4265, 4263, etc.), Esacure (registered trademark) manufactured by Sartomer (KIP100F) , KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like.

In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, published in 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 127, 907) manufactured by BASF.
0.5-10 mass parts is preferable with respect to 100 mass parts of monomers, and, as for the usage-amount of a photoinitiator, 1-5 mass parts is more preferable.
In addition to the photopolymerization initiator, a sensitizer may be used. Specific examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd. 0.1-5 mass parts is preferable with respect to 100 mass parts of monomers, and, as for the usage-amount of a photoinitiator, 0.5-3 mass parts is more preferable.

<< Leveling agent >>
The alignment film of the present invention can contain a leveling agent for controlling film thickness unevenness and suppressing coating defects such as repellency.
As the leveling agent, the following fluoropolymer (including formula (II) as a partial structure) is preferably used.
As the leveling agent, the fluorine-based polymer is preferably a copolymer containing a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following formula (II).

In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent; L is a divalent linking group selected from the following linking group group or 2 selected from the following linking group group. Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or phosphonoxy {—OP (═O) (OH) ₂ } or a salt thereof.
Specific examples of the fluoroaliphatic group-containing copolymer preferably used as the fluorine-based polymer include compounds described in paragraphs [0110] to [0114] of JP-A-2006-113500.
The amount of the leveling agent used is preferably from 0.01 to 1 part by weight, more preferably from 0.05 to 0.5 part by weight, based on 100 parts by weight of the monomer.

<< Solvent >>
The composition for forming an alignment film of the present invention may contain a solvent.
Solvents include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate, propyl acetate, Butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons ( Examples, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (eg, 1-methoxy) 2-propanol) and the like. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred. In particular, ethanol or methyl isobutyl ketone is preferable.
50-90 mass% is preferable and, as for the quantity of the solvent in the composition for alignment film formation, 60-80 mass% is more preferable.

<Method for producing alignment film>
The alignment film of the present invention can be produced using the composition for forming an alignment film containing the monomer described above. For example, the alignment film of the present invention is formed by applying an alignment film forming composition directly or via another layer on a substrate, drying, and irradiating active energy rays such as ultraviolet rays. Can do.

The base material is preferably one that can releasably carry a transfer layer (an alignment film and a retardation layer described later) and adhere the transfer layer on a film to be transferred. The substrate is preferably a transparent substrate. For example, a cellulose acylate film (preferably a triacetyl cellulose film), a polycarbonate film, a polyethylene terephthalate film, and the like are preferable. Regarding the cellulose acylate film, for example, the description in paragraphs 0019 to 0117 of JP2013-235232A can be referred to. Examples of the polycarbonate film include Pure Ace (manufactured by Teijin Chemicals Ltd.).
The method for applying the alignment film forming composition is preferably a spin 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, more preferably a wire bar coating method. preferable.

40-90 degreeC is preferable and, as for drying temperature, 50-80 degreeC is more preferable.
The drying time is preferably 20 seconds or more, and more preferably 100 to 150 seconds.
The active energy ray is not particularly limited as long as it is an active energy ray capable of polymerizing the monomer, but ultraviolet rays, electron beams and the like are preferable, and ultraviolet rays are more preferable.
Irradiation conditions of the active energy ray (such as ultraviolet rays) is preferably from ^{50~1000mJ / cm 2, 100~500mJ / cm} 2 is more preferable.

<Laminate>
The laminate of the present invention has a base material, the above-described alignment film of the present invention, and a retardation layer in the above order.
The alignment film of the present invention is preferably adjacent to the surface of the substrate. Moreover, it is preferable that a phase difference layer is adjacent to the surface on the opposite side to the base material of the orientation film of this invention.
The types and preferred examples of the substrate are as described above in the method for producing the alignment film.
The thickness of the substrate is not limited as long as it has manufacturing suitability so as not to be deformed by coating or the like, but a thickness of about 20 to 100 μm is preferable from the viewpoint of transportability.

<< retardation layer >>
In the retardation layer, the liquid crystal compound is preferably vertically aligned or horizontally aligned.
The vertical alignment or horizontal alignment of the liquid crystal compound can be achieved by adding a vertical alignment agent or a horizontal alignment agent described later. As for the liquid crystal compound being vertically aligned or horizontally aligned, there are various measuring methods such as a method obtained by microscopic observation and a method obtained by optical measurement. As an example, a method for evaluating orientation based on optical characteristics obtained from a retardation measurement method will be described below.
A transfer-type film is prepared, and transferred to the glass substrate with SK2057 manufactured by Soken Kagaku Co., Ltd. on the retardation layer side. Retardation of this transferred glass substrate is measured by the retardation measuring method described later, and Re and Rth are confirmed.
At this time, when the liquid crystal is vertically aligned, Re (λ) ≈0 and Rth ≠ 0. In particular, when the rod-like liquid crystal is vertically aligned, Rth shows a negative value, and when the disc-like liquid crystal is stacked and vertically aligned, Rth shows a positive value. In addition, when Rth = 0, it is regarded as isotropic alignment and liquid crystal alignment is not performed.
When the liquid crystal compound is horizontally aligned, Re indicates a value twice as large as the absolute value of Rth and is generally called an A plate. In particular, when the rod-like liquid crystal is horizontally aligned, Re / 2 = Rth, and when the disc-like liquid crystal is horizontally aligned, Re / 2 = −Rth.

(Measurement method of retardation)
In the present specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re is measured by making light with a wavelength of λ nm incident in the normal direction of the film in KOBRA21ADH (manufactured by Oji Scientific Instruments). Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the film normal direction with the above-mentioned Re and in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotary axis). The retardation value and the retardation value measured by making light of wavelength λ nm incident from a direction inclined −40 ° with respect to the normal direction of the film with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the measured retardation value. Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. By inputting the assumed value of the average refractive index and the film thickness, KOBRA 21ADH calculates nx, ny, and nz. Note that Re = (nx−ny) × d and Rth = {(nx + ny) / 2−nz} × d. nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the film thickness direction, and d is the thickness of the film. (Nm).
The measurement wavelength of the refractive index is a value at λ = 550 nm in the visible light region unless otherwise specified, and the measurement wavelength of Re and Rth is 550 nm unless otherwise specified.

The thickness of the retardation layer is preferably 0.3 to 3.0 μm, more preferably 0.5 to 2.0 μm.
The retardation layer can be produced using a composition containing a liquid crystal compound and, if desired, a vertical alignment agent or horizontal alignment agent, a polymerization initiator, a leveling agent, and a solvent.

<<< Liquid Crystal Compound >>>
As the liquid crystal compound that forms the retardation layer, a rod-like liquid crystal compound is preferable. For the rod-shaped liquid crystal compound that can be used, reference can be made, for example, to the descriptions in paragraphs 0045 to 0066 of JP-A-2009-217256, the contents of which are incorporated herein. For the additive that can be used in the retardation layer and the method for forming the liquid crystal layer, for example, the description of [0076] to [0079] of JP-A-2009-237421 can be referred to, and the contents thereof are described in this application. Incorporated in the description.

  The liquid crystal compound forming the retardation layer preferably contains at least one of a compound represented by the following general formula (IIIA) and a compound represented by the following general formula (IIIB).

Formula (IIIA)

Formula (IIIB)

R _{1 to} R ₄ are each independently — (CH ₂ ) _n —OCO—CH═CH ₂ , and n represents an integer of 2 to 5. X and Y each independently represent a hydrogen atom or a methyl group. From the viewpoint of suppressing crystal precipitation, in the general formula (IIIA) or (IIIB), X and Y preferably represent a methyl group.
The liquid crystal compound is preferably contained in the retardation layer in an amount of 70% by mass or more, particularly preferably 80% by mass or more.

<<< Vertical alignment agent >>>
The vertical alignment agent preferably contains a compound represented by the following general formula (IV). The onium compound acts as a vertical alignment agent that promotes homeotropic alignment at the alignment film interface of the liquid crystal compound.

In general formula (IV), ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocycle, X represents an anion; L ¹ represents a divalent linking group; L ² represents a single bond or a divalent group. Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure; Z represents a divalent linking group having 2 to 20 alkylene groups as a partial structure; P ¹ and P ² each independently represents a hydrogen atom, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, a cyano group, or a monovalent substituent having a polymerizable ethylenically unsaturated group.

  Ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocyclic ring. Examples of ring A include pyridine ring, picoline ring, 2,2′-bipyridyl ring, 4,4′-bipyridyl ring, 1,10-phenanthroline ring, quinoline ring, oxazole ring, thiazole ring, imidazole ring, pyrazine ring , Triazole ring, tetrazole ring and the like, preferably quaternary imidazolium ion and quaternary pyridinium ion.

  X represents an anion. Examples of X include a halogen anion (for example, fluorine ion, chlorine ion, bromine ion, iodine ion, etc.), sulfonate ion (for example, methanesulfonate ion, trifluoromethanesulfonate ion, methylsulfate ion, vinylsulfonate ion) , Allyl sulfonate ion, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion, p-vinylbenzene sulfonate ion, 1,3-benzene disulfonate ion, 1,5-naphthalene disulfonate ion, 2,6- Naphthalenedisulfonate ion), sulfate ion, carbonate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, benzoate ion, p-vinylbenzoate ion, formic acid Ion, trifle B acetate ion, phosphoric acid ion (e.g., hexafluorophosphate ion), such as a hydroxide ion. Preferred are halogen anions, sulfonate ions, and hydroxide ions. In particular, chlorine ion, bromine ion, iodine ion, methanesulfonic acid ion, vinylsulfonic acid ion, p-toluenesulfonic acid ion, and p-vinylbenzenesulfonic acid ion are preferable.

L ¹ represents a divalent linking group. Examples of L ¹ include an alkylene group, —O—, —S—, —CO—, —SO ₂ —, —NRa— (where Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), A divalent linking group having 1 to 20 carbon atoms, which is a combination with an alkenylene group, an alkynylene group or an arylene group. L ¹ is preferably -AL-, -O-AL-, -CO-O-AL-, or -O-CO-AL- having 1 to 10 carbon atoms, and -AL having 1 to 10 carbon atoms. -And -O-AL- are more preferable, and -AL- and -O-AL- having 1 to 5 carbon atoms are most preferable. AL represents an alkylene group.

L ² represents a single bond or a divalent linking group. Examples of L ² include an alkylene group, —O—, —S—, —CO—, —SO ₂ —, —NRa— (where Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), A divalent linking group having 1 to 10 carbon atoms consisting of a combination with an alkenylene group, an alkynylene group or an arylene group, a single bond, —O—, —O—CO—, —CO—O—, —O -AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O-CO-, -CO -O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO-, -O-CO-AL-CO-O-, and the like can be given. AL represents an alkylene group. L ² is preferably a single bond, -AL- having 1 to 10 carbon atoms, -O-AL-, or -NRa-AL-O-, a single bond, -AL- having 1 to 5 carbon atoms, —O—AL— and —NRa—AL—O— are more preferable, and —O—AL— and —NRa—AL—O— having a single bond and 1 to 5 carbon atoms are most preferable.

Y ¹ represents a divalent linking group having a 5- or 6-membered ring as a partial structure. Examples of Y ¹ include a cyclohexyl ring, an aromatic ring or a heterocyclic ring. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring, and a benzene ring, a biphenyl ring, and a naphthalene ring are particularly preferable. The hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. For example, a furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole Ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring Morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. The heterocycle is preferably a 6-membered ring. The divalent linking group having a 5- or 6-membered ring represented by Y ¹ as a partial structure may further have a substituent.

  Examples of the substituent include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 10, more preferably 1 to 5), and 2 to 12 carbon atoms (more preferably). An alkenyl group having 2 to 10 and more preferably 2 to 5), an alkoxy group having 1 to 12 carbon atoms (more preferably 1 to 10, more preferably 1 to 5), and the like can be mentioned. The alkyl group and the alkoxy group have an acyl group having 2 to 12 carbon atoms (more preferably 2 to 10 and more preferably 2 to 5) or 2 to 12 carbon atoms (more preferably 2 to 10 and more preferably). May be substituted with an acyloxy group of 2-5). The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.

The divalent linking group represented by Y ¹ is preferably a divalent linking group having two or more 5- or 6-membered rings, and preferably has a structure in which two or more rings are connected by a linking group. More preferred. Examples of linking groups include linking groups represented by L ¹ and L ^2, and —C≡C—, —CH═CH—, —CH═N—, —N═CH—, —N═N— and the like. Can be mentioned.

Z represents a divalent linking group having a combination of —O—, —S—, —CO—, and —SO ₂ — with a C 2-20 alkylene group as a partial structure, and an alkylene group May have a substituent. Examples of the divalent linking group include an alkyleneoxy group and a polyalkyleneoxy group. The number of carbon atoms of the alkylene group represented by Z is more preferably 2 to 16, more preferably 2 to 12, and particularly preferably 2 to 8.

P ¹ and P ² each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated group, or a hydrogen atom, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, or a cyano group.
As for the compound represented by the general formula (IV), for example, the description in paragraphs 0150 to 0183 of JP2013-235232A can be referred to, and the contents thereof are incorporated in the present specification.

（一般式（Ｖ）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、置換もしくは無置換の、脂肪族炭化水素基、アリール基又はヘテロ環基を表し、これらは互いに連結して環を形成してもよい。Ｒ³は置換もしくは無置換の、脂肪族炭化水素基、アリール基又はヘテロ環基を表す。）
一般式（Ｖ）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、置換もしくは無置換の、脂肪族炭化水素基、アリール基、またはヘテロ環基を表す。脂肪族炭化水素基としては、炭素数１〜２０の置換もしくは無置換の直鎖もしくは分岐のアルキル基（例えば、メチル基、エチル基、ｉｓｏ−プロピル基等）、炭素数３〜２０の置換もしくは無置換の環状アルキル基（例えば、シクロヘキシル基等）、炭素数２〜２０のアルケニル基（例えば、ビニル基等）が挙げられ、アリール基としては、炭素数６〜２０の置換もしくは無置換のフェニル基（例えば、フェニル基、トリル基など）、炭素数１０〜２０の置換もしくは無置換のナフチル基等が挙げられ、ヘテロ環基としては例えば、少なくとも一つのヘテロ原子（例えば、窒素原子、酸素原子、硫黄原子等）を含む、置換もしくは無置換の５員もしくは６員環の基であり、例えば、ピリジル基、イミダゾリル基、フリル基、ピペリジル基、モルホリノ基等が挙げられる。これらは互いに連結して環を形成しても良く、例えば、Ｒ¹及びＲ²のイソプロピル基が連結して、４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン環を形成しても良い。 A boronic acid compound can also be used as the vertical alignment agent. The boronic acid compound is preferably represented by the following general formula (V).

(In the general formula (V), R ¹ and R ² each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, an aryl group or a heterocyclic group, which are connected to each other to form a ring. R ³ represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or heterocyclic group.
In general formula (V), R ¹ and R ² each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, an aryl group, or a heterocyclic group. Examples of the aliphatic hydrocarbon group include a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, an iso-propyl group, etc.), Examples thereof include an unsubstituted cyclic alkyl group (for example, cyclohexyl group) and an alkenyl group having 2 to 20 carbon atoms (for example, a vinyl group). As the aryl group, substituted or unsubstituted phenyl having 6 to 20 carbon atoms. A group (for example, phenyl group, tolyl group, etc.), a substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms, and the like. Examples of the heterocyclic group include at least one hetero atom (for example, nitrogen atom, oxygen atom). A substituted or unsubstituted 5- or 6-membered ring group containing, for example, a pyridyl group, an imidazolyl group, a furyl group, a piperidyl group, Ruhorino group, and the like. These may be connected to each other to form a ring. For example, the isopropyl groups of R ¹ and R ² are connected to form a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane ring. You may do it.

In general formula (V), R ³ represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group, or heterocyclic group. Examples of the aliphatic hydrocarbon group include a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. Examples of the aryl group include substituted or unsubstituted phenyl groups having 6 to 50 carbon atoms (for example, phenyl group, tolyl group, styryl group, 4-benzoyloxyphenyl group, 4-phenoxycarbonylphenyl group, 4- Biphenyl group, 4- (4-octyloxybenzoyloxy) phenoxycarbonylphenyl group, etc.), substituted or unsubstituted naphthyl group having 10 to 50 carbon atoms (for example, unsubstituted naphthyl group, etc.), and heterocyclic group For example, substituted or non-substituted containing at least one hetero atom (for example, nitrogen atom, oxygen atom, sulfur atom, etc.) Substituted or 5-membered groups such as pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, Dibenzothiophene, indazolebenzimidazole, anthranyl, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine, morpholine And groups such as piperidine. Furthermore, one or more of these aliphatic hydrocarbon groups, aryl groups, and heterocyclic groups included in the heterocyclic group may be substituted with any substituent.
Details and preferred ranges of the boronic acid compound represented by the general formula (V) are described in paragraph Nos. 0016 to 0023 of JP-A No. 2014-129255, the contents of which are cited herein. Specific examples of the boronic acid compound include compounds described in paragraph numbers 0026 to 0029 of JP2014-129255A.

  The content of the vertical alignment agent in the composition for forming the retardation layer is not particularly limited, but is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass with respect to the total solid content. It is. When two or more kinds of vertical alignment agents are used, the total amount is preferably within the above range.

<<< Horizontal alignment agent >>>
The horizontal alignment agent preferably contains a polymer containing a repeating unit derived from the monomer represented by the following general formula 1 (hereinafter also simply referred to as “fluorine polymer”).

The polymer containing a repeating unit derived from the monomer represented by the general formula 1 is derived from a polymer of a repeating unit (polymerization unit) derived from the monomer (i) below or a monomer (i) below. Examples thereof include an acrylic resin, a methacrylic resin, and a copolymer with a vinyl monomer copolymerizable with the repeating unit (polymerized unit) and a repeating unit (polymerized unit) derived from the monomer (ii) below. . As such a monomer, those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 2, Pages 1-483 can be used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Can be mentioned.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula 1

In the general formula 1, R ¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, more preferably an oxygen atom or —N (R ¹² ) —, and still more preferably an oxygen atom. R ¹² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group. R _f represents —CF ₃ or —CF ₂ H.
M in the general formula 1 represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1.
N in the general formula 1 represents an integer of 1 to 11, more preferably 1 to 9, and still more preferably 1 to 6. R _f is preferably —CF ₂ H.
In addition, two or more kinds of polymer units derived from the fluoroaliphatic group-containing monomer represented by the general formula 1 may be contained in the fluorine-based polymer as a constituent component.

(Ii) Monomer represented by the following general formula 2 copolymerizable with the above (i)

In the general formula 2, R ¹³ represents a hydrogen atom, a halogen atom or a methyl group, a hydrogen atom, more preferably a methyl group. Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, more preferably an oxygen atom or —N (R ¹⁵ ) —, and still more preferably an oxygen atom. R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 1 to 60 carbon atoms, an aromatic group (for example, a phenyl group or a naphthyl group), or a linear, branched or cyclic alkylene having 1 to 60 carbon atoms. Represents a combination of a group and an aromatic group (for example, a phenyl group or a naphthyl group). The alkyl group may include a poly (alkyleneoxy) group. Furthermore, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is particularly preferable.

  The content of the horizontal alignment agent in the composition for forming the retardation layer is not particularly limited, but is preferably 0.05 to 5% by mass, more preferably 0.1 to 1% based on the total solid content. % By mass. When two or more kinds of vertical alignment agents are used, the total amount is preferably within the above range.

<<< Other ingredients >>>
In addition to the above, the composition for forming the retardation layer can contain a polymerization initiator, a sensitizer, a leveling agent, and / or a solvent. As a polymerization initiator, a leveling agent, and a solvent, the thing similar to what was described in the composition for alignment film formation can be used.

<Method for producing laminate>
The laminate of the present invention can be produced by a step of forming the alignment film described above on the substrate and a step of forming a retardation layer on the alignment film.

The step of forming the alignment film is the same as the method for manufacturing the alignment film described above.
The step of forming the retardation layer preferably includes applying a composition containing a liquid crystal compound to the surface of the alignment film and performing a heat treatment as necessary to fix the alignment state of the liquid crystal compound.
The method of applying the composition is synonymous with the method of applying the alignment film forming composition described above.
As for the conditions for the heat treatment, an optimal temperature is appropriately selected according to the type of the liquid crystal compound to be used, but it is usually 20 to 200 ° C. (preferably 60 to 160 ° C.) for 10 to 600 seconds (preferably Is preferably 30 to 300 seconds).
UV irradiation dose is preferably ^{50~1000mJ / cm 2, 100~500mJ / cm} 2 is more preferable.

<Optical film and method for producing optical film>
According to this invention, the optical film obtained by transferring the above-mentioned laminated body to a to-be-transferred film is provided. Furthermore, according to this invention, the manufacturing method of an optical film including the process of transferring the above-mentioned laminated body of this invention to a to-be-transferred film is provided.
As a transfer method, for example, as described in JP-A-4-57017 and JP-A-5-333313, the surface of a retardation layer is transferred to a film to be transferred (laminated layer) via an adhesive or an adhesive. After being laminated on another base material different from the base material constituting the body), the pressure-sensitive adhesive or adhesive is subjected to a curing treatment if necessary, and the base material is peeled off from the above-mentioned laminated body, so that the retardation layer and the orientation are aligned. A method of transferring the layer can be mentioned. The pressure-sensitive adhesive and adhesive are not particularly limited as long as they are optical grade, and include, for example, acrylic, epoxy resin, ethylene-vinyl acetate copolymer, rubber, urethane, and mixtures thereof, heat Various reactive types such as a curable type and / or a photo-curable type and an electron beam curable type can be exemplified. Since the reaction (curing) conditions vary depending on the components constituting the pressure-sensitive adhesive / adhesive, the viscosity, the reaction temperature, and the like, the conditions suitable for each may be selected.
Peeling of the substrate from the laminate can be carried out starting from physical bending, curling from the cut end face, heat, and wet heat treatment. Using differences in physical and mechanical properties (ductility, toughness) of each layer, using differences in physical properties such as dimensional changes due to heat and wet heat treatment, or using shear rate differences in the upper and lower film thickness directions, Peeling can also be performed.

  5-100 micrometers is preferable and, as for the thickness of the optical film of this invention, 5-60 micrometers is more preferable.

<Polarizing plate>
The polarizing plate of the present invention has a polarizer and at least one optical film of the present invention. The polarizing plate may further have a protective film. As the protective film, for example, a cellulose acylate film, an acrylic resin film, or the like can be used. Examples of the polarizer include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol film.

<Liquid crystal display device>
The present invention also relates to a liquid crystal display device including at least one polarizing plate of the present invention.
The liquid crystal display device includes a liquid crystal cell in which liquid crystal is supported between two electrode substrates, two polarizing plates disposed on both sides thereof, and at least one between the liquid crystal cell and the polarizing plate as necessary. It has a configuration in which a single optical compensation film is arranged.
The liquid crystal layer of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer. These layers are usually provided on the substrate.

  In a liquid crystal display device, a substrate including a liquid crystal cell is usually disposed between two polarizing plates (a viewing side polarizing plate and a backlight side polarizing plate). The polarizing plate of the present invention can be used as a viewing side polarizing plate and / or a backlight side polarizing plate in a liquid crystal display device.

  The polarizing plate of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroly Liquid Liquid Crystal), OCB (Optically QuantNW). Various display modes such as ECB (Electrically Controlled Birefringence) and HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above display mode is oriented and divided has been proposed. The optical film of the present invention can be used in a liquid crystal display device of any display mode,

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Formation of alignment layer>
100 parts by weight of the monomers listed in the following table, 3 parts by weight of a photopolymerization initiator (Irgacure 127, manufactured by BASF), 0.1 parts by weight of a leveling agent, and a solvent (with a solid content of the entire composition) The composition for forming an alignment film was prepared by mixing 30 parts by mass with respect to the mass.
The prepared composition for forming an alignment film is applied on the following substrate 1 or 2 with a wire bar coater # 3.0, dried at 60 ° C. for 2 minutes, and then in an atmosphere having an oxygen concentration of 1.0% by volume or less. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen, an alignment layer was formed by irradiating with an irradiation dose of 40 mJ / cm ² .

(monomer)
GLM: Bremmer GLM (manufactured by NOF Corporation) (structural formula is as described above in this specification)
GMR: Bremer GMR (manufactured by NOF Corporation) (Structure is as follows)
EA5321: NK oligo EA-5321 (manufactured by Shin-Nakamura Chemical Co., Ltd.) (structural formula is as described above in this specification)
EA5323: NK oligo EA-5323 (manufactured by Shin-Nakamura Chemical Co., Ltd.) (Structural formula is as described above in this specification)
U-4HA: NK oligo U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) (structural formula is as follows)
APG400: NK ester APG-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) (Structural formula is as follows)
PET30: KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.) (structural formula is as follows)
Glycerol 1,3-diglycerolate diacrylate (manufactured by Sigma-Aldrich) (structural formula is as described above in this specification)

(Leveling agent)

(Base material)
Base material 1: FUJITAC (registered trademark) TD60UC manufactured by FUJIFILM Corporation (triacetyl cellulose)
Base material 2: Pure Ace (registered trademark), manufactured by Teijin Limited (polycarbonate)

<Formation of retardation layer A (vertical alignment retardation layer)>
Liquid crystal compound A (80 parts by mass), liquid crystal compound B (20 parts by mass), photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) (3 parts by mass), sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) (Made) (1 part by mass), vertical alignment agent A (1 part by mass), vertical alignment agent B (0.5 part by mass), and the leveling agent (0.4 part by mass) dissolved in 215 parts by mass of methyl ethyl ketone, A solution for forming the retardation layer A was prepared. The prepared solution for forming the retardation layer A is applied onto the alignment layer with a # 3.0 wire bar, heated at 70 ° C. for 2 minutes, cooled to 40 ° C., and then the oxygen concentration is 1.0% by volume. Using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen to make the following atmosphere, the retardation layer was cured by irradiating with an irradiation amount of 300 mJ / cm ² . . The alignment layer used is shown in the table.

<Formation of retardation layer B (horizontal alignment retardation layer)>
Rod-like liquid crystal compound A (80 parts by mass), rod-like liquid crystal compound B (20 parts by mass), photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) (3 parts by mass), sensitizer (Kayacure DETX, Nippon Kayaku ( Co., Ltd.) (1 part by mass) and the following horizontal alignment agent (0.3 parts by mass) were dissolved in methyl ethyl ketone (193 parts by mass) to prepare a retardation layer B forming solution. On the alignment layer that has been rubbed so that the angle formed between the longitudinal direction of the film and the rotation axis of the rubbing roller is 90 °, the above retardation layer B forming solution is applied with a wire bar coater # 2.2. Heated at 60 ° C. for 2 minutes and maintained at 60 ° C., while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) ) Was used to cure the retardation layer by irradiating with an ultraviolet ray with an irradiation amount of 300 mJ / cm ² . The alignment layer used is shown in the table.

Horizontal alignment agent:

<Evaluation>
<< Evaluation of peelability >>
Tensillon universal material test for peel strength when 150mm x 25mm sample (sample with alignment layer and retardation layer formed on substrate) is bonded to glass substrate with only 80mm x 25mm part and peeled in 90 ° direction Measured by a machine (Orientec Co., Ltd.) and evaluated according to the following criteria.
Evaluation criteria A: 0.20 N / 25 mm or less B: More than 0.21 N / 25 mm and less than 0.50 N / 25 mm C: 0.51 N / 25 mm or more

<< Liquid crystal orientation >>
The surface of the prepared sample (sample in which an alignment layer and a retardation layer were formed on a substrate) on the retardation layer side was bonded to a glass substrate via an adhesive (SK2057 manufactured by Soken Kagaku Co., Ltd.). The retardations of the retardation layer A and retardation layer B produced on the glass substrate were measured. The measured value of retardation at a wavelength of 550 nm is shown in the table. When Re (550) ≈0 and Rth (550) ≠ 0, the vertical alignment is confirmed, and when Re is twice the absolute value of Rth, the horizontal alignment is confirmed. Note that “not oriented” means that leakage light was detected even under crossed Nicols due to scattered light caused by misalignment.

<Formation of transferred material>
(Preparation of cyclic olefin film HT1)
ZEONOR ZF14 is 1.5 times in the film transport direction (MD direction) and then 1.9 times in the direction perpendicular to the MD direction (TD direction) at a temperature of 155 ° C. and a stretching speed of 30 mm / min. The film was stretched under the following stretching conditions to obtain a film having a retardation Re (550) / Rth (550) = 140/80 with a film thickness of 20 μm.

(Preparation of cellulose acylate film HT2)
A cellulose acylate film was produced by the following method.
(1) Preparation of dope-prepared cellulose acylate solution:
The following solvent and solid were put into a mixing tank, stirred to dissolve each component, further heated to 90 ° C. for about 10 minutes, and then filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm.
Dope for preparing cellulose acylate film: 670 parts by mass of methylene chloride, 100 parts by mass of methanol, 100 parts by mass of cellulose acetate having a substitution degree of 2.43, 19 parts by mass of compound B1, 5 parts by mass of compound L2, and inorganic fine particles of matting agent (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) 0.02 parts by mass The above was mixed to prepare a dope for film formation.

(2) Casting The dope was cast using a band casting machine. The band was made of SUS stainless steel.
(3) Drying After the web (film) obtained by casting was peeled from the band, the pass roll was conveyed and dried at a drying temperature of 120 ° C. for 20 minutes. In addition, the drying temperature here means the film surface temperature of a film.
(4) Stretching The obtained web (film) is peeled from the band, sandwiched between clips, and in a direction perpendicular to the film transport direction (MD) using a tenter at a stretching temperature of 190 ° C. under the conditions of fixed-end uniaxial stretching ( TD) was stretched 1.88 times.

<Saponification treatment of protective film for making polarizing plate>
Fujifilm TJ25 (25 μm triacetylcellulose (TAC)) was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, the surface of the support was saponified.

<Saponification Treatment of Film HT2 for Making Polarizing Plate>
The produced film HT2 was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, the surface of the support was saponified.

<Corona treatment of film HT1 for making polarizing plate>
One surface of the produced film HT1 was treated with a discharge amount of 10 W / m ² / min, and this surface was used as a polarizer contact surface during the production of the polarizing plate.

<Preparation of polarizing plate>
The protective film, polyvinyl alcohol polarizer and film HT1 produced above were laminated so as to be in the above order. Thereafter, the retardation layer A was transferred to the surface of HT1 through SK2057 manufactured by Soken Kagaku. Thus, the polarizing plate with HT1 was produced.
Moreover, the film HT1 was changed to the film HT2, and the polarizing plate with HT2 was produced.

<Production of liquid crystal display device>
The polarizing plate on the viewing side was peeled off from a liquid crystal cell of iPad (registered trademark, manufactured by Apple) and used as an IPS mode liquid crystal cell.
Instead of the peeled polarizing plate, a polarizing plate with HT1 or a polarizing plate with HT2 was bonded to a liquid crystal cell to prepare a liquid crystal display device. At this time, it was bonded so that the absorption axis of the polarizing plate and the optical axis of the liquid crystal layer in the liquid crystal cell were perpendicular to each other when observed from the direction perpendicular to the liquid crystal cell substrate surface.
Confirm the display performance of this bonded iPad, and see that there is no unevenness visually, and using a measuring device (EZ-Contrast XL88, manufactured by ELDIM), the polar angle is 60 degrees with respect to the front in black display. Observed from the direction, azimuth angle 0-90 degrees (first quadrant), 90-180 degrees (second quadrant), 180-270 degrees (third quadrant), 270-360 degrees (fourth quadrant) It was confirmed that there was almost no color shift using an index obtained by averaging the maximum ΔE of each element. In addition, using a measuring machine (EZ-Contrast XL88, manufactured by ELDIM), the luminance at the time of black display and white display in a dark room is measured, and the average value of the minimum values of each quadrant in the direction of 60 degrees polar angle is obtained. The viewing angle contrast ratio (viewing angle CR) was defined and calculated, and it was confirmed that the viewing angle was CR100 or more.

(Summary of Examples)
As described above, as the monomer constituting the polymer, an example using only a monomer having an SP value of 22.0 or more and a ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer of 0.4% or more. In 1-7, both peelability and liquid crystal orientation were favorable. On the other hand, in Comparative Examples 1, 3 and 4 using a monomer having an SP value of less than 22.0, the peelability was inferior, and the ratio of the number of hydroxyl groups per monomer molecule to the monomer molecular weight was less than 0.4%. In certain Comparative Examples 2 to 4, the liquid crystal was not aligned.

Claims (15)

The monomer constituting the polymer contains only a monomer having an SP value of 22.0 or more and a ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer of 0.4% or more. An alignment film comprising a polymer obtained by curing with 1. The alignment film according to claim 1, wherein the SP value of the monomer is 23.0 to 25.0. The alignment film according to claim 1 or 2, wherein a ratio of the number of hydroxyl groups per molecule of the monomer to the molecular weight of the monomer is 0.4% or more and 2% or less. The alignment film according to any one of claims 1 to 3, wherein a polymerizable group equivalent of the monomer represented by the following formula is 100 to 200.
Monomer polymerizable group equivalent = monomer molecular weight / number of polymerizable groups per monomer molecule The alignment film according to claim 1, wherein the monomer has 2 to 8 polymerizable groups in one molecule. The alignment film according to claim 1, wherein the monomer has an acryloyl group or a methacryloyl group. The laminated body which has a base material, the orientation film as described in any one of Claims 1-6, and a phase difference layer in the said order. The laminate according to claim 7, wherein the substrate is a cellulose acylate film. The laminate according to claim 7 or 8, wherein the liquid crystal compound is vertically or horizontally aligned in the retardation layer. The laminate according to any one of claims 7 to 9, wherein the retardation layer contains a vertical alignment agent or a horizontal alignment agent. An optical film obtained by transferring the laminate according to any one of claims 7 to 10 to a film to be transferred. The manufacturing method of an optical film including the process of transcribe | transferring the laminated body as described in any one of Claim 7 to 10 to a to-be-transferred film. A polarizing plate comprising a polarizer and the optical film according to claim 11. A liquid crystal display device comprising the polarizing plate according to claim 13. The polymerization monomer contains only a monomer having an SP value of 22.0 or more and a ratio of the number of hydroxyl groups per monomer molecule to the molecular weight of the monomer of 0.4% or more, and further comprising a polymerization initiator and a leveling agent. A composition for forming an alignment film.