JP5652412B2 - Polymerizable liquid crystal composition for forming retardation layer, retardation film and method for producing retardation film - Google Patents

Description

  The present invention relates to a polymerizable liquid crystal composition for forming a retardation layer, a retardation film, and a method for producing a retardation film.

  In recent years, flat panel displays capable of three-dimensional display have begun to attract attention, and are also commercially available. In addition, it is expected that the future flat panel display is capable of three-dimensional display, and it is expected that the performance is naturally required, and a flat panel display capable of three-dimensional display is being studied in a wide range of fields.

  In order to perform three-dimensional display on a flat panel display, it is usually necessary to display a right-eye image and a left-eye image separately for the viewer in some way. As a method for separately displaying the right-eye video and the left-eye video, for example, a passive method is known. Such a passive three-dimensional display method will be described with reference to the drawings. FIG. 5 is a schematic diagram illustrating an example of a passive three-dimensional display. As shown in FIG. 5, in this method, first, the pixels constituting the flat panel display are divided into a plurality of types of pixels, that is, a right-eye video display pixel and a left-eye video display pixel. The pixel displays a right-eye image, and the other group of pixels displays a left-eye image. Also, using a linearly polarizing plate and a patterned retardation film on which a patterned retardation layer corresponding to the division pattern of the pixel is formed, a right-eye image and a left-eye image are orthogonal to each other. Convert to polarized light. In addition, the viewer wears circular polarizing glasses that employ circular polarizing lenses that are orthogonal to each other for the right-eye lens and the left-eye lens, so that the right-eye image passes only through the right-eye lens and the left-eye image is displayed. Pass only through the lens for the left eye. In this way, the passive method enables three-dimensional display by allowing the right-eye image to reach only the right eye and the left-eye image to reach only the left eye.

  Such a passive method has an advantage that three-dimensional display can be easily performed by using the pattern retardation film and the corresponding circular polarizing glasses.

  By the way, as described above, in the passive method, it is essential to use a pattern retardation film. However, such a pattern retardation film has not been widely researched and developed, and can be used as a standard technique. There is nothing that has been established. As an example, it has been proposed to form a polymer film having optical anisotropy by polymerizing a polymerizable liquid crystal composition containing a rod-shaped compound, and to use this polymer film as a retardation film ( Patent Document 1).

JP 2000-98133 A

  However, research and development of polymerizable liquid crystal compositions used for the formation of retardation layers are still under development, and further improvements in various properties such as stricter control of the orientation direction and improvement of appearance defects due to charging are required. ing.

  The present inventor has made extensive studies to solve the above-mentioned problems, and by using a polymerizable liquid crystal composition containing a polymerizable rod-shaped compound and a quaternary ammonium salt, the alignment direction is more strictly determined. It has been found that it can be controlled and that appearance defects due to charging can be improved, and the present invention has been completed. Specifically, the present invention provides the following.

  (1) The present invention includes a first rod-shaped compound having a cyano group at one end and (meth) acrylate at the other end, and a second rod-shaped compound having (meth) acrylate at both ends, A polymerizable liquid crystal composition for forming a retardation layer, comprising a quaternary ammonium salt.

(2) Moreover, this invention is a polymeric liquid crystal composition as described in (1) in which the said 1st rod-shaped compound contains the compound represented by following formula (1).

(3) Moreover, this invention is a polymerizable liquid crystal composition as described in (1) or (2) in which the said 2nd rod-shaped compound contains the compound represented by following formula (2).

  (4) In the present invention, an alignment layer is formed on a substrate, and a retardation layer made of the polymerizable liquid crystal composition according to any one of (1) to (3) is formed on the alignment layer. It is a retardation film.

  (5) Moreover, this invention consists of the process of forming an orientation layer on a elongate base material, and the polymeric liquid crystal composition in any one of (1) to (3) on this orientation layer. And a step of forming a retardation layer.

  (6) Further, in the present invention, the optical axis of the retardation layer may be 45 ° ± 2 ° and / or −45 ° ± 2 ° when the longitudinal direction of the elongated substrate is 0 degree. It is a manufacturing method of the retardation film as described in (5) which is within.

  According to the present invention, it is possible to provide a polymerizable liquid crystal composition that can be used for forming a pattern retardation film, more precisely controlling the orientation direction and improving appearance defects due to charging.

It is the schematic of the pattern phase difference film which concerns on this invention. It is the figure which showed typically the method of forming an alignment pattern by a photo-alignment system. It is the schematic which shows an example of the manufacturing method of the pattern phase difference film of FIG. It is a figure where it uses for description of the three-dimensional image display by a passive system.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Polymerizable liquid crystal composition for retardation layer formation>
In the present invention, the polymerizable liquid crystal composition for forming the retardation layer has a first rod-shaped compound having a cyano group at one end and a (meth) acrylate at the other end, and (meth) at both ends. A second rod-like compound having an acrylate and a quaternary ammonium salt are contained. This will be described in detail below.

[Bar-shaped compound]
The rod-shaped compound has a refractive index anisotropy, and has a function of imparting a desired retardation by regularly arranging the alignment material along an alignment pattern that is expressed by irradiating the photo-alignment material with polarized ultraviolet rays. Have. Examples of the rod-like compound include materials exhibiting a liquid crystal phase such as a nematic phase and a smectic phase, but the nematic phase is easier to arrange regularly than rod-like compounds exhibiting other liquid crystal phases. It is more preferable to use the rod-shaped compound shown.

  The rod-shaped compound has a polymerizable functional group in the molecule. By having a polymerizable functional group, it becomes possible to polymerize and fix the rod-like compound, so that it has excellent alignment stability and is less likely to change with time in retardation. Moreover, it is more preferable that one of the plurality of types of rod-shaped compounds has a polymerizable functional group capable of three-dimensional crosslinking in the molecule. By having a polymerizable functional group that can be cross-linked three-dimensionally, the sequence stability can be further enhanced. Note that “three-dimensional crosslinking” means that liquid crystal molecules are polymerized three-dimensionally to form a network structure.

  Examples of the polymerizable functional group include polymerizable functional groups that are polymerized by the action of ionizing radiation such as ultraviolet rays and electron beams, or heat. Representative examples of these polymerizable functional groups include radically polymerizable functional groups or cationic polymerizable functional groups. Further, representative examples of the radical polymerizable functional group include a functional group having at least one addition-polymerizable ethylenically unsaturated double bond, and specific examples include a vinyl group having or not having a substituent, An acrylate group (generic name including an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group) and the like can be given. Moreover, an epoxy group etc. are mentioned as a specific example of the said cation polymerizable functional group. In addition, examples of the polymerizable functional group include an isocyanate group and an unsaturated triple bond. Among these, from the viewpoint of the process, a functional group having an ethylenically unsaturated double bond is preferably used.

[First rod-like compound]
By the way, the rod-shaped compound of the present invention has a cyano group at one end and a (meth) acrylate at the other end (hereinafter referred to as having a cyano group at one end and (meth) acrylate at the other end. The rod-shaped compound having the above is also referred to as “first rod-shaped compound”). Since the first rod-like compound has a (meth) acrylate that is a polymerizable functional group at the end, it can be in a crosslinked structure state, so that it has row stability and excellent optical characteristics. The above can be formed. Moreover, since it has a cyano group at the terminal, charging can be prevented by adding a quaternary ammonium salt to the rod-like compound, and as a result, the orientation direction can be controlled more strictly. As an example of a 1st rod-shaped compound, the compound represented by following formula (1) can be illustrated.

[Second rod-like compound]
It is preferable to use a mixture of two or more rod-shaped compounds. For example, by combining a rod-shaped compound having one or more polymerizable functional groups at one end with a rod-shaped compound having one or more polymerizable functional groups at both ends, such as the above formula (1), The polymerization density (crosslinking density) and optical characteristics can be arbitrarily adjusted by adjusting the ratio. Further, from the viewpoint of ensuring reliability, a rod-like compound having one or more polymerizable functional groups at both ends is preferable, but from the viewpoint of liquid crystal alignment, it is preferable that one polymerizable functional group at both ends is provided.

  Moreover, it is preferable to use the material which has a spacer on both ends of a mesogen as a rod-shaped compound used together. Since a rod-shaped compound having spacers at both mesogen ends is excellent in flexibility, the use of such a rod-shaped compound can make the pattern retardation film excellent in transparency.

As an example of a rod-shaped compound having one polymerizable functional group at both ends and having spacers at both mesogen ends, a compound represented by the following formula (2) can be exemplified. Hereinafter, the rod-shaped compound having (meth) acrylates at both ends exemplified by the following formula (2) is also referred to as “second rod-shaped compound”.

Specific examples of the compound of the above formula (2) include the following formulas (2-1) to (2-6).

  The ratio of the first rod-shaped compound and the second rod-shaped compound is preferably within the range of 10:90 to 90:10. By using this ratio, charging can be prevented while maintaining the liquid crystal orientation, and as a result, the orientation direction can be more strictly controlled and the transparency of the pattern retardation film can be enhanced.

[Antistatic agent]
The polymerizable liquid crystal composition of the present invention contains a quaternary ammonium salt as an antistatic agent.

(Quaternary ammonium salt)
Examples of the compound containing a quaternary ammonium ion include those represented by the following formula (3).

  As an example of a quaternary ammonium salt-containing polymer, a dimethylaminoethyl methacrylate quaternary ammonium salt and a (meth) acrylate compound are preferably copolymerized. By using such a quaternary ammonium salt-containing polymer, not only can the liquid crystal layer to be formed have a higher hardness, but also the adhesion to other layers provided on the upper layer can be improved. .

  The (meth) acrylate compound preferably contains a linear hydrocarbon or a cyclic hydrocarbon. Specific examples of the (meth) acrylate compound include, for example, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate. As the (meth) acrylate compound, one of these may be used alone, or two or more may be used in combination. Moreover, these copolymers may be sufficient. Especially, it is preferable that it is at least 1 sort (s) selected from the group which consists of dodecyl (meth) acrylate, a tridecyl (meth) acrylate, and a cyclohexyl (meth) acrylate at the point which can express favorable antistatic performance.

  The quaternary ammonium salt-containing polymer preferably has a weight average molecular weight of 1000 to 50,000. When the above-described weight average molecular weight is less than 1000, a quaternary ammonium salt-containing polymer permeates into the substrate in the production of the optical laminate when the permeable solvent described later is used as the solvent, and the produced optical The antistatic property of the laminate may not be satisfied. In addition, if the content of the quaternary ammonium salt-containing polymer is too large in order to obtain an optical laminate having sufficient antistatic properties, the optical properties may be deteriorated and the liquid crystal layer may have insufficient hardness. When the weight average molecular weight exceeds 50,000, the viscosity of the resin composition increases, and the coatability may deteriorate. A more preferable lower limit of the weight average molecular weight is 1200, a more preferable upper limit is 30,000, a still more preferable lower limit is 5000, and a still more preferable upper limit is 20,000.

  In addition, the weight average molecular weight of the said quaternary ammonium salt containing polymer can be calculated | required by polystyrene conversion by gel permeation chromatography (GPC). Tetrahydrofuran or chloroform can be used as the solvent for the GPC mobile phase. As the measurement column, a commercially available column for tetrahydrofuran or chloroform may be used in appropriate combination. Examples of the commercial product column include Shodex GPC KF-801, GPC KF-802, GPC KF-803, GPC KF-804, and GPC-KF800D (all trade names, manufactured by Showa Denko KK). it can. As the detector, an RI (differential refractive index) detector and a UV detector may be used. Using such a solvent, column, and detector, the weight average molecular weight can be appropriately measured by a GPC system such as Shodex GPC-101 (manufactured by Showa Denko).

As a commercial item of the said quaternary ammonium salt containing polymer which can be used in this invention, H6100, H6100M, H6500 (made by Mitsubishi Chemical Corporation), Colcoat NR121X, Colcoat NR121X-9IPA (made by Colcoat), 1SX3000, 1SX3004 ( Taisei Fine Chemical Co., Ltd.), Uniresin AS-10 / M, Uniresin AS-12 / M, Uniresin AS-15 / M, Uniresin ASH26 (Shin Nakamura Chemical Co., Ltd.), UV-ASHC-01 (Nihon Kasei Co., Ltd.), etc. Can be mentioned. Especially, H6100, H6
100M, H6500 is preferably used.

In addition to the quaternary ammonium salt, a boric acid compound may be added. Examples of the boric acid compound include those represented by the following formula (4).

Specific examples of X ⁺ include organic ions such as tetramethylammonium, tetrabutylammonium, and benzyltrimethylammonium ions, pyridinium ions such as N-methylbilidinium and N-benzylpitidinium, tetraphenylphosphonium, tetra Examples thereof include phosphonium ions such as butylphosphonium, and inorganic ions include lithium ions, sodium ions, potassium ions, cesium ions, and the like.

Specific examples of X ²⁺ include magnesium ion, calcium ion, nickel ion, copper ion, divalent iron ion, zinc ion and the like.

Sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate in which the counter cation X ⁺ is a sodium ion can be synthesized by the following method. It is obtained by reacting 5-iodo-1,3-bis (trifluoromethyl) benzene with magnesium in an ether solution to give a Grignard reagent, then reacting with boron trifluoride ether adduct and adding it to an aqueous sodium carbonate solution. It is done. When the counter cation X ⁺ is other ions, it can be obtained by exchanging with sodium ions using an ion exchange resin column.

In addition to the quaternary ammonium salt, an electron accepting compound may be added. Examples of the electron accepting compound include tetracyanoquinodimethane, tetranitrofluorenone, and linear polyethers. Among the linear polyethers, those represented by the following formula (5) are preferable.

  Specific examples of those represented by the above formula (5) include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl. Examples include ether.

  The amount of the antistatic agent is preferably 0.1 parts by mass or more and 7.0 parts by mass or less with respect to 100 parts by mass of the rod-shaped compound. If the amount is less than 0.1 parts by mass, it is not preferable in that the rod-shaped compound may not be appropriately prevented from being charged. Exceeding 7.0 parts by mass is not preferable because it may affect the transparency of the pattern retardation film and the orientation of the liquid crystal.

[solvent]
The above rod-shaped compound is usually dissolved in a solvent. The solvent is not particularly limited as long as it can uniformly disperse the rod-like compound. For example, hydrocarbon solvents such as benzene and hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone (hereinafter referred to as “CHN”) and the like. Ketone solvents, tetrahydrofuran, 1,2-dimethoxyethane, ether solvents such as propylene glycol monoethyl ether (PGME), alkyl halide solvents such as chloroform and dichloromethane, methyl acetate, ethyl acetate, butyl acetate, propylene glycol Ester solvents such as monomethyl ether acetate, amide solvents such as N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide, anone solvents such as cyclohexane, methanol, ethanol, isopropyl alcohol Lumpur but (hereinafter referred to as "IPA".) Alcohol solvents such as may be exemplified, but the invention is not limited thereto. Moreover, one type of solvent may be sufficient and the mixed solvent of two or more types of solvents may be sufficient.

  The amount of the solvent is preferably 66 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the rod-shaped compound. If it is less than 66 parts by mass, the rod-like compound may not be uniformly coated and dissolved, which is not preferable. If it exceeds 900 parts by mass, a part of the solvent remains, which is not preferable in that reliability may be lowered and coating may not be performed uniformly.

[Other compounds]
The polymerizable liquid crystal composition of the present invention may contain other compounds as necessary. The other compound is not particularly limited as long as it does not impair the arrangement order of the rod-shaped compound described above, and examples thereof include a polymerization initiator, a polymerization inhibitor, a plasticizer, a surfactant, and a silane coupling agent. be able to.

(Polymerization initiator)
Examples of the polymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Hiller ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, naphthalenesulfonyl chloride , Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, N1717 manufactured by Adeka, carbon tetrabromide, tribromophenyl Examples include a combination of a photoreductive dye such as sulfone, benzoin peroxide, eosin, and methylene blue with a reducing agent such as ascorbic acid or triethanolamine. In this embodiment, these photoinitiators can be used 1 type or in combination of 2 or more types.

  The photopolymerization initiator needs to be added within a range that does not significantly impair the alignment of the liquid crystal, and is preferably 0.01 to 15 parts by mass, and 0.1 to 12 parts by mass with respect to 100 parts by mass of the rod-shaped compound. Is more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 10 parts by mass.

  In addition to the polymerization initiator, a polymerization initiation assistant may be used in combination. Examples of polymerization initiation aids include tertiary amines such as triethanolamine and methyldiethanolamine, and benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylamidebenzoate. It is not limited.

(Polymerization inhibitor)
The polymerization inhibitor is used to increase the storage stability of the rod-like compound. As a polymerization inhibitor, for example, reaction of diphenylpicrylhydrazide, tri-p-nitrophenylmethyl, p-benzoquinone, p-tert-butylcatechol, picric acid, copper chloride, methylhydroquinone, methoquinone, tert-butylhydroquinone, etc. Although a polymerization inhibitor can be used, a hydroquinone polymerization inhibitor is preferable from the viewpoint of storage stability, and methylhydroquinone is particularly preferable.

(Surfactant)
The surfactant is used to adjust the dynamic surface tension of the rod-like compound and suppress lateral unevenness of the retardation layer.

  An example of the surfactant is a fluorine-based surfactant. As the fluorosurfactant, a compound having a fluoroalkyl group or a fluoroalkylene group at at least one of the terminal, main chain, and side chain is preferable, and specific examples thereof include 1,1,2,2-tetra Fluorooctyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, octaethylene glycol di (1,1,1, 2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2) -Tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-penty ) Ether, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, par Anionic surfactants such as sodium fluoro-n-dodecyl sulfonate, sodium fluoroalkylbenzene sulfonate, sodium fluoroalkyl phosphonate, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxy Ethylene ether), perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylates, nonionic surfactants such as fluoroalkyl esters, cationic surfactants such as fluoroalkylammonium iodide, fluoroalkylbetaines, etc. It may be mentioned amphoteric surfactants. Among these, nonionic surfactants are particularly preferably used from the viewpoint that the voltage holding ratio when the retardation layer is used in a liquid crystal display element can be maintained satisfactorily.

  Examples of commercially available fluorosurfactants include BM-1000, -1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F183, F178, and the like. F191, F471, F475, F476 (above, manufactured by DIC), FLORARD FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112 S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105. SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), and FT-100 FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S ( As mentioned above, the Neos company) etc. can be mentioned.

  The fluorine-based surfactant is preferably added in a range that does not significantly impair the alignment of the liquid crystal, and is preferably added in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the rod-shaped compound. By adding an amount of 0.01 parts by mass or more, sufficient coating property can be imparted to the rod-shaped compound, and a good effect of preventing horizontal stripe unevenness is exhibited. Moreover, it can suppress that the alignment defect arises in the liquid crystal in a phase difference layer, and the electrical reliability of a phase difference layer falls by making addition amount into 1 mass part or less.

<Pattern retardation film 1>
FIG. 1 is a diagram showing a pattern retardation film 1 according to this embodiment. In the following, “pattern phase difference” is abbreviated as “phase difference”, but “phase difference” is synonymous with “pattern phase difference” unless otherwise specified. In the retardation film 1, a pattern alignment layer 12 including a photo-alignment material that exhibits photo-alignment properties by irradiation with polarized light is formed on a substrate 11, and the above-described retardation layer formation is formed on the pattern alignment layer 12. It is obtained by forming a retardation layer 13 containing a polymerizable liquid crystal composition.

[Substrate 11]
The base material 11 is a transparent film material, has a function of supporting the pattern alignment layer 12, and is formed in a long shape.

  The substrate 11 preferably has a small retardation, and an in-plane retardation (in-plane retardation value, hereinafter also referred to as “Re value”) is preferably in the range of 0 nm to 10 nm, and 0 nm to 5 nm. More preferably, it is in the range of 0 nm to 3 nm. If the Re value exceeds 10 nm, the display quality of the flat panel display using the pattern alignment film may be deteriorated, which is not preferable.

Here, the Re value is an index indicating the degree of birefringence in the in-plane direction of the refractive index anisotropic body. When the refractive index in the fast axis direction orthogonal to the axial direction is Ny, and the thickness in the direction perpendicular to the in-plane direction of the refractive index anisotropic body is d,
Re [nm] = (Nx−Ny) × d [nm]
It is a value represented by. The Re value can be measured by, for example, a parallel Nicol rotation method using a phase difference measuring device KOBRA-WR (manufactured by Oji Scientific Instruments). Further, in this specification, unless otherwise specified, the Re value means a value at a wavelength of 589 nm.

  The transmittance of the substrate 11 in the visible light region is preferably 80% or more, and more preferably 90% or more. Here, the transmittance | permeability of a transparent film base material can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

  The substrate 11 is preferably a flexible material having flexibility that can be wound into a roll. Such flexible materials include cellulose derivatives, norbornene polymers, cycloolefin polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer, polystyrene. And epoxy resins, polycarbonates, polyesters, and the like. Especially, it is preferable to use a cellulose derivative at the point which is excellent in optical isotropy and can manufacture the pattern orientation film excellent in the optical characteristic.

  Among the cellulose derivatives, cellulose esters are preferably used and cellulose acylates are more preferably used because they are widely used industrially and are easily available.

  As said cellulose acylates, C2-C4 lower fatty acid ester is preferable. The lower fatty acid ester may include only a single lower fatty acid ester such as cellulose acetate, and may include a plurality of fatty acid esters such as cellulose acetate butyrate and cellulose acetate propionate. There may be.

  Among the lower fatty acid esters, cellulose acetate can be particularly preferably used. As the cellulose acetate, it is most preferable to use TAC having an average degree of acetylation of 57.5% to 62.5% (substitution degree: 2.6 to 3.0). Here, the degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation can be determined by measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). In addition, the acetylation degree of TAC can be calculated | required by said method, after removing impurities, such as a plasticizer contained in a film.

  The thickness of the base material 11 is not particularly limited as long as it is within a range in which the necessary self-supporting property can be imparted to the retardation film, depending on the use of the retardation film produced using the pattern alignment film. Usually, it is preferably within the range of 25 μm to 125 μm, more preferably within the range of 40 μm to 100 μm, and even more preferably within the range of 60 μm to 80 μm. If it is less than 25 μm, the necessary self-supporting property may not be imparted to the retardation film, which is not preferable. When the retardation film is longer than 125 μm, when the retardation film is long, when the long retardation film is cut into a single-phase retardation film, the processing waste increases or the cutting blade is worn. May become faster, which is not preferable.

  The base material 11 is not restricted to the structure which consists of a single layer, You may have the structure by which the several layer was laminated | stacked. When it has the structure by which the several layer was laminated | stacked, the layer of the same composition may be laminated | stacked, and the several layer which has a different composition may be laminated | stacked.

[Pattern orientation layer 12]
The pattern alignment layer 12 has two types of alignment patterns alternately. This alignment pattern may be formed by a rubbing process of rolling with a roll having an uneven shape and transferring the uneven shape, or oriented by light irradiation using a photo-alignment material that exhibits photo-alignment properties by polarized light irradiation. It may be formed by a photo-alignment method. When the pattern alignment layer 12 is formed by rubbing, the pattern alignment layer 12 may be any material as long as it contains a widely used energy ray curable resin (such as an ultraviolet curable resin). . On the other hand, when forming the pattern alignment layer 12 by a photo-alignment method, the pattern alignment layer 12 needs to contain the composition for pattern alignment layers demonstrated below.

[Composition for pattern alignment layer]
When forming the pattern alignment layer 12 by a photo-alignment method, the pattern alignment layer 12 contains the composition for pattern alignment layers demonstrated below. This composition for pattern alignment layers contains the photo-alignment material which exhibits photo-alignment property by polarized light irradiation, and the solvent which dissolves this photo-alignment material.

(Photo-alignment material)
The photo-alignment material refers to a material that can exhibit an alignment regulating force by irradiation with polarized ultraviolet rays. The alignment regulating force means that when an alignment layer containing a photo-alignment material is formed and a layer made of a rod-shaped compound (polymerizable liquid crystal composition for forming a retardation layer in the present invention) is formed on this alignment layer, the rod-shaped compound Is a function of arranging the in a predetermined direction.

  The photo-alignment material is not particularly limited as long as it exhibits the above-mentioned alignment regulating force by irradiating polarized light. Such photo-alignment materials include photoisomerization materials that reversibly change the alignment regulation force by changing only the molecular shape by cis-trans changes, and photoreaction materials that change the molecules themselves by irradiating polarized light. It can be divided roughly. In the present invention, any of the photoisomerization material and the photoreaction material can be preferably used, but the photoreaction material is more preferably used. Since the photoreactive material is one in which molecules react with each other when polarized light is irradiated to express the alignment regulating force, it is possible to irreversibly express the alignment regulating force. Therefore, the photoreactive material is superior in the temporal stability of the orientation regulating force.

  The photoreactive material can be further classified according to the type of reaction caused by polarized light irradiation. Specifically, a photodimerization type material that develops an alignment regulation force by causing a photodimerization reaction, a photodegradable material that produces an orientation regulation force by producing a photodecomposition reaction, an orientation regulation by producing a photobinding reaction It can be divided into a photocoupled material that develops force, and a photodecomposition-coupled material that develops alignment regulating force by causing a photodecomposition reaction and a photocoupled reaction. In the present invention, any of the above-mentioned photoreactive materials can be suitably used, but it is more preferable to use a photodimerization type material from the viewpoint of stability and reactivity (sensitivity).

  The photodimerization type material is not particularly limited as long as it is a material capable of expressing an alignment regulating force by causing a photodimerization reaction. It is preferable that it is within a range of 280 nm to 400 nm, and more preferably within a range of 300 nm to 380 nm.

  Examples of such a photodimerization type material include polymers having cinnamate, coumarin, benzylidenephthalimidine, benzylideneacetophenone, diphenylacetylene, stilbazole, uracil, quinolinone, maleinimide, or a cinnamilidene acetic acid derivative. Among them, a polymer having one or both of cinnamate and coumarin is preferably used in that the orientation regulating force is good. Specific examples of such a photodimerization type material include compounds described in, for example, JP-A-9-118717, JP-T-10-506420, JP-T2003-505561, and WO2010 / 150748. Can be mentioned.

As the cinnamate and coumarin, those represented by the following formulas Ia and Ib are preferably used.

In the above formula, A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furylene, 1,4- or 2,6-naphthylene, Unsubstituted, fluorine, chlorine or cyclic, linear or branched alkyl residues of 1 to 18 carbon atoms (unsubstituted or mono- or polysubstituted by fluorine, chlorine, 1 Represents phenylene which is mono- or polysubstituted by two or more non-adjacent —CH ₂ — groups which may be independently substituted by the group C.

  In the above formula, B represents a hydrogen atom or a group capable of reacting or interacting with a second substance, such as a polymer, oligomer, monomer, photoactive polymer, photoactive oligomer and / or photoactive monomer or surface. Represents.

In the above formula, C represents —O—, —CO—, —CO—O—, —O—CO—, —NR ₁ —, —NR ₁ —CO—, —CO—NR ₁ —, —NR ₁ —. CO—O—, —O—CO—NR ₁ —, —NR ₁ —CO—NR ₁ —, —CH═CH—, —C≡C—, —O—CO—O— and Si (CH 3) 2 — A group selected from O—Si (CH 3) 2 — (wherein R ₁ represents a hydrogen atom or lower alkyl).

In the above formula, D represents —O—, —CO—, —CO—O—, —O—CO—, —NR ₁ —, —NR ₁ —CO—, —CO—NR ₁ —, —NR ₁ —. CO—O—, —O—CO—NR ₁ —, —NR ₁ —CO—NR ₁ —, —CH═CH—, —C≡C—, —O—CO—O— and Si (CH 3) 2 — A group selected from O—Si (CH 3) 2 — (R ₁ represents a hydrogen atom or lower alkyl), an aromatic group or an alicyclic group.

In the above formula, S ₁ and S ₂ are independently of each other a single bond or a spacer unit, for example a linear or branched alkylene group having 1 to 40 carbon atoms (unsubstituted, fluorine or chlorine One or more substituted and one or more non-adjacent —CH ₂ — groups may be independently substituted by the group D, but the oxygen atoms are not directly bonded to each other).

In the above formula, Q represents an oxygen atom or NR ₁ — (R ₁ represents a hydrogen atom or lower alkyl).

In the above formula, X and Y are independently of each other hydrogen, fluorine, chlorine, cyano, alkyl having 1 to 12 carbon atoms (optionally substituted by fluorine and optionally not one or more adjacent). alkyl -CH ₂ - groups are -O -, - CO-O - , - O-CO- and / or CH = CH- represents a) are replaced by.

  In addition, the photo-alignment material used for this invention may be only 1 type, and may use 2 or more types.

(solvent)
The solvent used in the composition for the pattern alignment layer is not particularly limited as long as it can dissolve the photo-alignment material or the like at a desired concentration. For example, hydrocarbon solvents such as benzene and hexane, methyl ethyl ketone, methyl isobutyl Ketone solvents such as ketone and cyclohexanone (hereinafter referred to as “CHN”), ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and propylene glycol monoethyl ether (PGME), and alkyl halide solvents such as chloroform and dichloromethane Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, amide solvents such as N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide, anone solvents such as cyclohexane, Lumpur, ethanol can be exemplified an alcohol solvent such as isopropyl alcohol (hereinafter. Referred to as "IPA"), but is not limited thereto. Moreover, one type of solvent may be sufficient and the mixed solvent of two or more types of solvents may be sufficient.

  The amount of the solvent is preferably 600 parts by mass or more and 3900 parts by mass or less with respect to 100 parts by mass of the photo-alignment material. If it is less than 600 parts by mass, the photo-alignment material may not be dissolved uniformly, which is not preferable. When the amount exceeds 3900 parts by mass, a part of the solvent remains, and the remaining solvent impregnates the base material when the composition for pattern alignment layer is applied onto the base material. It is not preferable in that both the adhesion to the substrate can be lowered.

(Adhesion improver)
Moreover, although it is not an essential component, it is preferable that the composition for pattern orientation layers of this invention contains an adhesion improving agent. When the composition for pattern alignment layer is applied on the base material, the adhesion improver causes a chemical reaction with the base material to roughen the surface of the base material. From the base material and a cured product of the pattern alignment layer composition It has a function to improve the adhesion with the alignment layer.

  Examples of the adhesion improver include polyfunctional acrylates such as pentaerythritol tetraacrylate (hereinafter referred to as “PETA”).

  When PETA or the like is used as an adhesion improver, the amount is preferably 25 parts by mass or less with respect to 100 parts by mass in total of the photo-alignment material. Since the evaporation rate of PETA is slower than the evaporation rate of PGME, when the amount of the adhesion improver exceeds 25 parts by mass, a part of the solvent is formed when the composition for pattern alignment layer is applied on the substrate. As a result, the photo-orientation can be lowered, which is not preferable.

(Other)
In addition, you may contain various additives as needed.

[Formation of pattern alignment layer]
As described above, the alignment pattern may be formed by a rubbing process or may be formed by an optical alignment method. Although not shown in the drawings, when formed by rubbing, an energy ray curable resin is applied to the substrate 11, and then the uneven shape is transferred to the substrate 11 using a roller having an uneven shape formed around it. The energy ray curable resin is cured by irradiation of the energy ray by the energy ray irradiation device. Thus, the manufacturing apparatus 10 transfers the uneven shape formed on the roll plate 13 to the base material 2.

  FIG. 2 is a diagram schematically showing a method of forming an alignment pattern by a photo-alignment method. First, after coating the pattern alignment layer composition on the substrate 11 and heating and drying the pattern alignment layer composition to form a thin film-shaped pattern alignment layer forming layer 12 ′, FIG. As shown in FIG. 5A, the mask 11 is not shielded from the first alignment preparation region 12′A corresponding to the right eye region, but is shielded from only the second alignment preparation region 12′B corresponding to the left eye region. Then, after orienting the first alignment preparation region 12′A that is not shielded in a desired direction by irradiating the pattern alignment layer forming layer 12 ′ with ultraviolet rays (polarized ultraviolet rays) by linearly polarized light, As shown in FIG. 2B, the entire surface of the pattern alignment layer forming layer 12 ′ is irradiated with linearly polarized light whose polarization direction is 90 degrees different from that of the first irradiation, and unexposed in the first irradiation. Align second alignment preparation region 12'B in desired direction To. The pattern alignment layer 12 having two types of alignment patterns is formed by these two UV irradiations.

  In the example of FIG. 2, the first alignment preparation region 12′A is first irradiated with polarized ultraviolet light, and then the second alignment preparation region 12′B is irradiated with polarized ultraviolet light. However, the order is not limited to this, First, the second alignment preparation region 12′B may be irradiated with polarized ultraviolet light, and then the first alignment preparation region 12′A may be irradiated with polarized ultraviolet light.

  The thickness of the pattern alignment layer 12 is not particularly limited as long as it is within a range in which a desired alignment regulating force can be expressed with respect to the rod-shaped compound, but is preferably within a range of 100 nm to 1000 nm. If it is less than 100 nm, the rod-like compound may not be able to express a desired alignment regulating force, which is not preferable. If it exceeds 1000 nm, the adhesion may be reduced, which is not preferable.

[Phase difference layer 13]
Returning to FIG. 1, the retardation layer 13 contains the polymerizable liquid crystal composition of the present invention. Since the retardation layer 13 is formed along the alignment pattern, the retardation layer 13 includes a first retardation region 13A corresponding to the region for the right eye and a second retardation region 13B corresponding to the region for the left eye.

  The amount of the polymerizable liquid crystal composition is not particularly limited as long as the viscosity of the coating liquid for forming the retardation layer can be set to a desired value depending on the coating method applied on the pattern alignment layer 12. In the working solution, it is preferably in the range of 5 to 40 parts by mass, and more preferably in the range of 10 to 30 parts by mass. If the amount is less than 5 parts by mass, the amount of the polymerizable liquid crystal composition is too small, and thus there is a possibility that the incident light to the retardation layer 13 may not be properly aligned, which is not preferable. If the amount exceeds 30 parts by mass, the viscosity of the retardation layer forming coating solution becomes too high, and the workability is inferior.

  The thickness of the retardation layer 13 is not particularly limited as long as it is within a range in which a predetermined retardation can be achieved, but the in-plane retardation of the retardation layer 13 corresponds to λ / 4 minutes. It is preferable to do. Here, λ is a wavelength of 500 nm. As a result, the linearly polarized light passing through the retardation layer 13 can be made into circularly polarized light orthogonal to each other, so that a three-dimensional image can be displayed with higher accuracy.

  The orientation deviation angle defined by the absolute value of the angle difference between the optical axis at the time of polarized light irradiation (+45 degrees or −45 degrees with respect to the longitudinal direction) and the orientation axis of the retardation layer 13 is within 3 degrees. Preferably, it is preferably within 2 degrees. If it exceeds 3 degrees, there is a possibility that uniform orientation cannot be obtained.

<Flat panel display>
The retardation film 1 is preferably used for a flat panel display for three-dimensional display, and has an exceptional effect that it has excellent photo-alignment properties when used for a flat panel display for three-dimensional display.

<Method for producing retardation film 1>
Below, although the manufacturing method of the retardation film 1 in the case of forming by a photo-alignment system is demonstrated, the retardation film 1 may be formed by the rubbing process.

  FIG. 3 shows a method for producing the retardation film 1 by the photo-alignment method. First, (A) The base material 11 is provided from the long film wound up by the roll 31, and the composition coating process which coats the composition 32 for pattern orientation layers on this base material 11 is performed. Subsequently, (B) a pattern alignment layer forming layer forming process is performed in which the composition is thermally cured by a dryer 33 to form a thin film pattern alignment layer forming layer 12 ′. Subsequently, (C) the ultraviolet irradiation process of irradiating the pattern alignment layer forming layer 12 ′ with ultraviolet rays from the ultraviolet irradiation devices 34 and 35 is performed. The pattern alignment layer 12 is formed by the processes (A) to (C).

  Subsequently, (D) a retardation layer forming coating solution is applied from the retardation layer forming coating solution supply apparatus 36 containing the polymerizable liquid crystal composition for forming the retardation layer according to the present invention, A coating solution for forming a retardation layer for forming a layer for forming a retardation layer is applied. Thereafter, (E) a leveling process is performed using the leveling device 37 to make the thickness of the retardation layer forming layer uniform. Then, the pattern alignment layer 12 has the above-mentioned pattern alignment layer 12 by heating the rod-shaped compound contained in the coating film of the retardation layer forming coating solution to a temperature higher than the liquid crystal phase forming temperature by using the dryer 38. An alignment process is performed in which rod-shaped compounds are arranged along different alignment directions of the first alignment region 12A corresponding to the region of the second region and the second alignment region 12B corresponding to the region for the left eye. By this alignment treatment, the retardation layer forming layer becomes the retardation layer 13. Then, the cooling process which cools the laminated body which consists of (G) cooler 39 and which consists of the base material 11 / pattern orientation layer 12 / retardation layer 13 is performed, (H) Polymerization property using the ultraviolet irradiation device 40 A curing process for polymerizing and curing the rod-shaped compound is performed. Then, (I) after the film is taken up on the take-up reel 41, a cutting process for cutting it out to a desired size is performed. The retardation film 1 is produced through the above steps.

[(A) Composition coating treatment]
First, in providing the base material 11, there is no particular limitation as long as the long film can be continuously conveyed, and a method using a general conveying means can be used. Specific examples include a method using an unwinder that feeds a roll-shaped long film, a winder that winds the long film, and a method that uses a belt conveyor, a transport roll, and the like. Moreover, the method of using the floating-type conveyance stand which conveys in the state which floated the film for elongate alignment film formation by discharging and sucking | sucking air may be used.

  In addition, the presence or absence of tension applied to the long film at the time of conveyance is not particularly limited as long as it is a method capable of stably and continuously conveying the long film, but the film is conveyed with a predetermined tension applied. It is preferable. This is because continuous conveyance can be performed more stably.

  The color of the conveying means is preferably a color that does not reflect polarized ultraviolet light that has passed through the long film when it is disposed at a site where the polarized film is irradiated with polarized ultraviolet light. Specifically, black is preferable. Examples of such a black method include a method of chromium treatment of the surface.

  The shape of the roll 31 is not particularly limited as long as the long film can be stably conveyed. However, when the roll 31 is disposed at a site where the long film is irradiated with polarized ultraviolet rays. It is preferable that the distance between the surface of the long film and the ultraviolet irradiation device can be kept constant, and it is usually preferable to have a perfect circular shape.

  In the present embodiment, the composition for pattern alignment layer is applied by applying a gravure coating technique, but is not limited thereto. Specifically, in addition to the gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip pulling method, curtain coating method A die coating method, a casting method, a bar coating method, an extrusion coating method, an E-type coating method, or the like can be used.

  The thickness of the pattern alignment layer forming layer 12 ′ is not particularly limited as long as the desired planarity can be achieved, but is preferably in the range of 0.03 μm to 10 μm. More preferably, it is within the range of 03 μm to 5 μm, and even more preferably within the range of 0.05 μm to 3 μm.

[(B) Layer formation processing for pattern alignment layer formation]
In the pattern alignment layer forming layer forming process, the pattern alignment layer composition is thermally cured using the dryer 33. In this process, the substrate 11 is turned upside down by a reversing roller (not shown), and then guided to the dryer 33, where the pattern alignment layer composition is thermally cured, and then the next step is performed in a semi-dry state. Send it out.

  The curing temperature of the pattern alignment layer composition is preferably 100 ° C. or higher and 130 ° C. or lower. When the temperature is lower than 100 ° C., the composition cannot be uniformly heat-cured, which is not preferable because the thin film may be non-uniform. If it exceeds 130 ° C., the substrate 11 and the thin film may shrink, which is not preferable.

  The curing time of the pattern alignment layer composition is preferably 1 minute or more and less than 10 minutes. If it is less than 1 minute, it cannot be thermally cured, and this is not preferable in that the thin film may become non-uniform. Exceeding 10 minutes is not preferable because repelling or defects may occur and the base material 11 or the thin film may shrink.

[(C) UV irradiation treatment]
Next, an ultraviolet irradiation process for irradiating the pattern alignment layer forming layer 12 ′ with ultraviolet rays will be described in detail with reference to FIG.

  First, as shown in FIG. 2A, the first alignment preparation region 12′A corresponding to the right eye region is not shielded, and only the second alignment preparation region 12′B corresponding to the left eye region is formed. By irradiating the pattern alignment layer forming layer 12 ′ with ultraviolet rays (polarized ultraviolet rays) by linearly polarized light through the mask 11 that is shielded from light, the first alignment preparation region 12′A that is not shielded from light is directed in a desired direction. Orient. Subsequently, as shown in FIG. 2B, ultraviolet rays are irradiated on the entire surface of the pattern alignment layer forming layer 12 ′ by linearly polarized light whose polarization direction is 90 degrees different from that of the first irradiation. The unexposed second alignment preparation region 12′B is aligned in a desired direction. Two types of alignment patterns are formed by these two UV irradiations.

  In the example of FIG. 2, the first alignment preparation region 12′A is first irradiated with polarized ultraviolet light, and then the second alignment preparation region 12′B is irradiated with polarized ultraviolet light. However, the order is not limited to this, First, the second alignment preparation region 12′B may be irradiated with polarized ultraviolet light, and then the first alignment preparation region 12′A may be irradiated with polarized ultraviolet light.

  The pattern of the mask, that is, the pattern irradiation pattern, is stable in the first alignment region 12A (see FIG. 1) corresponding to the region for the right eye and the second alignment region 12B (the same) corresponding to the region for the left eye. If it can form in this, it will not specifically limit, For example, a strip | belt-shaped pattern, a mosaic pattern, a zigzag pattern, etc. can be mentioned. Among them, a belt-like pattern is preferable, and in particular, a belt-like pattern parallel to each other in the longitudinal direction of the long film, that is, pattern irradiation becomes a belt-like pattern parallel to each other in the longitudinal direction of the long film. It is preferable to irradiate polarized ultraviolet rays. It is because it can form easily by fixing the irradiation position of polarized ultraviolet rays and conveying a long film in a longitudinal direction. Moreover, it is because it can irradiate with pattern shape with sufficient precision. In the retardation layer 13, a pattern in which a first retardation region 13A corresponding to the region for the right eye and a second retardation region 13B corresponding to the region for the left eye are formed, and a color filter used in the display device This is because it is easy to make the correspondence with the pattern in which the pixels are formed.

  The pattern width of the mask, that is, the irradiation width and the irradiation interval (non-irradiation width) of polarized ultraviolet rays may be the same or different, but the width of the region corresponding to the region for the right eye and the left eye Preferably, the width of the region corresponding to the region for use is the same. The pattern in which the first phase difference region 13A and the second phase difference region 13B are formed in the phase difference layer 13 and the pattern in which the pixel portion is formed can be easily associated with each other. This is because a panel display can be easily manufactured. When aligning the position with the stripe line of the color filter, the pattern in which the region corresponding to the region for the right eye and the region corresponding to the region for the left eye are formed and the stripe pattern of the color filter have a corresponding relationship. It is preferable to irradiate with a width.

  In the case of a three-dimensional display application, the pattern width is preferably in the range of 50 μm to 1000 μm, and more preferably in the range of 100 μm to 600 μm. In addition, the pattern width here refers to the pattern width of the pattern orientation layer 12 in the base material 11 contained in the phase difference film 1 in a stable contraction state.

  The material constituting the mask is not particularly limited as long as a desired opening can be formed, and examples thereof include metals and quartz that are hardly deteriorated by ultraviolet rays. Specifically, a metal substrate such as SUS that has been patterned by etching, laser processing, or electroforming, and further subjected to surface treatment such as nickel plating as necessary can be used. Further, a light shielding film made of emulsion (silver salt) or chromium can be provided on a substrate made of soda lime glass or quartz.

  Among them, it is preferable that Cr is patterned on synthetic quartz. The pattern alignment layer forming layer 12 'made of a cured product of the pattern alignment layer composition is excellent in dimensional stability and ultraviolet transmittance with respect to changes in temperature and humidity, etc., and can be irradiated with ultraviolet rays with high accuracy, resulting in a highly accurate pattern. This is because the alignment layer 12 can be formed.

  The thickness of the synthetic quartz mask is not particularly limited as long as it can form a pattern with high dimensional accuracy, but it is preferably within a range of 1 mm to 20 mm, and within a range of 5 mm to 18 mm. Is more preferable, and it is still more preferable to be in the range of 9 mm to 16 mm. This is because when the thickness is within the above-mentioned range, the thickness can be reduced, the dimensional accuracy can be improved, and the photomask is not excessively heavy. .

  The polarization direction of the polarized ultraviolet light is not particularly limited as long as the polarization direction with respect to the region corresponding to the region for the right eye and the polarization direction with respect to the region corresponding to the region for the left eye are different. It is preferable that the difference is 90 °. Since the direction (slow axis direction) in which the refractive index is maximum between the first phase difference region 13A and the second phase difference region 13B can be orthogonal to each other, a display device capable of three-dimensional display It is because it can manufacture more suitably.

  The direction different by 90 ° is not particularly limited as long as it can perform three-dimensional display with high accuracy when a display device capable of three-dimensional display is formed using the retardation film 1. Usually, it is preferably within a range of 90 ° ± 3 °, more preferably within a range of about 90 ° ± 2 °, and further preferably within a range of about 90 ° ± 1 °. This is because a display device capable of high-performance three-dimensional display can be obtained.

  The polarized ultraviolet light may be collected or may not be collected. However, when the pattern irradiation is performed on the long film on the transport roll, that is, the polarized ultraviolet light. When there is a difference in the distance from the light source of polarized ultraviolet light within the region irradiated with, the light is preferably condensed with respect to the transport direction. This is because the influence of the distance from the light source can be reduced and the alignment region can be formed with high pattern accuracy.

  Examples of the condensing method include a generally used method, for example, a method using a condensing reflector or a condensing lens having a desired shape. In the present invention, it is preferable that the polarized ultraviolet light is parallel light with respect to the direction (width direction) orthogonal to the transport direction. As a parallelization method, a generally used method, for example, a desired shape is used. Examples thereof include a method using a condensing reflector or a condensing lens.

  The wavelength of the polarized ultraviolet light is appropriately set according to the photo-alignment material and the like, and can be a wavelength used when expressing the alignment regulating force in a general photo-alignment material. Specifically, It is preferable to use irradiation light having a wavelength of 210 nm to 380 nm, preferably 230 nm to 380 nm, more preferably 250 nm to 380 nm.

  Low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps) Etc. can be illustrated. Of these, a metal halide lamp, a xenon lamp, a high-pressure mercury lamp, and the like can be preferably used.

  The method for generating polarized ultraviolet rays is not particularly limited as long as it is a method capable of stably irradiating polarized ultraviolet rays. it can.

  As such a polarizer, one that is generally used for generation of polarized light can be used. For example, a wire grid polarizer having a slit-shaped opening or a plurality of quartz plates are laminated. Examples thereof include a method of performing polarization separation using a Brewster angle, and a method of using a method of performing polarization separation using a Brewster angle of vapor-deposited multilayer films having different refractive indexes.

The irradiation amount of polarized ultraviolet rays is not particularly limited as long as an alignment region having a desired alignment regulating force can be formed. For example, when the wavelength is 310 nm, 3 mJ / cm ^{2 to} 500 mJ / cm. ² is preferable, 4 mJ / cm ^{2 to} 300 mJ / cm ² is more preferable, and 5 mJ / cm ^{2 to} 100 mJ / cm ² is further preferable. This is because an alignment region having a sufficient alignment regulating force can be formed.

The irradiation distance of polarized ultraviolet rays, that is, the distance in the conveyance direction of the long film that receives irradiation of polarized ultraviolet rays is not particularly limited as long as it can be the above-mentioned irradiation amount in each exposure process, It can be set as appropriate according to the line speed or the like. When the irradiation distance is short, it becomes easy to achieve high pattern accuracy, and when the irradiation distance is long, the advantage is that an alignment region having a sufficient alignment regulating force can be obtained even when the line speed is high. There is. In addition, as a method of lengthening the irradiation distance, a method of increasing the number of irradiation times of polarized ultraviolet rays in each exposure process or increasing the irradiation area in the transport direction can be exemplified.
When irradiating the thin film with polarized ultraviolet light, it is preferable to adjust the temperature so that the temperature of the thin film becomes constant. This is because the alignment region can be formed with high accuracy. The temperature of the thin film is preferably 15 ° C to 90 ° C, and more preferably 15 ° C to 60 ° C. Examples of the temperature control method include a method using a temperature control device such as a general heating / cooling device. Specifically, a method using a blower capable of blowing air at a predetermined temperature, a method using a temperature-adjustable as the conveying means, more specifically, a temperature-adjustable conveying roll, The method using a belt conveyor etc. can be mentioned.

[(D) Retardation layer forming coating liquid coating treatment]
Returning to FIG. 3, the retardation layer forming coating solution coating process will be described. In the present embodiment, the retardation layer forming coating solution is applied from the retardation layer forming coating solution supply device 36. A specific coating method is not particularly limited as long as it is a method capable of stably forming a coating film made of a retardation layer forming coating solution on the pattern alignment layer 12. The same thing as what was demonstrated by the material coating process can be illustrated.

  The retardation layer 13 contains a rod-shaped compound, so that the retardation is developed. The degree of the retardation depends on the type of the rod-shaped compound and the thickness of the retardation layer 13. It is to be decided. Therefore, the thickness of the retardation layer 13 is not particularly limited as long as it is within a range in which a predetermined retardation can be achieved, and is appropriately determined according to the use of the retardation film 1 and the like. It is.

[(E) Leveling process]
Subsequently, the leveling device 37 is used to perform a leveling process for making the thickness of the retardation layer forming layer uniform. The thickness of the retardation layer forming layer made of the retardation layer forming coating liquid is in a range such that the in-plane retardation of the retardation layer 13 formed thereafter corresponds to λ / 4 minutes. It is preferable to apply to. As a result, the linearly polarized light passing through the first retardation region 13A and the second retardation region 13B can be made into circularly polarized light that is orthogonal to each other, and as a result, a three-dimensional image can be displayed with higher accuracy. is there.

  When the thickness of the retardation layer 13 is set to a distance within a range in which the in-plane retardation of the retardation layer 13 corresponds to λ / 4 minutes, the specific distance is determined by the rod-shaped compound. It will be determined appropriately depending on the type. When a general rod-shaped compound is used, the distance is in the range of 0.5 μm to 2 μm, but is not limited thereto.

[(F) Orientation treatment]
Subsequently, the rod-shaped compound contained in the coating film of the retardation layer forming coating solution is converted into a rod-shaped compound along different alignment directions of the first alignment region 12A and the second alignment region 12B included in the pattern alignment layer 12. Array. The method for arranging the rod-shaped compounds is not particularly limited as long as the rod-shaped compounds can be arranged in a desired direction. For example, the rod-shaped compounds are heated to a temperature higher than the liquid crystal phase formation temperature by using a dryer 38. Can be mentioned.

  The pattern of the retardation layer 13 formed by this process is the same as the pattern of the pattern alignment layer 12, and the first position corresponding to the right eye region is present on the first alignment region 12 A corresponding to the right eye region. A phase difference region 13A is formed, and a second phase difference region 13B corresponding to the region for the left eye is formed on the second alignment region 12B corresponding to the region for the left eye.

  Whether or not the first retardation region 13A and the second retardation region 13B are formed in the retardation layer 13 is determined, for example, when a sample is put in a polarizing plate crossed Nicol and the sample is rotated. It can be evaluated by confirming that the dark line is reversed. At this time, when the pattern composed of the area A for the right eye and the area B for the left eye is fine, it may be observed with a polarizing microscope. Alternatively, the direction (angle) of the slow axis in each pattern may be measured using an AxoScan manufactured by AXOMETRICS (USA).

  The in-plane retardation of the retardation layer 13 is preferably in the range of 100 nm to 160 nm, more preferably in the range of 110 nm to 150 nm, and still more preferably in the range of 120 nm to 130 nm. In the retardation layer 13, the in-plane retardations indicated by the first retardation region 13A and the second retardation region 13B are substantially the same except that the direction of the slow axis is different.

  By the way, when the rod-shaped compound is heated to the liquid crystal phase formation temperature or higher using the dryer 38, the rod-shaped compound is not only arranged in a desired direction, but also the coating film of the retardation layer forming coating liquid is dried. The The drying of the coating film may be appropriately adjusted according to the amount of solvent remaining, but the wind speed of the drying air applied to the coating film is preferably 3 m / second or less, particularly 0.5 m / second or less. It is preferable.

  The temperature condition depends on the liquid crystal → isotropic phase transition temperature of the liquid crystal used, but is preferably in the range of 40 ° C. to 150 ° C., more preferably in the range of 50 ° C. to 120 ° C. In particular, it is more preferably in the range of 55 ° C to 110 ° C. The drying time is preferably in the range of 0.2 to 30 minutes, more preferably in the range of 0.5 to 20 minutes, and particularly in the range of 1 to 10 minutes. More preferably it is. This is because the solvent can be removed stably under these conditions.

[(G) Cooling treatment]
Then, the cooling process which cools the laminated body which consists of the base material 11 / pattern orientation layer 12 / retardation layer 13 using the cooler 39 is performed. The cooling process may be performed until the stack reaches room temperature.

[(H) Curing treatment]
Subsequently, a curing treatment for polymerizing and curing the polymerizable rod-shaped compound is performed. The method for polymerizing the polymerizable rod-shaped compound may be arbitrarily determined according to the type of the polymerizable functional group possessed by the polymerizable rod-shaped compound. However, an appropriate amount of a polymerization initiator is added and cured by irradiation with actinic radiation. The method is preferred. The actinic radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable rod-like compound, but it is usually preferable to use ultraviolet light or visible light from the viewpoint of the ease of the apparatus. Specifically, it can be the same as the ultraviolet rays used when forming the pattern alignment layer 12. By undergoing such a curing treatment, they can be polymerized to form a network structure, so that the retardation layer 13 having column stability and excellent optical properties can be obtained. Can be formed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Examples and Comparative Examples>

The chemical formula of the rod-shaped compound is as follows.

<Example 1>
10 parts by mass of the first rod-like compound represented by Table 2, 90 parts by mass of the second rod-like compound A, and 3 parts by mass of a quaternary ammonium ion-containing compound (trade name: 1SX-3000, manufactured by Taisei Fine Chemical Co., Ltd.) Part and 3 parts by mass of a photopolymerization initiator (trade name: IRG907, manufactured by BASF) were dissolved in 900 parts by mass of methyl isobutyl ketone (hereinafter also referred to as “MIBK”), and the polymerizable liquid crystal composition of Example 1 was dissolved. Obtained.

<Example 2>
A polymerizable liquid crystal composition of Example 2 was obtained in the same manner as in Example 1 except that the first rod-shaped compound was 90 parts by mass and the second rod-shaped compound A was 10 parts by mass.

<Example 3>
Example 1 except that the composition of the rod-shaped compound is 34 parts by mass of the first rod-shaped compound represented by Table 2, 33 parts by mass of the second rod-shaped compound A, and 33 parts by mass of the second rod-shaped compound B. A polymerizable liquid crystal composition of Example 3 was obtained in the same manner.

<Comparative Example 1>
A polymerizable liquid crystal composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that the quaternary ammonium ion-containing compound was not used.

<Comparative example 2>
A polymerizable liquid crystal composition of Comparative Example 2 was obtained in the same manner as in Example 2 except that the quaternary ammonium ion-containing compound was not used.

<Comparative Example 3>
A polymerizable liquid crystal composition of Comparative Example 3 was obtained in the same manner as in Example 3 except that the quaternary ammonium ion-containing compound was not used.

<Manufacture of retardation film>
The retardation film which concerns on an Example and a comparative example was obtained through the manufacturing process demonstrated in FIG. In that case, the base material used was a TAC base material (trade name: TD60UL-P, thickness: 60 μm, manufactured by Fuji Film Co., Ltd.) whose surface was antiglare-treated, and the conveyance speed was 12 m / min.

  First, 100 parts by mass of a photo-alignment material (trade name: ROP-103, manufactured by Lorick) having both a photodimerization site and a thermal cross-linking site is dissolved in 900 parts by mass of MEK (solvent name) and used for a pattern alignment layer A composition was obtained. Then, the said composition for pattern orientation layers was apply | coated to the back surface of the said TAC base material by the die-coating method so that the film thickness after hardening might be set to 200 nm. And it was made to flow for 2 minutes in the dryer adjusted to 100 degreeC, the solvent was evaporated, and the composition was thermoset. Thereby, a thin film having a thickness of 200 nm was formed.

Synthetic quartz with a stripe pattern of width 500μm in the direction parallel to the transport direction of the original fabric with polarized ultraviolet rays (polarization axis is 45 ° with respect to the transport direction of the film) passed through the wire grid. Irradiation was through the mask formed above. Subsequently, polarized ultraviolet rays (with a polarization axis of −45 ° with respect to the film transport direction) that passed through a wire grid without passing through a mask were irradiated. At this time, “H bulb” (manufactured by Fusion) was used as the ultraviolet irradiation device. The wavelength of polarized ultraviolet light was 313 nm, and the integrated light quantity was 40 mJ / cm ² . The integrated light quantity was measured using an ultraviolet light quantity meter “UV-351” (manufactured by Oak Manufacturing Co., Ltd.).

Subsequently, the polymerizable liquid crystal composition according to the example or the comparative example was applied on the pattern alignment layer of the pattern alignment film by a die coating method, and leveled so that the final layer thickness was 1 μm. Then, it flows for 1 minute in the first dryer adjusted to 60 ° C., 0.5 minute in the second dryer adjusted to 95 ° C., and 0.5 minute in the third dryer adjusted to 105 ° C., and is cooled to near room temperature. After that, ultraviolet rays having a wavelength of 260 nm were irradiated using the same type of ultraviolet irradiation apparatus as the above-described ultraviolet irradiation apparatus until the integrated light amount reached 300 mJ / cm ² . The retardation film which concerns on an Example and a comparative example was obtained through said process.

<Evaluation of orientation state of rod-like compound>
First, the orientation state of the rod-shaped compound was evaluated. The alignment state was performed by measuring an alignment angle by a parallel Nicol rotation method using a phase difference measuring device KOBRA-WR (manufactured by Oji Scientific Instruments). The results are shown in Table 3.

<Appearance evaluation>
Moreover, the external appearance of the retardation film which concerns on an Example and a comparative example was evaluated. Appearance evaluation is carried out by attaching polarizing plates (trade name: HCL2-5618HCS, manufactured by Sanlitz) on both sides of the retardation film so as to be in a crossed Nicol arrangement, and placing the bonded members on a liquid crystal backlight. The degree of cloudiness on the front was visually observed in a dark room. The case where the degree of white turbidity was small and no orientation failure was observed was indicated as “◯”, and the case where the degree of white turbidity was high and orientation failure was observed was indicated as “x”. The results are shown in Table 3.

<Evaluation of charging on the web>
Moreover, the charge on a web was evaluated about the retardation film which concerns on an Example and a comparative example. 7 positions shown in FIG. 3, that is, a: after application of a coating solution for forming a retardation layer, b: after leveling, c: after first drying, d: after second drying, e: after third drying, The amount of charge on the web was measured after f: cooling and g: before ultraviolet irradiation. The charge amount was measured using a digital electrostatic potential measuring device MODEL KSD-2000 (Kasuga Denki Co., Ltd.) according to the instructions in the attached instruction manual. The results are shown in Table 3.

  Contains a first rod-shaped compound having a cyano group at one end and (meth) acrylate at the other end, a second rod-shaped compound having (meth) acrylate at both ends, and a quaternary ammonium salt It was confirmed that the pattern retardation film using the polymerizable liquid crystal composition to be made can be in a desired alignment state and has an excellent appearance (Examples 1 to 3). This seems to be because the charge on the web is changing at a low value in the entire manufacturing process of the retardation film.

  On the other hand, the pattern retardation film using the polymerizable liquid crystal composition containing no quaternary ammonium salt is in an actual alignment state even when the polarization axis is aligned in a direction of ± 45 ° with respect to the film transport direction. It was confirmed that deviation occurred. Moreover, it was confirmed that an external appearance is also inferior compared with the pattern phase difference film of an Example (comparative examples 1-3). This is considered to be due to a significant increase in the amount of charge on the web after cooling the laminate composed of the substrate 11 / pattern alignment layer 12 / retardation layer 13.

DESCRIPTION OF SYMBOLS 1 Pattern retardation film 11 Base material 12 Pattern orientation layer 13 Phase difference layer

Claims (5)

A retardation film in which an alignment layer is formed on a substrate and a retardation layer made of a polymerizable liquid crystal composition is formed on the alignment layer,
The polymerizable liquid crystal composition is
A first rod-shaped compound having a cyano group at one end and (meth) acrylate at the other end;
A second rod-shaped compound having (meth) acrylate at both ends;
A quaternary ammonium salt-containing polymer obtained by copolymerizing a quaternary ammonium salt and a (meth) acrylate compound, containing 7.0 parts by mass or less with respect to 100 parts by mass of the rod-shaped compound;
A fluorine-based interface having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain, contained in an amount of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the rod-shaped compound Containing an active agent ,
The retardation film whose in-plane retardation of the said retardation layer is 100 nm or more and 160 nm or less . The retardation film according to claim 1, wherein the first rod-shaped compound contains a compound represented by the following formula (1).

The retardation film according to claim 1 or 2, wherein the second rod-shaped compound contains a compound represented by the following formula (2).

Forming an alignment layer on an elongated substrate, and forming a retardation layer made of heavy polymerizable liquid crystal composition to the alignment layer observed including,
The polymerizable liquid crystal composition is
A first rod-shaped compound having a cyano group at one end and (meth) acrylate at the other end;
A second rod-shaped compound having (meth) acrylate at both ends;
A quaternary ammonium salt-containing polymer obtained by copolymerizing a quaternary ammonium salt and a (meth) acrylate compound, containing 7.0 parts by mass or less with respect to 100 parts by mass of the rod-shaped compound;
A fluorine-based interface having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain, contained in an amount of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the rod-shaped compound Containing an active agent,
A method for producing a retardation film, wherein an in-plane retardation of the retardation layer is from 100 nm to 160 nm . Optical axis of the retardation layer, the long case of the elongated direction of 0 degrees elongated substrates, according to claim 4 is within 45 degrees ± 2 degrees and / or -45 ° ± 2 ° A method for producing a retardation film.

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