JP2012063387A - Polymerizable liquid crystal composition and optical film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an optical member, by which an optical member having a high dichroic ratio can be produced.SOLUTION: The production method of an optical member includes steps of: (1) forming a film by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a solvent on a first substrate and removing the solvent; (2) mounting a second substrate to cover the surface of the film obtained in the step (1); (3) aligning the polymerizable liquid crystal compound included in the film obtained in the step (2) where the second substrate is mounted, so as to obtain a film having a liquid crystal phase formed therein; and (4) polymerizing the polymerizable liquid crystal compound included in the film having the liquid crystal phase formed therein, obtained in the step (3) so as to obtain the optical member having a composition layer comprising the polymerized liquid crystal compound layered between the two substrates.

Description

  The present invention relates to a method for manufacturing an optical member.

  In the liquid crystal display device, optical members such as a polarizing plate and a retardation plate are used. In addition, as a method for producing such an optical member, a single substrate is used, and a polymerizable liquid crystal composition is applied to the substrate by a spin coating method, heated, and then exposed to an optical member. Methods for obtaining membranes are known.

Special table 2008-547062 gazette

  In a conventionally known method for manufacturing an optical member, it may not always be easy to manufacture an optical member having a high dichroic ratio.

The present invention provides the following [1] to [6].
[1] A method for producing an optical member including the steps described in (1) to (4).
(1) Step (2) of forming a film by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a solvent to the first substrate and removing the solvent. The surface of the film obtained in (1) Steps of placing a second substrate so as to cover (3) Steps of obtaining a film in which a liquid crystal phase is formed by aligning the polymerizable liquid crystal compound contained in the film on which the second substrate obtained in (2) is placed (4) By polymerizing the polymerizable liquid crystal compound contained in the film formed with the liquid crystal phase obtained in (3), a composition layer in which the polymerizable liquid crystal compound is polymerized is laminated between the two substrates. Process for obtaining an optical member

[2] The production method according to [1], further including the step described in (5).
(5) A step of removing at least one substrate from an optical member in which a composition layer obtained by polymerizing a polymerizable liquid crystal compound is laminated between two substrates.

[3] The manufacturing method according to [1] or [2], wherein the second substrate is a substrate on which an alignment film is formed.
[4] The production method according to any one of [1] to [3], wherein the liquid crystal phase is a smectic phase.
[5] The production method according to any one of [1] to [4], wherein the polymerizable liquid crystal composition further includes a dichroic dye.
[6] A display device including an optical member obtained by the manufacturing method according to any one of [1] to [5].

  According to the polymerizable liquid crystal composition of the present invention, an optical member having a high dichroic ratio can be easily obtained.

It is the schematic showing the optical member 1 obtained by the manufacturing method of this invention. It is the schematic showing the liquid crystal display device 10 of this invention. It is the schematic showing the liquid crystal display device 24 of this invention. It is the schematic showing the EL display apparatus 30 of this invention. It is the schematic showing the EL display apparatus 44 of this invention. It is the schematic showing the projection type liquid crystal display device of this invention.

The optical member refers to a member that can transmit light and has an optical function. The optical function means absorption, reflection, diffraction, scattering, refraction, birefringence and the like. A retardation plate which is a kind of optical member is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.
A polarizing plate, which is a kind of optical member, is used to decompose incident light that is not polarized into two orthogonally polarized light components, transmit one polarized light component, and absorb the other polarized light component. . The axial direction of the transmitted polarization component is called the transmission axis, and the axial direction of the polarized component to be absorbed is called the absorption axis.

(1) It is a manufacturing method of an optical member including the process described in (4).
(1) Step (2) of forming a film by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a solvent to the first substrate and removing the solvent. The surface of the film obtained in (1) Steps of placing a second substrate so as to cover (3) Steps of obtaining a film in which a liquid crystal phase is formed by aligning the polymerizable liquid crystal compound contained in the film on which the second substrate obtained in (2) is placed (4) A composition layer in which the polymerizable liquid crystal compound is polymerized by polymerizing the polymerizable liquid crystal compound contained in the film in which the liquid crystal phase obtained in (3) is formed (hereinafter sometimes referred to as “polymer layer”). A process for obtaining an optical member laminated between two substrates.

  Step (1) is a step in which a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a solvent is applied to a first substrate, and the solvent is removed to form a film. The polymerizable liquid crystal composition will be described later.

  Examples of the method for applying the polymerizable liquid crystal composition to the first substrate include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, die coating, dip coating, bar coating, and spin coating. Etc.

As a 1st board | substrate, glass, a plastic sheet, a plastic film, or a translucent film can be mentioned, for example. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, and polyethylene naphthalate films. , Polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film, or polyphenylene oxide film.
By using the first substrate, the optical film can be easily handled without being broken when it is manufactured, transported, or stored.

  In the method for producing an optical member of the present invention, an alignment film is preferably formed on the substrate. The alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied. Moreover, it is preferable to have heat resistance in the heat treatment for solvent removal and liquid crystal alignment. Furthermore, an alignment film that does not peel off due to friction due to rubbing or the like is preferable. Such an alignment film is preferably composed of an alignment polymer or a composition containing an alignment polymer.

  Examples of the orientation polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyacrylamide which are hydrolysates thereof. Mention may be made of polymers such as oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters. These polymers may be used alone, or two or more kinds thereof may be mixed or copolymerized. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  The orientation polymer can be applied after being dissolved in a solvent. The solvent is not particularly limited, but specifically water; alcohol solvent such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene Ester solvents such as glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; pentane, hexane or heptane Aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene or xylene; nitrile solvents such as acetonitrile; tetra Ether solvents such as Dorofuran or dimethoxyethane; chlorinated hydrocarbon solvents such as chloroform or chlorobenzene; and the like. These organic solvents may be used alone or in combination.

In order to form the alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optmer (registered trademark, manufactured by JSR).
If such an alignment film is used, unevenness is reduced, so that an optical film with improved environmental resistance and mechanical resistance can be provided.

  As a method for forming an alignment film on the support substrate, for example, the solution of the alignment polymer or a commercially available alignment film material is applied on the support substrate, and then annealed, and then the support substrate is annealed. An alignment film can be formed thereon. The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm.

  In order to impart an alignment regulating force to the alignment film, it is preferable to perform rubbing or polarized UV irradiation as necessary. By providing the alignment regulating force, the polymerizable liquid crystal compound can be aligned in a desired direction.

  Examples of the method for rubbing the alignment film include a method in which a rubbing cloth is wound and a rotating rubbing roll is brought into contact with the alignment film being transported on a stage. If masking is performed when rubbing or polarized UV irradiation is performed, a plurality of regions (patterns) having different slow axis directions can be formed in the obtained polarizer.

  After coating on the substrate, volatile components such as a solvent contained in the film are dried. Examples of the drying method include a natural drying method, a ventilation drying method, and a vacuum drying method. As drying temperature, 0-250 degreeC is preferable, 30-200 degreeC is more preferable, and 40-130 degreeC is further more preferable. The drying time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

  Step (2) is a step of placing a second substrate so as to cover the surface of the film obtained in step (1). The second substrate preferably covers the surface of the film obtained in the step (1) and is placed in close contact. In addition, it is preferable to place the second substrate at a temperature equal to or higher than the temperature at which the polymerizable liquid crystal composition exhibits an isotropic phase. By placing the second substrate at the above temperature, the polymerizable liquid crystal composition easily flows, so that the second substrate and the film made of the polymerizable liquid crystal composition are easily adhered.

  As the second substrate, the same substrate as the first substrate can be used. As the second substrate, a substrate having transparency is preferable. The first substrate and the second substrate may be the same type of substrate or different types of substrates. A plastic substrate is preferable as the second substrate. Since the plastic substrate is flexible, bubbles are prevented from being mixed between the second substrate and the film made of the polymerizable liquid crystal composition, and are easily adhered to each other.

  An alignment film is preferably formed on the second substrate. Examples of the alignment film include the same alignment films as those used for the first substrate. The alignment film is more preferably subjected to rubbing treatment for imparting alignment regulating force or polarized UV irradiation. When the alignment film is formed on the second substrate, the second substrate is placed so that the alignment film is in contact with the film obtained in the step (1).

  In the case where an alignment film is formed on both the first substrate and the second substrate, it is preferable to place the second substrate so that the direction of the alignment regulating force of the alignment film is the same. Thus, a horizontally oriented film can be obtained more easily. The direction of the alignment regulating force refers to the direction in which the liquid crystal compound laminated on the alignment film is aligned. In the rubbing process, the direction of the rubbing process applied to the alignment film. It is the vibration direction of polarized light.

  Step (3) is a step of obtaining a film in which a liquid crystal phase is formed by aligning the polymerizable liquid crystal compound contained in the film on which the second substrate obtained in step (2) is placed.

  In order to form the liquid crystal phase, the polymerizable liquid crystal compound contained in the film on which the second substrate obtained in step (2) is placed may be heated to a temperature at which the liquid crystal phase is exhibited. The liquid crystal phase is preferably a smectic phase. In addition, a film having a smectic phase formed is obtained by heating to a temperature at which the polymerizable liquid crystal compound contained in the coating film transitions to a nematic phase and then cooling to a temperature at which the polymerizable liquid crystal compound exhibits a smectic phase. It is more preferable. By passing through the nematic phase, the leveling agent contained in the polymerizable liquid crystal composition can easily flow, and a horizontally aligned film can be easily obtained. The heating temperature is preferably a temperature not lower than the nematic phase transition point and not higher than 100 degrees higher than the nematic phase transition point, and more preferably not lower than the nematic phase transition point and not higher than 50 degrees higher than the nematic phase transition point.

Step (4) is an optical member in which a polymer layer is laminated between two substrates by polymerizing the polymerizable liquid crystal compound contained in the film formed with the liquid crystal phase obtained in step (3). It is the process of obtaining. A highly durable optical member can be obtained by polymerizing the polymerizable liquid crystal compound contained in the film in which the liquid crystal phase is formed.
The method for polymerizing the polymerizable liquid crystal compound may be selected according to the type of polymerizable group possessed by the polymerizable liquid crystal compound. If the polymerizable group is a photopolymerizable group, it can be polymerized by a photopolymerization method, and if it is a thermopolymerizable group, it can be polymerized by a thermal polymerization method. In the method for producing an optical member of the present invention, a photopolymerization method is preferable. In the case of the photopolymerization method, since it is not always necessary to heat to a high temperature, a substrate having low heat resistance can be used. The photopolymerization method is performed by irradiating visible light, ultraviolet light, or laser light onto the film on which the liquid crystal phase is formed. In view of easy handling, ultraviolet light is preferable. The light irradiation is performed in a state where a liquid crystal phase is formed on the film. Light irradiation may be performed at the temperature at which the liquid crystal phase is formed in the step (3). At this time, the optical member can be patterned by masking or developing. The exposure amount of light irradiation is preferably ^{200~6000mJ / cm 2, 1000~4000mJ / cm} 2 is more preferable.

The production method of the present invention may include a step (5). Step (5) is a step of removing at least one substrate from the optical member in which the polymer layer is laminated between the two substrates.
As a method of removing the substrate, a method of removing the substrate from the optical member on which the substrate is laminated, a method of removing the substrate by dissolving it with an acid or a solvent, a method of removing the substrate by polishing the laminated substrate, etc. Is mentioned.

  Moreover, in addition to the process of peeling a board | substrate, the process of peeling an alignment film may be further included. By removing the two substrates and the formed alignment film, a film having only a polymer layer can be obtained. The film thickness of the polymer layer is preferably 0.5 to 20 μm.

  As an optical member 1 obtained by the production method of the present invention, an optical member composed of a laminate of a polymer layer and an alignment film and / or a substrate as shown in FIGS. The optical member which consists of a film | membrane only of the polymer layer 5 as shown to i) is mentioned.

  The polymerizable liquid crystal composition used in the production method of the present invention includes a polymerizable liquid crystal compound and a solvent. When the optical member obtained by the production method of the present invention is used as a polarizing plate, it is preferable that a dichroic dye is further included.

The polymerizable liquid crystal composition used in the production method of the present invention contains a polymerizable liquid crystal compound. The polymerizable liquid crystal compound is a compound having a polymerizable group and exhibiting liquid crystallinity. The polymerizable group means a group involved in the polymerization reaction of the polymerizable liquid crystal compound.
The polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound exhibiting a smectic phase. A polymerizable liquid crystal compound exhibiting a nematic phase is more preferable between a temperature exhibiting a smectic phase and a temperature exhibiting an isotropic phase. When the polymerizable liquid crystal compound is such a compound, a horizontally aligned smectic phase tends to be easily obtained.

  Examples of the smectic phase include a smectic A phase, a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, and a smectic K phase. Among these, a smectic B phase, a smectic F phase, a smectic I phase, a tilted smectic F phase and a tilted smectic I phase are preferable, and a smectic B phase is more preferable. When the liquid crystal phase represented by the polymerizable liquid crystal compound is such a liquid crystal phase, a polymer layer having a high degree of alignment order can be obtained.

Examples of the polymerizable liquid crystal composition include a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).
^{U 1 -V 1 -W 1 -X 1} -Y 1 -X 2 -Y 2 -X 3 -W 2 -V 2 -U 2 (1)
[In Formula (1), X ¹ , X ² and X ³ represent a p-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. . However, at least one of X ¹ , X ² and X ³ represents a p-phenylene group which may have a substituent.
Y ¹ and ^{Y 2,} independently of one _{another, -CH 2 CH 2 -, -} CH 2 O -, - COO -, - OCOO-, a single ^{bond, -N = N -, - CR} a = CR b -, - C≡C— or —CR ^a ═N— is represented. Represents.
R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
U ¹ represents a hydrogen atom or a polymerizable group.
U ² represents a polymerizable group.
W ¹ and W ² each independently represent a single bond, —O—, —S—, —COO— or —OCOO—.
V ¹ and V ² each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, — S- or -NH- may be substituted. ]

X ¹ , X ² and X ³ are each independently a p-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent. . However, at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent.
At least two of X ¹ , X ² and X ³ are preferably a p-phenylene group which may have a substituent.
The p-phenylene group is preferably unsubstituted. The cyclohexane-1,4-diyl group is preferably a trans-cyclohexane-1,4-diyl group, and more preferably unsubstituted.

Examples of the substituent that the p-phenylene group may have include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group; a cyano group; a halogeno group such as a fluoro group, a chloro group, and a bromo group Etc.
Examples of the substituent that the cyclohexane-1,4-diyl group may have include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group; a cyano group; a fluoro group, a chloro group, Examples include halogeno groups such as bromo group. Hexane-1,4-diyl -CH group ₂ cycloheteroalkyl - is, -O -, - may be substituted with S- or -NR-. R is a C1-C6 alkyl group or a phenyl group.

Y ¹ and ^{Y 2,} independently of one _{another, -CH 2 CH 2 -, -} CH 2 O -, - COO -, - OCOO-, a single ^{bond, -N = N -, - CR} a = CR b -, - C≡C— or —CR ^a ═N—. The bonding position of these groups may be any direction.
R ^a and R ^b are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a butyl group.
Y ¹ is preferably —CH ₂ CH ₂ —, —COO—, or a single bond.
Y ² is preferably —CH ₂ CH ₂ — or —CH ₂ O—.

U ¹ is a hydrogen atom or a polymerizable group, and preferably a polymerizable group. U ² is a polymerizable group. U ¹ and U ² are preferably both photopolymerizable groups. Here, the photopolymerizable group refers to a group that can participate in polymerization by an active radical, an acid, or the like generated from a photopolymerization initiator. U ¹ and U ² are preferably the same type of group.
Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.

V ¹ and V ² are each independently an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the alkanediyl group is —O—, — S- or -NH- may be substituted.
Examples of the alkanediyl group having 1 to 20 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5. -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group and icosane -1,20-diyl group etc. are mentioned, Preferably it is a C2-C12 alkanediyl group, More preferably, it is a C6-C12 alkanediyl group.
Examples of the substituent that the alkanediyl group may have include a cyano group; a halogeno group such as a fluoro group, a chloro group, and a bromo group.
The alkanediyl group is preferably an unsubstituted alkanediyl group, and more preferably an unsubstituted linear alkanediyl group.

W ¹ and W ² are each independently a single bond, —O—, —S—, —COO— or —OCOO—, preferably a single bond or —O—.

  Examples of the compound (1) include compounds represented by formula (1-1) to formula (1-21). In the formula, the cyclohexane-1,4-diyl group is preferably a trans isomer.

  70-99.9 mass% is preferable with respect to solid content of a composition, and, as for content of a compound (1), 90-99.9 mass% is more preferable. If it is in the said range, there exists a tendency for the orientation of a compound to become high. Here, solid content means the total amount of the component remove | excluding the solvent from the composition. Compound (1) may be used alone or in combination of two or more.

  The polymerizable liquid crystal composition used in the production method of the present invention preferably contains a dichroic dye. When the polymerizable liquid crystal composition of the present invention is a composition containing a polymerizable liquid crystal compound, a dichroic dye, and a solvent, the obtained optical member has a function as a polarizing plate. The dichroic dye refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction.

  The dichroic dye is not particularly limited, and may be a dye or a pigment. The dichroic dye preferably has a maximum absorption wavelength at 300 to 700 nm. Examples of the dichroic dye include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes. The dichroic dye may be used alone or in combination with a plurality of dichroic dyes.

  As the dichroic dye, an azo dye is preferable. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbene azo dye, and a bisazo dye and a trisazo dye are preferable.

As an azo dye, the compound represented by Formula (2) is mentioned, for example.
_{^{A 1 (-N = N-A}} 2) p -N = N-A 3 (2)
[In Formula (2), A ¹ and A ³ may each independently have a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent. Represents a good monovalent heterocyclic group. A ² is each independently a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a substituent 2 which may have a substituent. Represents a valent heterocyclic group. p represents an integer of 1 to 4. When p is an integer greater than or equal to ² , several A2 may mutually be same or different. ]

  The monovalent heterocyclic group is a group in which one hydrogen atom is removed from a heterocyclic ring such as a quinoline ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an imidazole ring, a benzimidazole ring, an oxazole ring, or a benzoxazole ring. Is mentioned. Moreover, as a bivalent heterocyclic group, the group remove | excluding two hydrogen atoms from said heterocyclic ring is mentioned.

  Examples of the substituent that the phenyl group, naphthyl group, monovalent heterocyclic group, p-phenylene group, naphthalene-1,4-diyl group and divalent heterocyclic group may have include a methyl group and an ethyl group. An alkyl group having 1 to 4 carbon atoms such as butyl group; an alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group and butoxy group; a fluorinated alkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; Cyano group; nitro group; halogeno group such as fluoro group, chloro group and bromo group; amino group; amino group substituted by alkyl group having 1 to 4 carbon atoms such as diethylamino group and pyrrolidino group (substituted by amino group) Two alkyl groups may be bonded to each other to form a ring).

As the azo dye, compounds represented by the following formulas (2-1) to (2-6) are preferable. In formulas (2-1) to (2-), B ^{1 to} B ²⁰ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, an amino group, An amino group substituted with an alkyl group having 1 to 4 carbon atoms (two alkyl groups substituted with an amino group may be bonded to each other to form a ring), a chloro group or a trifluoromethyl group. n1-n4 represents the integer of 0-3. If n1 is an integer of 2 or more, a plurality of ^{B 2} may be the same or different from each other, similarly when n2~n4 is an integer of 2 or more, a plurality of ^B 6, ^{B 9} and ^{B 14} are They may be the same or different from each other.

  As said anthraquinone pigment | dye, the compound represented by Formula (2-7) is preferable.

[In Formula (2-7), R ^{1 to} R ⁸ each independently represents a hydrogen atom, —R ^x , an amino group, —NHR ^x , —NR ^x ₂ , —SR ^x, or a halogen atom. R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

  As the acridine dye, a compound represented by the formula (2-8) is preferable.

[In Formula (2-7), R ^{9 to} R ¹⁵ each independently represent a hydrogen atom, —R ^x , an amino group, —NHR ^x , —NR ^x ₂ , —SR ^x, or a halogen atom. R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

  As the oxazone dye, a compound represented by the formula (2-9) is preferable.

[In Formula (2-9), R ^{9 to} R ¹⁵ each independently represent a hydrogen atom, —R ^x , an amino group, —NHR ^x , —NR ^x ₂ , —SR ^x, or a halogen atom. R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]
Examples of the alkyl group having 1 to 4 carbon atoms in R ^x include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the aryl group having 6 to 12 carbon atoms in R ^x include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

  As the cyanine dye, a compound represented by the formula (2-10) and a compound represented by the formula (2-11) are preferable.

[In Formula (2-10), D ¹ and D ² each independently represent a group represented by Formula (2-10a) to Formula (2-10d). n5 represents an integer of 1 to 3. ]

[In Formula (2-11), D ³ and D ⁴ each independently represent a group represented by Formula (2-11a) to Formula (2-11h). n6 represents an integer of 1 to 3. ]

  The content of the dichroic dye is preferably 50 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. Is more preferable. If it is in the said range, it can superpose | polymerize, without disturbing the orientation of a polymerizable liquid crystal compound. If the content of the dichroic dye exceeds 50 parts by mass, the orientation of the polymerizable liquid crystal compound may be unfavorable.

The polymerizable liquid crystal composition used in the production method of the present invention contains a solvent. The solvent is preferably a solvent that can dissolve components other than the solvent contained in the polymerizable liquid crystal composition. Moreover, it is preferable that it is a solvent inactive to the polymerization reaction of a polymeric liquid crystal composition.
Solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone Or ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene And aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile; Hydrofuran and ether solvents such as dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and the like. These solvents may be used alone or in combination.

  The content of the solvent is preferably 50 to 98% by mass with respect to the total amount of the polymerizable liquid crystal composition. In other words, the solid content in the polymerizable liquid crystal composition is preferably 2 to 50% by mass. When the solid content is 2% by mass or more, the film thickness does not become too thin, and the dichroism necessary for the polarizer is obtained. Moreover, since the viscosity of a composition is low as it is 50 mass% or less, there exists a tendency for nonuniformity to become difficult to produce in the film thickness of a coating film. Solid content means the quantity remove | excluding the solvent from the polymeric liquid crystal composition.

  The polymerizable liquid crystal composition used in the production method of the present invention preferably contains a polymerization initiator. The polymerization initiator is a compound that initiates polymerization of the polymerizable liquid crystal compound, and generates an active radical or an acid by the action of light and / or heat. Especially, it is preferable that it is a polymerization initiator (namely, photoinitiator) which generate | occur | produces an active radical or an acid by the effect | action of light, and the photoinitiator which generate | occur | produces a radical by light irradiation is more preferable.

  Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1 -[4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- ON oligomers.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.
Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6 Such as [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  As photopolymerization initiators, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all are manufactured by Ciba Japan Co., Ltd.), Sake All BZ, Sequol Z, Sequol BEE (and above) , All manufactured by Seiko Chemical Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 or Adekaoptomer SP-170 (or more) Commercially available photopolymerization initiators such as TAZ-A, TAZ-PP (manufactured by Nippon Shibel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) can also be used.

  Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile; peroxides such as hydrogen peroxide, persulfate, and benzoyl peroxide.

  The content of the polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. . If it is in the said range, it can superpose | polymerize, without disturbing the orientation of a polymerizable liquid crystal compound.

  When using a photoinitiator as a polymerization initiator, you may use a photosensitizer together. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone and 2-isopropylthioxanthone); anthracene such as anthracene and an alkoxy group-containing anthracene (for example, dibutoxyanthracene). Compound; phenothiazine; rubrene and the like.

  By using a photosensitizer, the polymerization of the polymerizable liquid crystal compound can be made highly sensitive. 0.1-30 mass parts is preferable with respect to 100 mass parts of polymerizable liquid crystal compounds, and the usage-amount of a photosensitizer has more preferable 0.5-10 mass parts, and 0.5-8 mass parts is further. preferable.

  The polymerizable liquid crystal composition used in the production method of the present invention may contain a leveling agent. Examples of the leveling agent include a leveling agent having a polyacrylate compound as a main component, a leveling agent having a fluorine atom-containing compound as a main component, and a leveling agent having a compound having a silicone chain as a main component. The leveling agent has a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the applied film, and examples thereof include a surfactant.

  As a leveling agent mainly composed of a polyacrylate compound, BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380, BYK-381, BYK -392 (both trade names: BYK Chemie) and the like.

  As a leveling agent having a fluorine atom-containing compound as a main component, Megafac (trade name) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-471, F-477, F-479, F-482, F-482 (all of which are manufactured by DIC Corporation), Surflon (trade name) S-381, S-382, S-383, S-393, SC-101, SC-101, SC-105, KH-40, SA-100 (all are manufactured by AGC Seimi Chemical Co., Ltd.), products Name E1830, E5844 (made by Daikin Fine Chemical Laboratories Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352 (all of which are made by Mitsubishi Materials Electronic Chemicals), Florinato (trade) Name) FC-72, the FC-40, the FC-43, the FC-3283 (above all Sumitomo 3M include, Ltd.).

As a leveling agent composed mainly of a compound having a silicone chain, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 As mentioned above, all are Shin-Etsu Chemical Co., Ltd.).

  Content of a leveling agent is 0.01 to 5 mass parts with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 0.05 to 3 mass parts. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the formed liquid crystal phase.

  The polymerizable liquid crystal composition used in the production method of the present invention may contain a polymerization inhibitor. When the polymerizable liquid crystal composition of the present invention contains a polymerization inhibitor, the polymerization of the polymerizable liquid crystal compound can be controlled, and the stability of the polymerizable liquid crystal composition of the present invention can be improved.

Examples of the polymerization inhibitor include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (for example, butyl catechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical, and the like. , Thiophenols, β-naphthylamines, β-naphthols and the like.
The content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. . If it is in the said range, it can superpose | polymerize, without disturbing the orientation of a polymerizable liquid crystal compound.

  The optical member of the present invention obtained as described above can be used for various display devices. A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device (SED). )), Electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg, display device having a grating light valve (GLV) display device, digital micromirror device (DMD)), Examples of the liquid crystal display device include a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, and a projection liquid crystal display device. The display device may be a display device that displays a two-dimensional image, or tertiary. Image may be a stereoscopic display apparatus for displaying.

  FIG. 2 is a schematic view showing the liquid crystal display device 10 of the present invention. The liquid crystal layer 17 is sandwiched between two substrates 14a and 14b.

A color filter 15 is disposed on the liquid crystal layer 17 side of the substrate 14a. The color filter 15 is disposed at a position facing the pixel electrode 22 across the liquid crystal layer 17, and the black matrix 20 is disposed at a position facing the boundary between the pixel electrodes. The transparent electrode 16 is disposed on the liquid crystal layer 17 side so as to cover the color filter 15 and the black matrix 20. An overcoat layer may be provided between the color filter 15 and the transparent electrode 16.
Thin film transistors 21 and pixel electrodes 22 are regularly arranged on the liquid crystal layer 17 side of the substrate 14b. The pixel electrode 22 is disposed at a position facing the color filter 15 with the liquid crystal layer 17 interposed therebetween. An interlayer insulating film 18 having a connection hole (not shown) is disposed between the thin film transistor 21 and the pixel electrode 22.

  Examples of the substrate 14a and the substrate 14b include a glass substrate and a plastic substrate. When manufacturing the color filter 15 and the thin film transistor 21 formed on these substrates, a glass substrate is preferable when a process of heating to a high temperature is required.

  Examples of the thin film transistor 21 include a high-temperature polysilicon transistor formed on a quartz substrate, a low-temperature polysilicon transistor formed on a glass substrate, and an amorphous silicon transistor formed on a glass substrate or a plastic substrate. In order to reduce the size of the liquid crystal display device, a driver IC may be formed on the substrate 14b.

A liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22. In the liquid crystal layer 17, spacers 23 are arranged in order to keep the distance between the substrate 14a and the substrate 14b constant.
Of the layers formed on the substrate 14a and the substrate 14b, an alignment film for aligning the liquid crystal in a desired direction may be disposed on the surface in contact with the liquid crystal layer 17.
Each member is laminated in the order of the substrate 14a, the color filter 15 and the black matrix 20, the transparent electrode 16, the liquid crystal layer 17, the pixel electrode 22, the interlayer insulating film 18 and the thin film transistor 21, and the substrate 14b.

Polarizers (for example, linear polarizers) 12a and 12b and retardation plates (for example, quarter-wave plates and optical compensation plates) are provided as optical members on the outside of the substrate 14a and the substrate 14b with the liquid crystal layer 17 interposed therebetween. 13a and 13b are stacked in this order. At least one selected from the group consisting of the polarizing plates 12a and 12b and the retardation plates 13a and 13b is an optical member obtained by the production method of the present invention. By disposing the optical member obtained by the manufacturing method of the present invention, the liquid crystal display device 10 is provided with a function of converting incident light into linearly polarized light and circularly polarized light and a function of optically compensating for phase shift caused by liquid crystal. can do. The retardation films 13a and 13b may not be arranged depending on the structure of the liquid crystal display device and the type of liquid crystal compound contained in the liquid crystal layer 17. An antireflection film 11 for preventing reflection of external light is disposed outside the polarizing plate 12a. According to the optical member obtained by the manufacturing method of the present invention, the display device can be thinned.
As at least one selected from the group consisting of the polarizing plates 12a and 12b and the retardation plates 13a and 13b, the optical member 1 obtained by the production method of the present invention shown in FIGS. Any of these members may be used.

  A backlight unit 19 that is a light source is disposed outside the polarizing plate 12b. The backlight unit 19 includes a light source, a light guide, a reflection plate, a diffusion sheet, and a viewing angle adjustment sheet. Examples of the light source include electroluminescence, a cold cathode tube, a hot cathode tube, a light emitting diode (LED), a laser light source, and a mercury lamp. What is necessary is just to select the polarizer of this invention according to the characteristic of a light source.

  When the liquid crystal display device 10 of the present invention is a transmissive liquid crystal display device, the white light emitted from the light source in the backlight unit 19 enters the light guide, and the path is changed by the reflector and diffused by the diffusion sheet. Has been. The diffused light is adjusted to have a desired directivity by the viewing angle adjusting sheet, and then enters the polarizing plate 12b from the backlight unit 19.

  Of the incident light that is non-polarized light, only one linearly polarized light is transmitted through the polarizing plate 12b of the liquid crystal panel. This linearly polarized light is converted into circularly polarized light by the phase difference plate 13b, and sequentially passes through the substrate 14b, the pixel electrode 22 and the like and reaches the liquid crystal layer 17.

  Here, depending on the presence or absence of a potential difference between the pixel electrode 22 and the transparent electrode 16 facing the pixel electrode 22, the alignment state of the liquid crystal molecules contained in the liquid crystal layer 17 changes, and the luminance of the light emitted from the liquid crystal display device 10 is controlled. The When the liquid crystal layer 17 is in an alignment state in which the circularly polarized light converted by the phase difference plate 13b is transmitted as it is, the circularly polarized light is transmitted through the liquid crystal layer 17 and the transparent electrode 16, and light in a specific wavelength range is transmitted through the color filter. The liquid crystal display device displays the color determined by the color filter brightest when it passes through 15 and reaches the phase difference plate 13a and further passes through the polarizing plate 12a and the antireflection film 11.

  On the contrary, when the liquid crystal layer 17 is in an alignment state in which the circularly polarized light converted by the retardation plate 13b is converted and transmitted, the light transmitted through the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 is the retardation plate. It is absorbed by 13a and the polarizer 12a. As a result, this pixel displays black. In the intermediate alignment state between these two states, the luminance of the light emitted from the liquid crystal display device 10 is also intermediate between the two, so that this pixel displays an intermediate color.

  In the case where the liquid crystal display device 10 of the present invention is a transflective liquid crystal display device, the pixel electrode 22 has a transmissive portion formed of a transparent material and a reflective portion formed of a material that reflects light. An image is displayed in the same manner as the above-described transmission type liquid crystal display device. On the other hand, in the reflection portion, external light enters the liquid crystal display device from the direction of the antireflection film 11, and circularly polarized light that has passed through the polarizing plate 12 a and the retardation plate 13 a passes through the liquid crystal layer 17 and is reflected by the pixel electrode 22. Used for display.

  FIG. 2 is a schematic diagram showing a liquid crystal display device 24 in which an optical film is arranged inside the substrate (the liquid crystal 17 side). In the liquid crystal display device 24, each member includes an antireflection film 11, a substrate 14a, a polarizing plate 12a, a retardation plate 13a, a color filter 15 and a black matrix 20, a transparent electrode 16, a liquid crystal layer 17, a pixel electrode 22, and an interlayer insulating film. 18, the thin film transistor 21, the retardation plate 13b, the polarizing plate 12b, the substrate 14b, and the backlight unit 19 are laminated in this order. At least one selected from the group consisting of the polarizing plates 12a and 12b and the retardation plates 13a and 13b is an optical member obtained by the production method of the present invention. As this optical member, you may use any member of the optical member 1 obtained by the manufacturing method of this invention shown by Fig.1 (a)-(i). By providing the optical member obtained by the manufacturing method of the present invention, the liquid crystal display device 24 is provided with a function of converting incident light into linearly polarized light and circularly polarized light and a function of optically compensating for phase shift due to liquid crystal. Can do. The retardation films 13a and 13b may not be arranged depending on the structure of the liquid crystal display device and the type of liquid crystal compound contained in the liquid crystal layer 17.

  FIG. 3 is a schematic diagram showing an EL display device 30 of the present invention. In the EL display device 30, an organic functional layer 36 that is a light source and a cathode electrode 37 are laminated on a substrate 33 on which a pixel electrode 35 is formed. A phase difference plate 32 and a polarizing plate 31 are disposed on the opposite side of the organic functional layer 36 with the substrate 33 interposed therebetween. At least one selected from the group consisting of the retardation plate 32 and the polarizing plate 31 is an optical member obtained by the production method of the present invention. By applying a positive voltage to the pixel electrode 35 and a negative voltage to the cathode electrode 37 and applying a direct current between the pixel electrode 35 and the cathode electrode 37, the organic functional layer 36 emits light. The organic functional layer 36 that is a light emitting source includes an electron transport layer, a light emitting layer, a hole transport layer, and the like. The light emitted from the organic functional layer 36 passes through the pixel electrode 35, the interlayer insulating film 34, the substrate 33, the phase difference plate 32 and the polarizing plate 31. Although the organic EL display device having the organic functional layer 36 will be described, the present invention may be applied to an inorganic EL display device having an inorganic functional layer.

  In order to manufacture the EL display device 30 of the present invention, first, the thin film transistor 40 is formed in a desired shape on the substrate 33. Then, an interlayer insulating film 34 is formed, and then a pixel electrode 35 is formed by sputtering and patterned. Thereafter, the organic functional layer 36 is laminated.

  Examples of the substrate 33 include a sapphire glass substrate, a quartz glass substrate, a soda glass substrate, a ceramic substrate such as alumina, a metal substrate such as copper, and a plastic substrate. A heat conductive film may be formed on the substrate. An example of the thermally conductive film is a diamond thin film (DLC or the like). When the pixel electrode 35 is a reflection type, light is emitted in the opposite direction to the substrate 33. Therefore, not only a transparent material but also a non-permeable material such as stainless steel can be used. A single substrate may be formed, or a plurality of substrates may be bonded together with an adhesive to form a laminated substrate. These substrates are not limited to plates but may be films.

  As the thin film transistor 40, a normal polycrystalline silicon transistor may be used. The thin film transistor 40 is provided at the end of the pixel electrode 35 and has a size of about 10 to 30 μm. The size of the pixel electrode 35 is about 20 μm × 20 μm to 300 μm × 300 μm.

  On the substrate 33, wiring electrodes of the thin film transistor 40 are provided. The wiring electrode has a low resistance and has a function of suppressing the resistance value by being electrically connected to the pixel electrode 35. Generally, the wiring electrode includes Al, Al and transition metals (except for Ti), Ti or One containing one or more of titanium nitride (TiN) is used.

An interlayer insulating film 34 is provided between the thin film transistor 40 and the pixel electrode 35. The interlayer insulating film 34 is formed by sputtering or vacuum deposition of an inorganic material such as silicon oxide such as SiO ₂ or silicon nitride, a silicon oxide layer formed by SOG (spin-on-glass), a photoresist, a polyimide. Any film may be used as long as it has insulating properties, such as a coating film of a resin material such as an acrylic resin.

  A rib 41 is formed on the interlayer insulating film 34. The rib 41 is disposed in the peripheral portion (between adjacent pixels) of the pixel electrode 35. Examples of the material of the rib 41 include acrylic resin and polyimide resin. The thickness of the rib 41 is preferably 1.0 μm or more and 3.5 μm, more preferably 1.5 μm or more and 2.5 μm or less.

  Next, an EL element including a pixel electrode 35 that is a transparent electrode, an organic functional layer 36 that is a light emission source, and a cathode electrode 37 will be described. Each of the organic functional layers 36 includes at least one hole transport layer and a light emitting layer. For example, the organic functional layer 36 sequentially includes an electron injection transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

Examples of the pixel electrode 35 include ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), IGZO, ZnO, SnO ₂ , and In ₂ O ₃ , and ITO and IZO are particularly preferable. The thickness of the pixel electrode 35 may be a certain thickness that can sufficiently inject holes, and is preferably about 10 to 500 nm.
The pixel electrode 35 can be formed by an evaporation method (preferably a sputtering method). The sputtering gas is not particularly limited, and an inert gas such as Ar, He, Ne, Kr, Xe, or a mixed gas thereof may be used.

As the constituent material of the cathode electrode 37, for example, K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn, Zr or the like, or the stability is improved. It is preferable to use a two-component or three-component alloy system containing them. Examples of alloy systems include Ag · Mg (Ag: 1 to 20 at%), Al·Li (Li: 0.3 to 14 at%), In · Mg (Mg: 50 to 80 at%), Al · Ca (Ca: 5 to 20 at%) and the like are preferable.
The cathode electrode 37 is formed by vapor deposition, sputtering, or the like. The thickness of the cathode electrode 37 is 0.1 nm or more, preferably 1 to 500 nm or more.

The hole injection layer has a function of facilitating the injection of holes from the pixel electrode 35, and the hole transport layer has a function of transporting holes and a function of blocking electrons. Also called transport layer.
The thickness of the light emitting layer, the combined thickness of the hole injection layer and the hole transport layer, and the thickness of the electron injection transport layer are not particularly limited, and may vary depending on the formation method, but may be about 5 to 100 nm. preferable. Various organic compounds can be used for the hole injection layer and the hole transport layer. For the formation of the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer, it is preferable to use a vacuum deposition method because a homogeneous thin film can be formed.

  Examples of the organic functional layer 36 that is a light emission source include those that use light emission (fluorescence) from singlet excitons, those that use light emission (phosphorescence) from triplet excitons, and those from singlet excitons. Including those using luminescence (fluorescence) and those using triplet excitons (phosphorescence), formed by organic matter, formed by inorganic matter, formed by organic matter A material including an inorganic material, a high molecular material, a low molecular material, a high molecular material and a low molecular material, or the like can be used. Note that the present invention is not limited to this, and EL display devices using various EL elements can be used.

  A desiccant 38 is disposed in the space between the cathode electrode 37 and the sealing lid 39. This is because the organic functional layer 36 is vulnerable to humidity. The desiccant 38 absorbs moisture and prevents the organic functional layer 36 from being deteriorated.

  The polarizing plate 31 formed on the light incident surface or the light emitting surface of the EL display device 30 is not limited to a polarizing plate that converts to linearly polarized light, and may be a polarizing plate that converts to elliptically polarized light. Further, a plurality of polarizing plates or retardation plates may be bonded together.

FIG. 4 is a schematic view showing an EL display device 44 of the present invention. The EL display device 44 has a sealing structure using the thin-film sealing film 42 and can obtain emitted light from the opposite surface of the array substrate.
As the thin film sealing film 42, it is preferable to use a DLC film obtained by evaporating DLC (diamond-like carbon) on a film of an electrolytic capacitor. The DLC film has extremely poor moisture permeability and high moisture-proof performance. Further, a DLC film or the like may be directly deposited on the surface of the cathode electrode 37. Further, the thin film sealing film 42 may be formed by laminating a resin thin film and a metal thin film in multiple layers.

FIG. 6 is a schematic view showing a projection type liquid crystal display device of the present invention.
The optical member obtained by the production method of the present invention can be used as a polarizing plate 142 and / or a polarizing plate 143 in a projection type liquid crystal display device (projector).
A light bundle emitted from a light source (for example, a high-pressure mercury lamp) 111 that is a light emission source first passes through a first lens array 112, a second lens array 113, a polarization conversion element 114, and a superimposing lens 115. The luminance is uniformed and polarized in the cross section of the anti-beam bundle.

  Specifically, the light bundle emitted from the light source 111 is divided into a number of minute light bundles by the first lens array 112 in which minute lenses 112a are formed in a matrix. The second lens array 113 and the superimposing lens 115 are provided so that each of the divided light bundles irradiates the entire three liquid crystal panels 140R, 140G, and 140B that are illumination targets. The liquid crystal panel incident side surface has almost uniform illuminance as a whole.

  The polarization conversion element 114 is configured by a polarization beam splitter array, and is disposed between the second lens array 113 and the superimposing lens 115. As a result, random polarized light from the light source is converted into polarized light having a specific polarization direction in advance, thereby reducing the amount of light loss in the incident side polarizer described later, thereby improving the screen brightness.

  The light whose luminance is uniformed and polarized as described above is sequentially converted into the red channel, the green channel, and the blue channel by the dichroic mirrors 121, 123, and 132 for separation into the three primary colors of RGB via the reflection mirror 122. These are separated and enter the liquid crystal panels 140R, 140G, and 140B, respectively.

  In the liquid crystal panels 140R, 140G, and 140B, the polarizer film 142 of the present invention is disposed on the incident side, and the polarizer film 143 of the present invention is disposed on the exit side.

  The polarizing plate 142 and the polarizing plate 143 arranged in the RGB optical paths are arranged so that the respective absorption axes are orthogonal to each other. Each of the liquid crystal panels 140R, 140G, and 140B arranged in each optical path has a function of converting the polarization state controlled for each pixel by an image signal into a light amount.

  The optical member of the present invention is useful as a polarizing plate having excellent durability in any optical path of a blue channel, a green channel, and a red channel by selecting a type of dichroic dye suitable for the corresponding channel.

  An optical image created by transmitting incident light with different transmittance for each pixel according to the image data of the liquid crystal panels 140R, 140G, and 140B is synthesized by the cross dichroic prism 150, and is projected by the projection lens 170 to the screen 180. Is enlarged and projected.

  Electronic paper is displayed by molecules such as optical anisotropy and dye molecule orientation, displayed by particles such as electrophoresis, particle movement, particle rotation, and phase change, and one end of the film moves And the like, those displayed by molecular color development / phase change, those displayed by light absorption of molecules, and those displayed by self-emission by combining electrons and holes. More specifically, microcapsule type electrophoresis, horizontal movement type electrophoresis, vertical movement type electrophoresis, spherical twist ball, magnetic twist ball, cylindrical twist ball method, charged toner, electronic powder fluid, magnetophoretic type, magnetic thermosensitive Formula, electrowetting, light scattering (transparency / translucency change), cholesteric liquid crystal / photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroic dye / liquid crystal dispersion type, movable film, leuco dye And color erasing, photochromic, electrochromic, electrodeposition, flexible organic EL, and the like. The electronic paper may be used not only for personal use of text and images but also for advertisement display (signage) or the like. According to the optical film of the present invention, the thickness of the electronic paper can be reduced.

  As a stereoscopic display device, for example, a method of arranging different polarizing films alternately like a micropole method has been proposed (Japanese Patent Laid-Open No. 2002-185983). Since patterning is easy by lithography or the like, the manufacturing process of the display device can be shortened.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

In the examples, the following polymerizable liquid crystal compounds were used.
Compound (1-6) (compound represented by the following formula (1-6))
In addition, a compound (1-6) is Lubetal.Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

(Measurement of phase transition temperature)
While heating the compound on the glass substrate on which the alignment film was formed, the phase transition temperature was confirmed by texture observation with a polarizing microscope (BX-51, manufactured by Olympus Corporation). The compound represented by the formula (1-6) exhibits a smectic A phase from a crystal phase at 95 ° C. at a temperature rise, phase transition to a nematic phase at 111 ° C., and a phase to an isotropic liquid phase at 113 ° C. Metastasized. When the temperature was lowered, it was confirmed that the phase transitioned to the nematic phase at 112 ° C., the phase transition to the smectic A phase at 110 ° C., and the phase transition to the smectic B phase at 94 ° C.

(Adjustment of polymerizable liquid crystal composition)
The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition A.
Polymerizable liquid crystal compound; Compound (1-6) 97 parts Dichroic dye; Azo dye (NKX2029; manufactured by Hayashibara Biochemical Laboratories) 2 parts Polymerization initiator; 2,2-dimethoxy-1,2-diphenylethane-1 -ON (Irgacure 651; manufactured by BASF Japan) 6 parts Solvent; 250 parts of cyclohexanone

Example 1
(Production of optical member)
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied on a glass substrate by a spin coating method, and dried to form an alignment film having a thickness of 89 nm. Subsequently, the surface of the obtained alignment film was rubbed. The rubbing process uses a semi-automatic rubbing apparatus (trade name: LQ-008, manufactured by Joyo Engineering Co., Ltd.) and a push-in amount of 0.15 mm using a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.). , Under the conditions of 500 rpm and 16.7 mm / s. Two substrates were manufactured by the same method and used as the first substrate and the second substrate.
On the alignment film of the first substrate after rubbing, the polymerizable liquid crystal composition A was applied by a spin coating method and dried by heating on a hot plate at 120 ° C. for 3 minutes to obtain a film. An alignment film formed on the second substrate was adhered so as to cover the film. At this time, the rubbing process applied to the alignment film on the first substrate was placed in the same direction as the rubbing process applied to the alignment film on the second substrate.
Next, by using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) and irradiating ultraviolet rays with an exposure amount of 2400 mJ / cm ² (365 nm standard) at room temperature, it is represented in FIG. The optical member of the form was obtained.

[Dichroic ratio measurement]
Using a device in which a folder with a polarizer is set in an ultraviolet-visible spectrophotometer UV-3150 manufactured by Shimadzu Corporation, the absorbance in the transmission axis direction at the maximum absorption wavelength (A ¹ ) and the absorbance in the absorption axis direction (A ² ) are double-beamed. Measured by the method. The folder was provided with a mesh that cuts the light amount by 50% on the reference side. The ratio (A ¹ / A ² ) was calculated from the measured absorbance (A ¹ ) in the direction of the transmission axis and absorbance (A ² ) in the direction of the absorption axis, and the dichroic ratio was 25. The maximum absorption wavelength of the optical member was 400 nm.

[Measurement of film thickness]
The film thickness (μm) of the polymerizable liquid crystal composition layer obtained by polymerizing the polymerizable liquid crystal compound contained in the obtained optical member was 2 μm when measured using a laser microscope (LEXT3000, manufactured by Olympus Corporation). It was.

Example 2
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied on a triacetylcellulose film substrate by spin coating, and after drying, an alignment film having a thickness of 89 nm was formed. Formed. Subsequently, the surface of the obtained alignment film was rubbed. The rubbing process uses a semi-automatic rubbing apparatus (trade name: LQ-008, manufactured by Joyo Engineering Co., Ltd.) and a push-in amount of 0.15 mm using a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.). , Under the conditions of 500 rpm and 16.7 mm / s.
An optical member having the form shown in FIG. 1A was obtained by the same method as in Example 1 except that the triacetyl cellulose film substrate on which the alignment film was formed was used as the second substrate.
When the dichroic ratio and the film thickness were measured in the same manner as in Example 1, the dichroic ratio was 23 and the film thickness was 2 μm.

Example 3
From the optical film laminated between the glass substrate obtained in Example 2 and the triacetyl cellulose film substrate, the glass substrate and the alignment film formed on the glass substrate were peeled off and represented in FIG. An optical member of the form to be obtained was obtained.
When the dichroic ratio and the film thickness were measured in the same manner as in Example 1, the dichroic ratio was 23 and the film thickness was 2 μm.

Comparative Example 1
The following components were mixed to obtain a polymerizable liquid crystal composition B.
Polymerizable liquid crystal compound; Compound (1-6) 16.5 parts Polymerizable liquid crystal compound; Compound (1-7) 16.5 parts Dichroic dye; Azo dye (NKX2029; manufactured by Hayashibara Biochemical Laboratories) 1 part Polymerization Initiator; 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651; manufactured by BASF Japan Ltd.) 1 part Solvent; 65 parts of chlorobenzene

In the same manner as in Example 1, an alignment film was formed on a glass substrate, and a rubbing treatment was performed. On the alignment film after rubbing, the polymerizable liquid crystal composition B was applied by spin coating, and heated on a hot plate at 120 ° C. for 3 minutes to obtain a film. This film was not exposed to a second substrate and exposed.
When the dichroic ratio and the film thickness were measured in the same manner as in Example 1, the dichroic ratio was 2.

  Since the optical member manufactured by the manufacturing method of an Example shows high dichroic ratio, it turns out that it is useful as a polarizing plate.

  According to the polymerizable liquid crystal composition of the present invention, an optical member having a high dichroic ratio can be easily obtained.

DESCRIPTION OF SYMBOLS 1 Optical member 2 1st board | substrate 3 2nd board | substrate 4, 4 'Alignment film 5 Polymer layer 10 Liquid crystal display device 11 Antireflection film 12a, 12b Polarizing plate 13a, 13b Phase difference plate 14a, 14b Substrate 15 Color filter 16 Transparent electrode 17 Liquid crystal layer 18 Interlayer insulating film 19 Backlight unit 20 Black matrix 21 Thin film transistor 22 Pixel electrode 23 Spacer 24 Liquid crystal display device 30 EL display device 31 Polarizing plate 32 Phase difference plate 33 Substrate 34 Interlayer insulating film 35 Pixel electrode 36 Light emitting layer 37 cathode electrode 38 desiccant 39 sealing lid 40 thin film transistor 41 rib 42 thin film sealing film 44 EL display device 111 light source 112 first lens array 112a lens 113 second lens array 114 polarization conversion element 115 superposed lenses 121, 123, 132 Dichroic Mirror 122 Reflection mirror 140R, 140G, 140B Liquid crystal panel 142, 143 Polarizing plate 150 Cross dichroic prism 170 Projection lens 180 Screen

Claims (6)

The manufacturing method of the optical member containing the process described in (1)-(4).
(1) Step (2) of forming a film by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a solvent to the first substrate and removing the solvent. The surface of the film obtained in (1) Steps of placing a second substrate so as to cover (3) Steps of obtaining a film in which a liquid crystal phase is formed by aligning the polymerizable liquid crystal compound contained in the film on which the second substrate obtained in (2) is placed (4) By polymerizing the polymerizable liquid crystal compound contained in the film formed with the liquid crystal phase obtained in (3), a composition layer in which the polymerizable liquid crystal compound is polymerized is laminated between the two substrates. Process for obtaining an optical member Furthermore, the manufacturing method of Claim 1 including the process described in (5).
(5) A step of removing at least one substrate from an optical member in which a composition layer obtained by polymerizing a polymerizable liquid crystal compound is laminated between two substrates.   The manufacturing method according to claim 1, wherein the second substrate is a substrate on which an alignment film is formed.   The manufacturing method according to claim 1, wherein the liquid crystal phase is a smectic phase.   The method according to claim 1, wherein the polymerizable liquid crystal composition is a composition further containing a dichroic dye.   The display apparatus containing the optical member obtained by the manufacturing method in any one of Claims 1-5.

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