KR20180111730A - Polymerizable liquid crystal composition - Google Patents

Abstract

The present invention relates to a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound exhibiting a smectic phase, a leveling agent and a solvent. In the polymerizable liquid crystal composition, the leveling agent is at least one selected from a group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component, and the leveing agent is contained in an amount of 0.3 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the polymerizable liquid crystal compound.

Description

[0001] POLYMERIZABLE LIQUID CRYSTAL COMPOSITION [0002]

The present invention relates to a polymerizable liquid crystal composition.

Optical films such as a polarizing film and a retardation film are used for a liquid crystal display device. Japanese Patent Publication No. 2008-547062 discloses a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound, a photopolymerization initiator and a solvent for producing such an optical film.

According to the present invention,

[1] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound exhibiting a stymatic phase, a leveling agent and a solvent, wherein the leveling agent comprises a leveling agent comprising a polyacrylate compound as a main component and a leveling agent comprising a fluorine atom- , And the content of the leveling agent is not less than 0.3 parts by mass and not more than 5 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound;

[2] The polymerizable liquid crystal composition according to [1], wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound exhibiting a nematic phase between a temperature showing a stymatic phase and a temperature showing an isotropic phase;

[3] The polymerizable liquid crystal composition according to [1] or [2], further comprising a dichroic dye;

[4] An optical film obtained by polymerizing a polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition described in any one of [1] to [3];

[5] a process for producing an optical film comprising the following steps (1), (2) and (3);

Step (1): A step of applying a polymerizable liquid crystal composition described in any one of [1] to [3] to a substrate to obtain a coating film

Step (2): Step of forming a liquid crystal phase in the coating film obtained in the step (1)

Step (3): A step of obtaining an optical film by polymerizing a polymerizable liquid crystal compound contained in a film on which a liquid crystal image is formed obtained in the step (2)

[6] The manufacturing method according to [5], wherein the liquid crystal phase is a smectic phase;

[7] The method according to any one of [1] to [5], wherein the step (2) comprises heating the coating film obtained in the step (1) to a temperature above the temperature at which the polymerizable liquid crystal compound contained in the coating film is transferred to a nematic phase, To obtain a film in which the polymerizable liquid crystal compound is oriented in a stymic state by cooling the solution to a temperature at which the polymerizable liquid crystal compound is cooled to a temperature at which the polymerizable liquid crystal compound is cooled.

[8] A display device comprising the optical film according to [4];

[9] A display device comprising an optical film obtained by the manufacturing method described in [5];

[10] A display device comprising an optical film obtained by the production method described in [6] or [7]

And the like.

1 is a schematic view showing a liquid crystal display device 10 which is one of the display devices of the present invention.
2 is a schematic view showing a liquid crystal display device 24 which is one of the display devices of the present invention.
3 is a schematic diagram showing an EL display device 30 which is one of the display devices of the present invention.
4 is a schematic view showing an EL display device 44 which is one of the display devices of the present invention.
5 is a schematic view showing a projection type liquid crystal display device which is one of display devices of the present invention.

In the present invention, the term "optical film" refers to a film capable of transmitting light and having an optical function. The optical function means absorption, reflection, diffraction, scattering, refraction, birefringence, and the like.

The retardation film, which is a type of optical film, is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or conversely convert circularly polarized light or elliptically polarized light into linearly polarized light.

A polarizing film, which is a kind of optical film, is used to decompose incident light that is not polarized into two polarizing components orthogonal to each other, transmit one polarizing component, and absorb the other polarizing component. The axial direction of the transmitted polarized light component is referred to as a transmission axis, and the axial direction of the polarized light component to be absorbed is referred to as an absorption axis.

The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound exhibiting a stymatic phase, a leveling agent and a solvent, wherein the leveling agent comprises a leveling agent comprising a polyacrylate compound as a main component and a leveling agent comprising a fluorine atom- And a leveling agent. The content of the leveling agent is not less than 0.3 parts by mass and not more than 5 parts by mass based on 100 parts by mass of the 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 nematic phase between a temperature showing a stymatic phase and a temperature showing an isotropic phase, which is a polymerizable liquid crystal compound exhibiting a stymatic phase. If the polymerizable liquid crystal compound is such a compound, there is a tendency that a smectic phase in a horizontal orientation can be easily obtained.

As the smectic phase, it is possible to use, as a steric 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, And a smectic K phase. Of these, a smectic B phase, a smectic F phase and a smectic I phase are preferable, and a smectic B phase is more preferable. If the liquid crystal phase represented by the polymerizable liquid crystal compound is in the liquid crystal phase, an optical film having high alignment order can be obtained.

As the polymerizable liquid crystal composition, a compound represented by the formula (1) (hereinafter sometimes referred to as " compound (1) ") may be mentioned.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1)

[In the 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. Provided that 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 represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N═N-, -CR ^a = CR ^b -, - C? C- or CR ^a = N-.

R ^a and R ^b 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 independently represent a single bond, -O-, -S-, -COO- or OCOO-.

V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the alkanediyl group is substituted with -O-, -S- or NH-, Maybe there is]

X ¹ , X ² and X ³ are, independently of each other, a p-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. Provided that 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 an amorphous group. The cyclohexane-1,4-diyl group is preferably a trans-cyclohexane-1,4-diyl group, and more preferably is an indeterminate group.

Examples of the substituent which may have a p-phenylene group 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 and a fluoro group (fluorine atom), a chloro- group (chlorine atom) (Halogen atom), and the like.

Examples of the substituent which may be contained in the cyclohexane-1,4-diyl group 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 and a fluoro group (fluorine atom) And a halogeno group (halogen atom) such as a mosquito (bromine atom). The -CH ₂ - of the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or NR-. R is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Y ¹ and Y ² independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N═N-, -CR ^a = CR ^b -, -C≡ C- or CR &^lt; a > = N-. The bonding position of these groups may be any direction.

R ^a and R ^b are independently of each other 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, preferably a polymerizable group. U ² is a polymerizable group. U ¹ and U ² are preferably a photopolymerizable group together. The term "photopolymerizable group" means a group capable of participating in polymerization by an active radical or an acid generated from a photopolymerization initiator.

U ¹ and U ² are preferably the same type of group.

Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group . Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

V ¹ and V ² are independently an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the alkanediyl group may be substituted with -O-, -S- or NH- .

Examples of the alkanediyl group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane- Dihexyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group, -1,20-diyl group, and the like, preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent which the alkanediyl group may have include a cyano group and a halogeno group (halogen atom) such as a fluoro group (fluorine atom), a chloro group (chlorine atom) and a bromo group (bromine atom).

An unsubstituted alkanediyl group is preferable, and an unsubstituted straight-chain alkanediyl group is more preferable.

W ¹ and W ² are independently a single bond, -O-, -S-, -CO-O- or -O-CO-O-, preferably a single bond or -O-.

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

The content of the compound (1) is preferably 70 to 99.9% by mass, more preferably 90 to 99.9% by mass, based on 100% by mass of the solid content of the polymerizable liquid crystal composition. Within the above range, orientation of the compound tends to be enhanced. In the present specification, "solid content" means a component other than the solvent among the entire components of the polymerizable liquid crystal composition. Two or more compounds (1) may be used.

The leveling agent is at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component. The leveling agent has a function of adjusting the fluidity of the polymerizable liquid crystal composition to flatten the applied film, and examples thereof include a surfactant and the like.

Examples of leveling agents based on polyacrylate compounds include BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK- 392 (both trade names: manufactured by BYK Chemie).

Examples of leveling agents containing a fluorine atom-containing compound as a main component include Megapak (trade name) R-08, R-30, R-90, F-410, F-411, F- , F-470, F-471, F-477, F-479, F-482 and F-483 (all manufactured by DIC Corporation) S-382, S-383, S-393, SC-101, SC-105, KH-40 and SA-100 (all manufactured by AGC SEIYAMA CHEMICAL CO., LTD.), Trade name E1830 E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), Efter (trade name) EF301, EF303, EF351 and EF352 (all manufactured by Mitsubishi Materials Corporation).

The content of the leveling agent is 0.3 parts by mass or more and 5 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above-mentioned range, it is easy to horizontally orient the components contained in the polymerizable liquid crystal composition, and the resulting optical film tends to become smooth. If the content of the leveling agent exceeds 5 parts by mass, unevenness easily occurs in the obtained optical film. These leveling agents may be at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component, and may be used in combination of two or more.

It is preferable that the leveling agent is a polyacrylate compound, a fluorine atom-containing compound, or both.

The polymerizable liquid crystal composition of the present invention preferably contains a dichromatic dye. When the polymerizable liquid crystal composition of the present invention contains a dichroic dye, the obtained optical film has a function as a polarizing film. The dichroic dye refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from that in the minor axis direction.

The dichroic dye may be a dye or a pigment. As the dichroic dye, a dichroic dye having a maximum absorption wavelength at 300 to 700 nm is preferable. Examples of the dichroic dye include an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye and an anthraquinone dye. Two or more dichroic dyes may be used in combination.

As the dichroic dye, an azo dye is preferable. Examples of the azo dye include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes and stilbenazo dyes, with bisazo dyes and trisazo dyes being preferred.

As the azo dye, a compound represented by the formula (2) can be mentioned.

A ¹ (-N = NA ² ) _p -N = NA ³ (2)

[In the formula (2), A ¹ and A ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a monovalent heterocyclic group which may have a substituent. A ² each independently represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents an integer of 1 to 4; When p is an integer of 2 or more, a plurality of A ² may be the same or different from each other]

Examples of the monovalent heterocyclic group include groups obtained by subtracting one hydrogen atom from a heterocycle such as a quinoline ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an imidazole ring, a benzoimidazole ring, an oxazole ring or a benzoxazole ring have. As the divalent heterocyclic group, there may be mentioned a limiting group of two hydrogen atoms in the above-mentioned heterocyclic ring.

Examples of the substituent which may have a phenyl group, a naphthyl group and a monovalent heterocyclic group in A ¹ and A ³ , a p-phenylene group in A ² , a naphthalene-1,4-diyl group and a divalent heterocyclic group include methyl, An alkyl group having 1 to 4 carbon atoms such as a butyl group; An alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; A fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; Cyano; A nitro group; Halogeno groups such as a fluoro group, a chloro group, and a bromo group; An amino group; An amino group substituted by an alkyl group having 1 to 4 carbon atoms such as a diethylamino group and a pyrrolidino group (two alkyl groups substituted with an amino group may be bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms) .

As the azo dye, compounds represented by the following formulas (2-1) to (2-6) are preferable.

(2-1) to (2-6), B ^{1 to} B ²⁰ each independently represent 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 substituted with an alkyl group having 1 to 4 carbon atoms (two alkyl groups substituted with an amino group may combine with each other to form an alkanediyl group having 2 to 8 carbon atoms), a chloro group (chlorine atom) or a trifluoromethyl group . n1 to n4 each independently represent an integer of 0 to 3;

The anthraquinone dye is preferably a compound represented by the formula (2-7).

Wherein R ¹ to R ⁸ each independently represent a hydrogen atom, -R ^x , an amino group, -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom, and R ^x represents a carbon number of 1 An alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

The acridine dye is preferably a compound represented by the formula (2-8).

Wherein 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, and R ^x represents a carbon number of 1 An alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

The oxazone dye is preferably a compound represented by the formula (2-9).

Wherein 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, and R ^x represents a carbon number of 1 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 tolyl 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 the formula (2-10), D ¹ and D ² each independently represent a group represented by the formulas (2-10a) to (2-10d).

n5 represents an integer of 1 to 3]

[In the formula (2-11), D ³ and D ⁴ each independently represent a group represented by the formulas (2-11a) to (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 still more preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the polymerization can be carried out without disturbing the orientation of the polymerizable liquid crystal compound. If the content of the dichroic dye exceeds 50 parts by mass, the alignment of the polymerizable liquid crystal compound may be disturbed, which is not preferable.

As the solvent, a solvent capable of dissolving each component of the polymerizable liquid crystal composition is preferable. Further, it is preferable that the solvent is inert to the polymerization reaction of the polymerizable liquid crystal composition.

Examples of the solvent 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, Esters such as butyrolactone, 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 toluene and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; and chlorine-containing solvents such as chloroform and chlorobenzene. These solvents may be used alone or in combination of two or more kinds.

The content of the solvent is preferably from 50 to 98% by mass based on the total amount of the polymerizable liquid crystal composition. When the amount of the solvent is 98% by mass or less, the optical film obtained from the polymerizable liquid crystal composition does not become too thin, and an optical film having properties required as an optical film can be easily obtained. When the amount of the solvent is 50% by mass or more, the viscosity of the polymerizable liquid crystal composition is low, and the film thickness of the coating film tends to be unlikely to be uneven.

The polymerizable liquid crystal composition of the present invention may contain a polymerization initiator. The polymerization initiator is a compound which initiates the polymerization reaction of the polymerizable liquid crystal compound and generates active radicals or acids by the action of light and / or heat. Among them, a polymerization initiator that generates an active radical or an acid by the action of light, that is, a photopolymerization initiator is preferable, and a photopolymerization initiator that generates 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'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- Benzyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2- 1-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan- 1-one, 1-hydroxycyclohexyl phenyl ketone and 2- (1-methylvinyl) phenyl] propan-1-one.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, .

Examples of the photopolymerization initiator include Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by Chiba Japan Co., Ltd.) SEAKUOL BZ, SEQUOOL Z, SEQUOOL BEE (all manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (Manufactured by Nippon Shiba Co., Ltd.) and TAZ-104 (manufactured by Nippon Shokubai Co., Ltd.), Adeka Optoma SP-152 or Adeka Optoma SP- A commercially available photopolymerization initiator system such as "

Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile and 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, further preferably 0.5 to 8 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the alignment of the polymerizable liquid crystal compound can be polymerized without clogging.

When a photopolymerization initiator is used as the polymerization initiator, a photosensitizer may be used in combination. Examples of the photosensitizer include xanthene compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone and 2-isopropylthioxanthone), anthracene, anthracene containing an alkoxy group (for example, dibutoxy Anthracene, etc.), phenothiazine, and rubrene.

By using a photosensitizer, the polymerization of the polymerizable liquid crystal compound can be highly sensitized. The amount of the photosensitizer is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 10 parts by mass, further preferably from 0.5 to 8 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound.

The polymerizable liquid crystal composition of the present invention may contain a polymerization inhibitor. By including the polymerization inhibitor in the polymerizable liquid crystal composition of the present invention, the polymerization of the polymerizable liquid crystal compound is easily controlled, and the stability of the polymerizable liquid crystal composition of the present invention can be improved.

Examples of the polymerization inhibitor include radical supplements such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (such as butyl catechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical , Thiophenols,? -Naphthyl amines and? -Naphthols.

The content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, further preferably 0.5 to 8 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the alignment of the polymerizable liquid crystal compound can be polymerized without clogging.

The optical film of the present invention is obtained by polymerizing a polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention.

The optical film of the present invention can be produced by a method including the following steps (1), (2) and (3):

Step (1): A step of applying a polymerizable liquid crystal composition of the present invention to a substrate to obtain a coating film

Step (2): Step of forming a liquid crystal phase in the coating film obtained in the step (1)

Step (3): A step of obtaining an optical film by polymerizing a polymerizable liquid crystal compound contained in a film on which a liquid crystal image is formed, obtained in the step (2).

Examples of the coating method on the substrate include extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, die coating method, dip coating method, bar coating method and spin coating method.

Examples of the substrate include glass, plastic sheet, plastic film and translucent film. Examples of the light transmitting film include a polyolefin film such as polyethylene, polypropylene and norbornene polymer, a polyvinyl alcohol film, a polyethylene terephthalate film, a polymethacrylic acid ester film, a polyacrylic acid ester film, a cellulose ester film, a polyethylene naphthalate film, A carbonate film, a polysulfone film, a polyethersulfone film, a polyether ketone film, a polyphenylene sulfide film and a polyphenylene oxide film.

By using the substrate, there is no tearing when the optical film is manufactured, transported, or stored, and can be easily handled.

In the method for producing an optical film of the present invention, it is preferable that an alignment film is formed on the substrate. In that case, the polymerizable liquid crystal composition of the present invention is applied on the alignment film. It is preferable that the alignment film has a solvent resistance that is not dissolved by application of the polymerizable liquid crystal composition of the present invention or the like. Further, it is preferable that it has a heat resistance in a heat treatment for removing a solvent or aligning a liquid crystal. Further, it is preferably an alignment film which does not cause peeling due to rubbing or the like due to rubbing. As such an orientation film, it is preferable to contain a composition containing an orienting polymer or an orientation polymer.

Examples of the oriented polymer include polyamides and gelatins having amide bonds in the molecule, polyimides having imide bonds in the molecule, and hydrolyzates thereof, polyamic acids, polyvinyl alcohols, alkyl-modified polyvinyl alcohols, polyacrylamides, And polymers such as sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among them, polyvinyl alcohol is preferable. These polymers may be used alone, or two or more kinds of them may be blended or copolymerized. These polymers can be easily obtained by chain polymerization, coordination polymerization or ring-opening polymerization such as polycondensation by dehydration or deamination, radical polymerization, anion polymerization and cation polymerization.

The oriented polymer can be dissolved in a solvent and applied. As the solvent, water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene. These organic solvents may be used alone or in combination of two or more.

Further, in order to form an alignment film, a commercially available alignment film material may be used as it is. Commercially available alignment film materials include SANEVA (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optomer (registered trademark, manufactured by JSR Corporation).

By using such an alignment film, it is possible to provide an optical film having improved environmental resistance and mechanical resistance since the unevenness is reduced.

As an example of a method for forming an alignment film on the supporting substrate, an alignment film can be formed on the supporting substrate by applying the solution of the orienting polymer or a commercially available alignment film material on the supporting substrate and then annealing . 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, rubbing or polarized UV irradiation is preferably performed if necessary. By giving the alignment regulating force, the polymerizable liquid crystal compound can be oriented in a desired direction.

As a method of rubbing the alignment film, for example, there is a method in which a rubbing cloth is wound and the rotating rubbing roll is brought into contact with an alignment film carried on the stage. When masking is performed in rubbing or polarized UV irradiation, it is possible to form a plurality of regions (patterns) different in the direction of the slow axis (phase axis) from the obtained polarizer.

It is preferable to dry a volatile component such as a solvent contained in the coating film from the viewpoint of film forming property with respect to the coating film obtained by coating on the substrate. Examples of the drying method include a natural drying method, a ventilation drying method and a reduced pressure drying method. The drying temperature is preferably 0 to 250 캜, more preferably 50 to 220 캜. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In order to form a liquid crystal phase by the component of the polymerizable liquid crystal composition contained in the coating film, the polymerizable liquid crystal compound contained in the coating film may be heated to a temperature at which the liquid crystal phase is exhibited. The liquid crystal phase is preferably a smectic phase. It is also preferable to obtain a film in which a smectic phase is formed by heating to a temperature at which the polymerizable liquid crystal compound contained in the coating film is transferred to a nematic phase and then cooling the polymerizable liquid crystal compound to a temperature at which the polymerizable liquid crystal compound exhibits a stymatic phase desirable.

When the polymerizable liquid crystal composition contains two or more polymerizable liquid crystal compounds, the temperature at which the liquid crystalline phase is measured is measured for a mixture in which the polymerizable liquid crystal compound is adjusted to the content ratio of the polymerizable liquid crystal composition, The temperature at which the liquid crystal phase is formed by the components of the composition can be determined.

By passing the nematic phase, the leveling agent contained in the polymerizable liquid crystal composition is easily flowed, and a horizontally oriented film can be easily obtained. The temperature for heating is preferably not higher than the nematic phase transition point by at least 100 degrees higher than the nematic phase transition point and more preferably not higher than the nematic phase transition point and not higher than the nematic phase transition point by 50 degrees. The heating for orientation in the liquid crystal phase and the above drying may be performed at the same time.

Subsequently, an optical film can be obtained by polymerizing the polymerizable liquid crystal compound contained in the film in which the liquid crystal phase is formed. By polymerization, an optical film having durability is obtained. The polymerization method may be selected depending on the type of the polymerizable group of 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 thermo-polymerizable group, it can be polymerized by a thermal polymerization method. In the method for producing an optical film of the present invention, a photopolymerization method is preferable. In the case of the photopolymerization method, since it is not necessary to necessarily heat at a high temperature, a substrate having low heat resistance can be used. The photopolymerization method is performed by irradiating a visible light, ultraviolet light, or laser light to a film having a liquid crystal phase formed thereon. Ultraviolet light is preferable because it is easy to handle. Light irradiation is performed in a state in which a liquid crystal phase is formed on the film. It may be irradiated with light at a temperature which indicates a liquid crystal phase as described above. At this time, the optical film may be patterned by performing masking or development.

The optical film formed on the substrate may be peeled off from the substrate after polymerization of the polymerizable liquid crystal compound contained in the film. In addition to the step of peeling the substrate, the method may further include a step of peeling off the alignment film. Thus, a single-layered optical film of the present invention can be obtained. The film thickness of the optical film of the present invention is preferably 0.3 to 20 탆, more preferably 0.5 to 10 탆, and still more preferably 0.5 to 5 탆. If the film thickness is within the above-mentioned range, an optical film horizontally aligned in a smectic phase can be easily obtained.

The optical film of the present invention is useful as a polarizing film excellent in two color ratio when it contains a dichroic dye. When the dichroic dye is not contained, it is useful as a retardation film having excellent contrast.

The display device of the present invention includes the optical film of the present invention. The display device is an apparatus having a display element, and includes a light emitting element or a light emitting element 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 (e.g., a full field emission display device (FED), a surface field emission display device (SED) , Electronic paper (a display device using electronic ink or an electrophoretic element, a plasma display device, a projection display device (e.g., a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD) Examples of the liquid crystal display device include a transmission type liquid crystal display device, a transflective liquid crystal display device, a reflection type liquid crystal display device, a direct viewing type liquid crystal display device, and a projection type liquid crystal display device. Or may be a three-dimensional display device for displaying a three-dimensional image.

1 is a schematic view showing a liquid crystal display device 10 which is one of the display devices of the present invention. The liquid crystal layer 17 is sandwiched between the 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 with the liquid crystal layer 17 therebetween and the black matrix 20 is disposed at a position facing the boundary between the pixel electrodes. The transparent electrodes 16 cover them. An overcoat layer may be provided between the color filter 15 and the transparent electrode 16. [

The thin film transistor 21 and the pixel electrode 22 are properly disposed 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 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. The substrate 14a and the substrate 14b are preferably glass substrates when it is necessary to heat the color filter 15 and the thin film transistor 21 formed on these substrates at a high temperature.

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 miniaturize 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. [ A spacer 23 is formed in the liquid crystal layer 17 in order to maintain a constant distance between the substrate 14a and the substrate 14b. Alignment films for aligning the liquid crystal compound contained in the liquid crystal layer 17 in a desired direction may be respectively disposed on the surfaces of the layers formed on the substrate 14a and the substrate 14b in contact with the liquid crystal layer 17. [

Each member includes a substrate 14a, a color filter 15 and a black matrix 20, a transparent electrode 16, a liquid crystal layer 17, a pixel electrode 22, an interlayer insulating film 18 and a thin film transistor 21, And a substrate 14b are stacked in this order.

For example, a polarizing film (for example, a linear polarizer) or a retardation film (for example, a quarter wave plate, a quarter wave plate, or a quarter wave plate) may be provided on the outer side of the substrate 14a and the substrate 14b with the liquid crystal layer 17 therebetween. An optical compensation film) is laminated. 1, a retardation film 13a and a polarizing film 12a are laminated in this order on the outer side of the substrate 14a and a retardation film 13b and a polarizing film 12b are laminated on the outer side of the substrate 14b Are stacked in this order. At least one kind selected from the group consisting of the polarizing film 12a, the polarizing film 12b, the retardation film 13a and the retardation film 13b is the optical film of the present invention. By disposing the optical film of the present invention, the liquid crystal display device 10 can be provided with a function of converting incident light into linearly polarized light or circularly polarized light and a function of optically compensating for phase shift due to liquid crystal. On the other hand, the retardation films 13a and 13b may not be arranged depending on the structure of the liquid crystal display device and the type of the liquid crystal compound contained in the liquid crystal layer 17. [ An antireflection film 11 for preventing the reflection of external light is disposed outside the polarizing film 12a. According to the optical film of the present invention, it is possible to achieve a thin display device.

At least one kind selected from the group consisting of the polarizing films 12a and 12b and the retardation films 13a and 13b and the laminated body in which the optical film of the present invention and the substrate used for producing the optical film are stacked, May be used.

A backlight unit 19 is disposed on the outer side of the polarizing film 12b. The backlight unit 19 includes a light source, a light guide, a reflection plate, a diffusion sheet, and a viewing angle adjustment sheet. As the light source, various light sources such as electroluminescence (EL), cold cathode tubes, hot cathode tubes, light emitting diodes (LED), laser light sources, and mercury lamps can be used. The optical film of the present invention may be selected according to the characteristics of the light source.

When the liquid crystal display device 10 is a transmissive liquid crystal display device, the white light emitted from the light source in the backlight unit 19 is incident on the light guide body, and is changed by the reflection plate to diffuse into the diffusion sheet. The diffused light is adjusted to have a desired directivity by the viewing angle adjusting sheet, and then enters the polarizing film 12b from the backlight unit 19. [

Of the incident light that is unpolarized, only one of the linearly polarized light passes through the polarizing film 12b of the liquid crystal panel. The linearly polarized light is converted into circularly polarized light by the phase difference film 13b and sequentially transmitted through the substrate 14b and the pixel electrode 22 to the liquid crystal layer 17. [

The alignment state of the liquid crystal compound included in the liquid crystal layer 17 changes depending on the presence or absence of a potential difference between the pixel electrode 22 and the transparent electrode 16 opposed to the liquid crystal display device 10, Is controlled. When the liquid crystal layer 17 is in the alignment state in which the circularly polarized light converted by the phase difference film 13b is transmitted as it is, the circularly polarized light passes through the liquid crystal layer 17 and the transparent electrode 16, When light in a specific wavelength range passes through the color filter 15 to reach the retardation film 13a and also transmits the polarizing film 12a and the antireflection film 11, Display the brightest. Conversely, when the liquid crystal layer 17 is in the alignment state in which the circularly polarized light converted by the phase difference film 13b is converted and transmitted, the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 When light is almost completely absorbed by the retardation film 13a and the polarizer 12a, this pixel displays black. If the liquid crystal layer 17 is in an intermediate state between these two states, the brightness of light emitted from the liquid crystal display device 10 is also intermediate between the two, so that the pixel displays an intermediate color.

In the case where the liquid crystal display device 10 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 reflecting light. In the transmissive portion, An image is displayed. On the other hand, in the reflective portion, the external light is incident on the liquid crystal display device in the direction of the antireflection film 11, and the circularly polarized light transmitted through the polarizing film 12a and the retardation film 13a passes through the liquid crystal layer 17, 22 to be used for display.

Fig. 2 is a schematic view showing a liquid crystal display device 24 in which the optical film of the present invention is arranged inside the substrate (liquid crystal 17 side). In the liquid crystal display device 24, the respective members are provided with the antireflection film 11, the substrate 14a, the polarizing film 12a, the phase difference film 13a, the color filter 15 and the black matrix 20, The liquid crystal layer 17, the pixel electrode 22, the interlayer insulating film 18 and the thin film transistor 21, the retardation film 13b, the polarizing film 12b, the substrate 14b, the backlight unit 19 Are stacked in this order. At least one kind selected from the group consisting of the polarizing film 12a, the polarizing film 12b, the retardation film 13a and the retardation film 13b is the optical film of the present invention. A laminate obtained by laminating the optical film of the present invention, the alignment film, and the substrate used for producing the optical film may be used. By disposing the optical film of the present invention, it is possible to give the liquid crystal display device 24 a function of converting incident light into linearly polarized light or circularly polarized light or a function of optically compensating for phase shift due to liquid crystal. On the other hand, the retardation films 13a and 13b may not be arranged depending on the structure of the liquid crystal display device and the type of the liquid crystal compound contained in the liquid crystal layer 17. [

3 is a schematic diagram showing an EL display device 30 which is one of the display devices of the present invention. The EL display device 30 is formed by laminating the organic functional layer 36 and the cathode electrode 37 on the substrate 33 on which the pixel electrode 35 is formed. The retardation film 32 and the polarizing film 31 are disposed on the opposite side of the organic functional layer 36 with the substrate 33 interposed therebetween. At least one kind selected from the group consisting of the retardation film 32 and the polarizing film 31 is the optical film of the present invention. A positive voltage is applied to the pixel electrode 35 and a negative voltage is applied to the cathode electrode 37 and a DC current is applied between the pixel electrode 35 and the cathode electrode 37 to cause the organic functional layer 36 to emit light . The organic functional layer 36 serving as a light emitting source is composed of an electron transporting layer, a light emitting layer, and a hole transporting layer. The light emitted from the organic functional layer 36 passes through the pixel electrode 35, the interlayer insulating film 34, the substrate 33, the retardation film 32 and the polarizing film 31. An inorganic EL display device having an inorganic functional layer instead of the organic functional layer 36 is also one of the display devices of the present invention.

In order to manufacture the EL display device 30, first, the thin film transistor 40 is formed on the substrate 33 in a desired shape. Then, an interlayer insulating film 34 is formed, and then a pixel electrode 35 is formed by a sputtering method 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 thermally conductive film may be formed on the substrate. As the thermally conductive film, a diamond thin film (DLC or the like) can be mentioned. When the pixel electrode 35 is of a reflective type, light is emitted in a direction opposite to the substrate 33. Therefore, not only a transparent material but also a non-transparent material such as stainless steel can be used. The substrate may be formed of a single material, or may be a laminated substrate by bonding a plurality of substrates with an adhesive. These substrates may be plate type or film type.

As the thin film transistor 40, a usual 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 mu m. On the other hand, the size of the pixel electrode 35 is about 20 mu m x 20 mu m to 300 mu m x 300 mu m.

On the substrate 33, a wiring electrode of the thin film transistor 40 is provided. In general, the wiring electrode is made of Al, Al, and a transition metal (except for Ti), Ti, or a transition metal. The wiring electrode has a low resistance and a function of electrically connecting to the pixel electrode 35 to suppress the resistance value. And titanium nitride (TiN) may be used.

An interlayer insulating film 34 is provided between the thin film transistor 40 and the pixel electrode 35. The interlayer insulating film 34 may be formed by depositing an inorganic material such as silicon oxide or silicon nitride such as SiO ₂ by sputtering or vacuum evaporation, a silicon oxide layer formed by SOG (spin on glass), a photoresist, a polyimide, Or the like, and any insulating material may be used.

And the ribs 41 are formed on the interlayer insulating film 34. The ribs 41 are arranged in the peripheral portion (between adjacent pixels) of the pixel electrode 35. [ As the material of the ribs 41, acrylic resin, polyimide resin and the like can be given. The thickness of the ribs 41 is preferably 1.0 mu m or more and 3.5 mu m or less, more preferably 1.5 mu m or more and 2.5 mu m or less.

Next, an EL element including a pixel electrode 35 as a transparent electrode, an organic functional layer 36 as a light emitting source, and a cathode electrode 37 will be described. Each of the organic functional layers 36 has at least one hole transporting layer and a light emitting layer, and has, for example, an electron injection transporting layer, a light emitting layer, a hole transporting layer, and a hole injecting layer in sequence.

As the pixel electrode 35, ITO (tin doped indium oxide), IZO (zinc doped indium oxide), IGZO, ZnO, SnO ₂ and In ₂ O ₃ can be mentioned, and ITO and IZO are particularly preferable. The thickness of the pixel electrode 35 may have a thickness equal to or larger than a certain value sufficient for hole injection, and is preferably about 10 to 500 nm.

The pixel electrode 35 can be formed by a vapor deposition method, and is preferably formed by a sputtering method. The sputter gas is not particularly limited, and inert gases such as Ar, He, Ne, Kr, and Xe, or a mixed gas thereof may be used.

As the constituent material of the cathode electrode 37, for example, a metal element such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn, Zr, It is preferable to use an alloy system of two components and three components including these. Al: Li (Li: 0.3 to 14 at%), In-Mg (Mg: 50 to 80 at%), Al-Ca (Ca: 5 to 20 at%).

The cathode electrode 37 is formed by a vapor deposition method, a sputtering method, or the like. The thickness of the cathode electrode 37 is 0.1 nm or more, preferably 1 nm to 500 nm.

The hole injection layer has a function of facilitating injection of holes from the pixel electrode 35, and the hole transport layer has a function of transporting holes and a function of interfering with electrons, and is also called a charge injection layer and a charge transport layer.

The thickness of the light emitting layer, the sum of the hole injection layer and the hole transporting layer, and the thickness of the electron injection transporting layer are not particularly limited and may vary depending on the method of forming them, but are preferably 5 nm to 100 nm. Various organic compounds can be used for the hole injecting layer and the hole transporting layer. Since a homogeneous thin film can be formed in forming the hole injection transport layer, the light emitting layer, and the electron injection transport layer, it is preferable to use the vacuum deposition method.

As the organic functional layer 36 serving as a light emitting source, it is possible to use light emission from a singlet exciton (fluorescence), use of light emitted from triplet excitons (phosphorescence), use of light emitted from singlet excitons (fluorescence) (Phosphorescence) from excitons, those formed by organic materials, those formed by inorganic materials, those formed by organic materials and those formed by inorganic materials, polymer materials, low molecular materials, high molecular materials and low molecular materials Materials and the like may be used. However, the present invention is not limited to this, and an EL display device using various EL elements can be used.

A desiccant 38 is disposed in a space between the cathode electrode 37 and the sealing lid 39. This is because the organic functional layer 36 is weak in humidity. And the moisture is absorbed by the desiccant 38 to prevent deterioration of the organic functional layer 36.

The polarizing film 31 formed on the light incident surface or the light exit surface of the EL display device 30 is not limited to a polarizing film that is converted into linearly polarized light but may be a polarizing film that is converted into elliptically polarized light. The polarizing film 31 may be an optical film of the present invention, or a polarizing film or a retardation film other than the optical film of the present invention may be used in combination.

4 is a schematic view showing an EL display device 44 which is one of the display devices of the present invention. The EL display device 44 has a sealing structure using the thin film sealing film 42, and emitted light can also be obtained from the opposite side of the array substrate.

As the thin film sealing film 42, it is preferable to use a DLC film obtained by depositing DLC (diamond-like carbon) on a film of an electrolytic capacitor. The DLC film has very poor moisture permeability and high moisture-proof performance. Alternatively, a DLC film or the like may be directly deposited on the surface of the cathode electrode 37. The thin film sealing film 42 may be formed by laminating a resin thin film and a metal thin film in multiple layers.

At least one selected from the group consisting of the polarizing film 31 and the retardation film 32 is the optical film of the present invention.

5 is a schematic view showing a projection type liquid crystal display device which is one of display devices of the present invention.

The polarizing film 142 of the present invention and the polarizing film 143 of the present invention are used, for example, in a projection type liquid crystal display (projector).

The bundle of rays emitted from a light source (for example, a high-pressure mercury lamp) 111 serving as a light emitting source is first transferred to the first lens array 112, the second lens array 113, the polarization conversion element 114, The uniformity of the luminance and the polarization of the half-beam bundle cross-section are achieved.

Specifically, the bundle of rays emitted from the light source 111 is divided into a plurality of minute bundles of rays by the first lens array 112 in which the 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 bundles of rays irradiates the entire three liquid crystal panels 140R, 140G, and 140B to be illuminated. The entire surface of the side surface becomes almost uniform in roughness.

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

The luminance uniformized and polarized light is sequentially reflected by the dichroic mirrors 121, 123, and 132 for separating the three primary colors of R, G, and B via the reflective mirror 122 into red channels ("R" (Shown by solid line arrows), a green channel (indicated by "G" in FIG. 5, a one-dot chain line arrow), and a blue channel (indicated by a broken line arrow in FIG. 5) and enters the liquid crystal panels 140R, 140G and 140B .

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

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

The optical film of the present invention is useful as an optical film having excellent durability in either of the blue channel, the green channel and the red channel by selecting the kind of the dichroic dye suitable for the corresponding channel.

The optical image created by transmitting the incident light with different transmittance for each pixel in accordance with each image data of the liquid crystal panels 140R, 140G, 140B is synthesized by the cross dichroic prism 150, (180).

The optical film of the present invention can also be used as an optical film of an electronic paper.

Examples of the electronic paper include a display by performing alignment by optically anisotropic molecules such as a liquid crystal or a dye molecule, a display by a movement of particles such as electrophoresis, particle movement, particle rotation, or phase change, For example, display by performing color / phase change of molecules, display by light absorption of molecules, display by self-emission by combining electrons and holes, and the like. Specific examples of the display method include a microcapsule type electrophoresis method, a horizontal transfer type electrophoresis method, a vertical transfer type electrophoresis method, a spherical twist ball method, a magnetic twist ball method, a circumferential twist ball method, a charged toner method, A cholesteric liquid crystal system, a bistable nematic liquid crystal system, a ferroelectric liquid crystal system, a dichroic dye system, an electro-optic system, A liquid crystal dispersion system, a moving film system, a leuco dye-based coloring system, a photochromic system, an electrochromic system, an electro-deposition system, and a flexible organic EL system. The electronic paper may be used not only for personal use of text or images but also for advertisement signage. According to the optical film of the present invention, the thickness of the electronic paper can be reduced.

As a stereoscopic display device, there has been proposed a method (for example, Japanese Patent Application Laid-Open No. 2002-185983) in which different retardation films are alternately arranged as in the micropole system. However, when the optical film of the present invention is used as a polarizing film, , And photolithography. Therefore, the manufacturing process of the display device can be shortened, and a phase difference film is not required.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, "%" and "part" are mass% and mass part, respectively, unless otherwise specified.

In the examples, the following polymerizable liquid crystal compounds were used.

The compound (1-6) (the compound represented by the following formula (1-6)

Compound (1-6) can be prepared according to Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[Measurement of Phase Transition Temperature]

The phase transition temperature was confirmed by texture observation with a polarization microscope (BX-51, manufactured by Olympus Corporation) while heating the compound on the glass substrate on which the alignment film was formed. The compound represented by the formula (1-6) exhibited a smectic A phase from the crystalline phase at 95 ° C at the time of elevated temperature, underwent phase transitions to a nematic phase at 111 ° C and a phase transition to an isotropic liquid phase at 113 ° C. At the time of lowering the temperature, it was confirmed that the phase transition occurred at 112 캜 in a nematic phase, the phase transition occurred at 110 캜 in a smectic A phase, and the phase transition occurred at 94 캜 in a smectic B phase.

The compound (1-7) (the compound represented by the following formula (1-7)

Compound (1-7) can be prepared according to Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[Measurement of Phase Transition Temperature]

The phase transition temperature was confirmed by observing the texture with a polarizing microscope. The compound represented by the formula (1-7) exhibited a smectic A phase at 81 ° C from the crystalline phase at the temperature elevation, transitioned to a nematic phase at 121 ° C, and a phase transition to an isotropic liquid phase at 137 ° C. Phase transition to a nematic phase at 133 占 폚 and a phase transition to a smectic A phase at 118 占 폚 and a phase transition to a smectic B phase at 78 占 폚 were observed.

Example 1

[Preparation of polymerizable liquid crystal composition]

The following components were mixed and the resulting mixture was stirred at 80 占 폚 for 1 hour to obtain a polymerizable liquid crystal composition.

Polymerizable liquid crystal compound: Compound (1-6) 100 copies

Dichromatic dye: Azo dye (NKX2029; Hayashibara Seibutsu Kagaku Kankokujo)

Part 2

Polymerization initiator: 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; BASF Japan) Part 6

Polymerization initiator: Isopropyl thioxanthone (manufactured by Nippon Shiba Co., Ltd.) Part 2

Leveling agent: polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) 1.2 part

Solvent: Cyclopentanone 250 parts

[Production of optical film]

On the glass substrate, a 2 mass% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied by a spin coat method, and after drying, an alignment film with a thickness of 89 nm was formed. Then, the surface of the obtained alignment film was rubbed. The rubbing treatment was carried out by using a semi-automatic rubbing device (trade name: LQ-008 type, manufactured by Joyo Kogaku Co., Ltd.) with a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Kako Co., Ltd.) 500 rpm, and 16.7 mm / s.

The polymerizable liquid crystal composition was coated on the alignment layer after rubbing by the spin coating method and heated and dried on a hot plate at 120 캜 for 3 minutes and then cooled rapidly to 70 캜 (temperature showing a smith image at the time of temperature decrease) Thereby obtaining a coated film. An ultraviolet ray having an exposure amount of 2400 mJ / cm 2 (365 nm standard) was irradiated to the coated film by using a UV irradiator (SPOT CURE SP-7; manufactured by Ushio DENKI KK) to obtain an optical film on the glass substrate.

[Measurement of two-color ratio]

The absorbance (A ¹ ) in the transmission axis direction at the maximum absorption wavelength and the absorbance (A ² ) in the absorption axis direction were measured using a spectrophotometer UV-3150 manufactured by Shimadzu Seisakusho Co., Ltd. in which a folder having a polarizer was set And measured by the double beam method. On the reference side of the folder, a mesh 50% light cut is installed. The ratio (A ² / A ¹ ) was calculated from the measured values of the absorbance (A ¹ ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction to obtain a two color ratio. The results are shown in Table 2. The higher the two-color ratio, the more useful it is as a polarizing film.

[Measurement of film thickness]

The obtained optical film was measured for film thickness using a laser microscope (LEXT 3000, manufactured by Olympus Corporation). The results are shown in Table 2.

[Measurement of Haze]

The haze value of the obtained optical film was measured using a haze meter (HZ-2; manufactured by Suga Shikeki Co., Ltd.). The results are shown in Table 2.

[Observation of liquid crystal phase]

The liquid crystal phase shown by the obtained optical film was observed with a polarization microscope (BX-51, manufactured by Olympus). Observation was carried out in such a manner that the slow axis of the obtained optical film was oriented at 45 degrees with respect to the transmission axis of the polarizer, between two polarizers in which the transmission axes were perpendicular to each other.

As a result of observation, it was evaluated as " o " when it was confirmed that horizontally aligned mono domain was formed, and " x " The results are shown in Table 2.

[Observation of unevenness]

The optical film thus obtained was placed so that the absorption axis thereof was orthogonal to the urea-PVA polarizing plate (SRW842A; manufactured by Sumitomo Chemical Co., Ltd.), and observed by direct observation on a direct-type backlight. &Quot; & cir & • • • • • • The results are shown in Table 2.

Examples 2 to 15, Reference Examples 1 and 2

The polymerizable liquid crystal compound and leveling agent shown in Table 1 were used in the same manner as in Example 1 to obtain a polymerizable liquid crystal composition.

The leveling agents shown in Table 1 were used as follows.

A polyacrylate compound (BYK-361N, manufactured by BYK-Chemie)

A polyacrylate compound (BYK-352; manufactured by BYK-Chemie)

A polyacrylate compound (BYK-354, manufactured by BYK-Chemie)

A polyacrylate compound (BYK-381; manufactured by BYK-Chemie)

A polyacrylate compound (BYK-392, manufactured by BYK-Chemie)

Fluorine-containing oligomer (Megafox F471, manufactured by DIC Corporation)

Fluorine-containing oligomer (Megafox F477, manufactured by DIC Corporation)

The polymerizable liquid crystal compositions of Examples 2 to 15 and Reference Examples 1 and 2 obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 16

[Preparation of polymerizable liquid crystal composition]

The following components were mixed and the resulting mixture was stirred at 80 占 폚 for 1 hour to obtain a polymerizable liquid crystal composition.

Polymerizable liquid crystal compound: Compound (1-6) 100 copies

Polymerization initiator: 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; BASF Japan) Part 6

Polymerization initiator: Isopropyl thioxanthone (manufactured by Nippon Shiba Co., Ltd.) Part 2

Leveling agent: polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) 1.2 part

Solvent: Cyclopentanone 250 parts

[Production of optical film]

Using the polymerizable liquid crystal composition obtained above, the same procedure as in Example 1 was carried out to obtain an optical film.

[Observation of liquid crystal phase]

As to the obtained optical film, the liquid crystal phase was observed in the same manner as in Example 1, and it was recognized that horizontally aligned mono-domains were formed.

[Measurement of film thickness]

The film thickness of the obtained optical film was measured in the same manner as in Example 1 and found to be 1.8 탆.

[Measurement of phase difference value]

With respect to the obtained optical film, the front retardation value at a wavelength of 587.7 nm was measured using a birefringence measuring apparatus (KOBRA-WR, manufactured by Oushikiso Sokki KK), and it was found to be 257 nm. On the other hand, since the glass substrate used as the base material does not have birefringence, the front retardation value of the optical film can be obtained by measuring the optical film with the glass substrate attached thereto with a measuring device.

[Industrial applicability]

According to the polymerizable liquid crystal composition of the present invention, an optical film having a smectic phase oriented in the horizontal direction can be easily obtained. An optical film formed with a horizontally oriented smectic phase and containing a dichroic dye is particularly useful as a polarizing film because of its excellent two-color ratio.

10: liquid crystal display device 11: antireflection film
12a, 12b: Polarizing film 13a, 13b:
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 film 32: retardation film
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: superimposing lenses 121, 123, 132: dichroic mirrors
122: reflection mirror 140R, 140G, 140B: liquid crystal panel
142, 143: polarizing film 150: cross dichroic prism
170: projection lens 180: screen

Claims (6)

1. An optical film formed from a polymerizable liquid crystal composition showing a stymatic phase, a leveling agent, a dichroic dye, and a solvent,
Wherein the leveling agent is at least one member selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-
The content of the leveling agent is not less than 0.3 parts by mass and not more than 5 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound,
An optical film having a haze of 0.4% to 2.4%. An optical film comprising a polymerizable liquid crystal compound polymer having a stymatic liquid crystal phase, a leveling agent, and a dichroic dye,
Wherein the leveling agent is at least one member selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-
The content of the leveling agent is not less than 0.3 parts by mass and not more than 5 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound,
An optical film having a haze of 0.4% to 2.4%. The optical film according to claim 1 or 2, wherein the polymerizable liquid crystal compound is a compound represented by the following formula (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 the 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. Provided that at least one of X ¹ , X ² and X ³ represents a p-phenylene group which may have a substituent.
Also, at least one of X ¹ , X ² and X ³ represents a cyclohexane-1,4-diyl group which may have a substituent.
Y ¹ and Y ² independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N═N-, -CR ^a = CR ^b -, - C? C- or CR ^a = N-.
R ^a and R ^b 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 independently represent a single bond, -O-, -S-, -COO- or -OCOO-.
V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the alkanediyl group is substituted with -O-, -S- or -NH- It may be.] A leveling agent and a dichroic dye (provided that the molecular length of the molecular long axis of the dichroic dye is longer than the molecular length of the molecular long axis of the polymerizable liquid crystal compound, (Excluding an optical film)
Wherein the leveling agent is at least one member selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-
Wherein the content of the leveling agent is not less than 0.3 parts by mass and not more than 5 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. The liquid crystal display device according to any one of claims 1 to 4, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound having a temperature exhibiting a nematic phase within a temperature range that exhibits a smectic phase and an isotropic phase Optical film. A display device comprising the optical film according to any one of claims 1 to 5.

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