KR101985258B1 - Liquid crystal aligning agent, liquid crystal alignment film, phase difference film, method for forming phase difference film, liquid crystal display device, and polymer - Google Patents

Abstract

A liquid crystal aligning agent capable of forming a liquid crystal alignment film exhibiting good liquid crystal alignability and having excellent adhesion to a liquid crystal layer, a liquid crystal alignment film formed of the liquid crystal aligning agent, a retardation film having the liquid crystal alignment film, A liquid crystal display element having a film, and a polymer as a suitable component of the liquid crystal aligning agent.
(Solution) The liquid crystal aligning agent of the present invention contains [A] a component having a photo-orienting group and a group containing a polymerizable double bond in the same or different molecules. The component [A] is preferably a polymer component. The photo-orientable group is preferably a group containing a cinnamic acid structure. The liquid crystal alignment film of the present invention is formed from the liquid crystal aligning agent. The retardation film of the present invention comprises the liquid crystal alignment film. Such a retardation film is preferably used for a liquid crystal display element. The liquid crystal display element of the present invention comprises the above-mentioned retardation film.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a retardation film, a method of producing a retardation film, a liquid crystal display element and a polymer, }

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a retardation film, a production method of a retardation film, a liquid crystal display element and a polymer.

BACKGROUND ART Liquid crystal displays (LCDs) are widely used in televisions and various monitors. As a display element of an LCD, for example, STN (Super Twisted Nematic) type, TN (Twisted Nematic) type, IPS (In Plane Switching) type, VA (Vertically Aligned) type, PSA (Polymer sustained alignment) (See Japanese Unexamined Patent Application Publication No. 56-91277 and Japanese Unexamined Patent Publication No. 1-120528). Various optical materials are used for the liquid crystal display element. For example, the retardation film included in the liquid crystal display element may be used for the purpose of eliminating the coloring of the display image, or the display color and the contrast ratio (See Japanese Unexamined Patent Application Publication No. 4-229828 and Japanese Unexamined Patent Publication No. 4-258923).

As a production method of this retardation film, there is known a roll-to-roll method in which a retardation film is continuously produced on a long base material film (see Japanese Patent Laid-Open Publication No. 2000-86786). In this roll-to-roll system, a liquid crystal alignment film is formed on a base film using a liquid crystal aligning agent, a polymerizable liquid crystal is applied on the formed liquid crystal alignment film, and the polymerizable liquid crystal is cured by light irradiation Thereby forming a liquid crystal layer.

However, when the conventional liquid crystal aligning agent is used, the adhesion between the liquid crystal alignment film and the liquid crystal layer formed thereon is not necessarily sufficient. For example, the retardation film included in the roll- The liquid crystal layer may be peeled off.

Japanese Laid-Open Patent Publication No. 56-91277 Japanese Unexamined Patent Application Publication No. 1-120528 Japanese Patent Application Laid-Open No. 4-229828 Japanese Patent Application Laid-Open No. 4-258923 Japanese Patent Application Laid-Open No. 2000-86786

The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film exhibiting good liquid crystal alignability and excellent adhesion to a liquid crystal layer.

According to an aspect of the present invention,

[A] A liquid crystal aligning agent containing a component having a photo-aligning group and a group containing a polymerizable double bond (hereinafter also referred to as "component (A)") in the same or different molecules.

According to another aspect of the present invention,

A liquid crystal alignment film formed of the liquid crystal aligning agent,

A retardation film having the liquid crystal alignment film,

A liquid crystal display element having the retardation film, and

A polymer having a group containing a photo-alignable group and a polymerizable double bond.

According to another aspect of the present invention,

(1) a step of forming a coating film on the substrate by using the liquid crystal aligning agent,

(2) a step of forming a liquid crystal alignment film by irradiation of the coating film with radiation,

(3) a step of forming a polymerizable liquid crystal film on the liquid crystal alignment film by using a polymerizable liquid crystal, and

(4) a step of curing the polymerizable liquid crystal film to form a liquid crystal layer.

Here, the polymerizable double bond refers to a double bond capable of easily forming a radical to carry out a growth reaction. The polymerizable double bond includes, for example, a terminal double bond.

Since the liquid crystal aligning agent and the polymer of the present invention have a group containing a photo-aligning group and a polymerizable double bond in a component such as a polymer, a liquid crystal alignment film exhibiting good liquid crystal alignability and excellent adhesion to the liquid crystal layer is formed . Therefore, the present invention can provide a retardation film having a liquid crystal alignment film which exhibits good liquid crystal alignability and excellent adhesion to the liquid crystal layer, a method for producing the same, and a liquid crystal display element comprising the retardation film, .

(Mode for carrying out the invention)

<Liquid Crystal Aligner>

The liquid crystal aligning agent contains the component [A]. The liquid crystal aligning agent may contain optional components such as a metal chelate compound [B], a curing accelerator, a surfactant, and the like within a range not to impair the effect of the present invention. Each component will be described in detail below.

<Component [A]>

The component [A] is a component having a group containing a photo-aligning group and a polymerizable double bond in the same or different molecules. Since the liquid crystal aligning agent contains the component [A], the liquid crystal alignment film formed with the liquid crystal aligning agent exhibits good liquid crystal alignability and is excellent in adhesion with the liquid crystal layer. This is considered to be because the cross-linking structure between the liquid crystal alignment layer and the liquid crystal layer is strengthened by the polymerizable double bonds contained in the molecule, thereby enhancing the interaction between the two.

Examples of the component (A) include (1) a compound having a photo-orienting group and a group containing a polymerizable double bond in the same molecule, (2) a compound having a group containing a polymerizable double bond in different molecules and a photo- have.

The component [A] is not particularly limited as long as it has a group having a photo-orienting group and a polymerizable double bond in the same or different molecules, and may be any of a polymer component and a non-polymer component, but it is preferably a polymer component (Hereinafter, the polymer component and the non-polymer component having a group having a photo-orienting group and a polymerizable double bond in the same or different molecules are also referred to as "[A] polymer component" and "[A] non-polymer component" ). When the component [A] is a polymer component, the hardness of the liquid crystal alignment film formed with the liquid crystal aligning agent can be increased. Hereinafter, the group containing a polymerizable double bond, the photo-orientable group, and the [A] polymer component will be described in this order.

[A group containing a polymerizable double bond]

The group containing a polymerizable double bond can react with the polymerizable liquid crystal applied on the liquid crystal alignment film to form a crosslinked structure. The liquid crystal aligning agent has a group [A] containing a polymerizable double bond, so that the adhesion between the liquid crystal alignment layer and the liquid crystal layer can be enhanced.

As the polymerizable double bond, a carbon-carbon double bond is preferable. As the group containing a carbon-carbon double bond, for example, a vinyl group, a (meth) acryloyl group and the like can be mentioned, but a (meth) acryloyl group is preferable.

When the component [A] is a polymer component, the group containing the polymerizable double bond may be, for example, a reaction in which a carboxy group is added to an epoxy group (hereinafter also referred to as "addition reaction"), an isocyanate group, A carboxyl group or a thiol group, and the like can be used to introduce into the polymer component [A]. Each of the above-mentioned groups provided for the addition reaction may be on the side of the polymer or on the side of the compound added to the polymer. Further, a reaction of adding a hydroxyl group to -COCl may be used. In this case, from the viewpoint of ease of introduction, it is preferable that a hydroxy group is on the polymer side and -COCl is on the compound side to which the polymer is added. When these addition reactions are used, usually the compound added to the polymer has a group containing the polymerizable double bond. Among them, from the viewpoint of ease of introduction, it is preferable to use a reaction of adding a carboxy group to an epoxy group. Hereinafter, a compound having a carboxyl group and an epoxy group, which are used in the addition reaction at the time of introducing a group containing a polymerizable double bond, will be described.

Examples of the compound having a polymerizable double bond and a carboxyl group (including a polyvalent carboxylic acid anhydride having a polymerizable double bond) (hereinafter also referred to as "unsaturated compound (a)") include (meth) acrylic acid, Unsaturated carboxylic acids such as ω-carboxy polycaprolactone, crotonic acid, α-ethyl acrylate, α-n-propyl acrylate, α-n-butyl acrylate, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid ; And unsaturated polycarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and cis-1,2,3,4-tetrahydrophthalic anhydride. Among them, (meth) acrylic acid and (meth) acrylic acid? -Carboxypolycaprolactone are preferable.

Examples of commercial products of the unsaturated compound (a) include ARONIX M-510, Aronix M-5300 (manufactured by TOAGOSEI), LIGHT ESTER HOMS (manufactured by Kyoeisha Kagaku), and the like .

Examples of the compound having a polymerizable double bond and an epoxy group (excluding the above unsaturated compound (a)) (hereinafter also referred to as "unsaturated compound (b)") include glycidyl (meth) acrylate, Glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4- (3-methyl-3-oxetanylmethyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyhexyl acrylate, Hydroxybutyl glycidyl ether, and the like. Among these, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate and 4-hydroxybutyl glycidyl ether desirable.

Further, when the polysiloxane is contained as the polymer component [A], the group containing the polymerizable double bond may be introduced by a silane compound having a group containing a polymerizable double bond described later.

The compound capable of giving a group containing a polymerizable double bond may be used alone or in combination of two or more. These compounds may be used as one of the components [A] as they are.

In the case where the component [A] is a non-polymeric component, the group containing the polymerizable double bond can be obtained, for example, in the non-polymeric compound by adding the carboxy group to the epoxy group and the isocyanate group A hydroxyl group, a hydroxyl group, an amino group, a carboxy group or a thiol group, and the like. Each of the groups described above for the addition reaction may be on the side of the non-polymer compound or on the side of the compound added to the non-polymer compound. In addition, from the viewpoint of easiness of introduction, it is preferable that the hydroxy group is present on the side of the compound added to the non-polymerizable compound at the side of the non-polymerizable compound and -COCl is added to the non-polymerizable compound . When these addition reactions are used, the compound added to the non-polymeric compound usually has a group containing the polymerizable double bond. Among them, from the viewpoint of ease of introduction, it is preferable to use a reaction of adding a carboxy group to an epoxy group. Examples of the compound having an epoxy group used in the addition reaction at the time of introducing a group containing a polymerizable double bond include those represented by the following formulas.

Examples of commercial products of the epoxy group-containing compound represented by the above formula include TETRAD-X (manufactured by Mitsubishi Gas Chemical), Celloxide 2021P (manufactured by Daicel), EX-850L (manufactured by Nagase Chemtech), TETRAD -C (manufactured by Mitsubishi Chemical Corporation) and the like.

[Optical alignment machine]

The photo-alignment group is a functional group capable of imparting anisotropy to the film by light irradiation. This anisotropy is imparted by a photo-isomerization reaction or a photo-dimerization reaction. When the component [A] of the liquid crystal aligning agent has a photo aligning group, photo alignment property can be imparted to the formed liquid crystal alignment film.

As the photo-alignment group, various groups derived from a compound showing optical alignment can be adopted. For example, a group including an azobenzene structure containing azobenzene or a derivative thereof as a basic skeleton, cinnamic acid or a derivative thereof as a basic skeleton A group containing a chalcone structure containing a chrysene group or a derivative thereof as a basic skeleton, a group containing a benzophenone structure containing a benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof As a basic skeleton, a group containing a polyimide structure containing a polyimide or a derivative thereof as a basic skeleton, and the like. Among these, from the viewpoints of excellent photo-alignment property and ease of introduction of the group, it is preferable that the group contains a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton. The liquid crystal alignment layer is a group containing a cinnamic acid structure as a photo-orientable group, and exhibits good photo-alignment property by irradiation with polarized ultraviolet light.

The structure of the group including a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton, and groups derived from cinnamic acid and cinnamic acid derivatives represented by the following formulas are preferable.

The method for synthesizing cinnamic acid and cinnamic acid derivatives is not particularly limited, and known methods can be used in combination. Representative synthetic methods include, for example, a method of reacting a compound having a benzene ring skeleton substituted with a halogen atom under basic conditions and acrylic acid or a derivative thereof in the presence of a transition metal catalyst; A method in which a compound having a benzene ring skeleton substituted with a halogen atom is reacted with a cinnamic acid in which a hydrogen atom of a benzene ring is substituted with a halogen atom in the presence of a transition metal catalyst under basic conditions.

The photo-orientable group-imparting compound is preferably used as a raw material for the polymer component [A] or the non-polymeric component [A] described later, but may be used as one of the components [A]. In these cases, the photo-orientable group-imparting compound may be used alone or in combination of two or more.

Examples of the raw material of the non-polymerizable component for imparting the photo-orientable group include the same compounds as those having an epoxy group used when a group containing a polymerizable double bond is introduced into a non-polymerizable compound.

&Lt; [A] Polymer Component >

[A] The polymer component is a polymer component having a group containing a photo-aligning group and a polymerizable double bond in the same or different polymers. The polymer component [A] is not particularly limited as long as it is a polymer component having the above specific group, and polysiloxane and (meth) acrylic polymer are preferable, and mixtures thereof are more preferable. In particular, the polysiloxane having a photo-alignment group exhibits excellent photo-alignment property, and the (meth) acrylic polymer can improve adhesion with the liquid crystal layer. As the polymer component [A], other polymers such as polyether, vinyl polymer and aromatic ring-containing polymer (hereinafter collectively referred to as "other polymer") may be used. Hereinafter, the polysiloxane, (meth) acrylic polymer and other polymers having the specific groups will be described.

[Polysiloxane]

The polysiloxane constituting the polymer component [A] is not particularly limited as long as it has a group containing a polymerizable double bond and / or a photo-orientable group,

(Hereinafter also referred to as &quot; silane compound (b) &quot;) having a polymerizable double bond and a silane compound containing an epoxy group (hereinafter also referred to as &quot; silane compound (Hereinafter also referred to as &quot; silane compound (c) &quot;) which is different from both of the silane compound (a) and the silane compound (b) according to the method of the present invention is hydrolyzed and condensed in a suitable organic solvent in the presence of water and a catalyst , A method of reacting a carbonic acid compound which further gives a photo-orientable group,

(P2) The silane compound (a) and, if necessary, the silane compound (b) or the silane compound (c) are hydrolyzed and condensed in the presence of water and a catalyst in a suitable organic solvent, And / or a method of reacting a carbonic acid compound which gives a photo-aligning group and the like. The silane compound (c) is not particularly limited as long as it is hydrolyzed to produce a silanol group.

Examples of the silane compound (a) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Of these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.

Examples of the silane compound (b) include 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, 3- (methacryloyloxy) Propyltriethoxysilane, 3- (methacryloyloxy) propylmethyldiethoxysilane, and the like. Among them, 3- (methacryloyloxy) propyltrimethoxysilane is preferable.

As the silane compound (c), for example,

Butoxy silane, tetra-sec-butoxy silane, tetra-tert-butoxy silane, tetra-n-propoxy silane, tetra- Tetrachlorosilane and the like;

Methyltriethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec Butoxysilane, methyltri-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso Butoxy silane, ethyl tri-sec-butoxysilane, ethyl tri-tert-butoxysilane, ethyl trichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl Trichlorosilane, hexamethylenebis (trimethoxysilane), 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane and the like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane and the like;

Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like.

Of these, tetramethoxysilane and tetraethoxysilane are preferable.

Examples of the carbonic acid compound which imparts a group containing a polymerizable double bond and the carbonic acid compound which imparts a photo-aligning group are the compounds of the [unsaturated compound (a) containing a polymerizable double bond] A carbonic acid compound in a compound having a photo-orientable group as described in the above can be applied.

Examples of the organic solvent include an alcohol-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent, and other aprotic organic solvents. These organic solvents may be used alone or in combination of two or more.

The reaction temperature for synthesizing the polysiloxane is preferably 0 deg. C to 100 deg. C, more preferably 15 deg. C to 90 deg. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 8 hours.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) when the polymer constituting the polymer component is polysiloxane is preferably 500 to 100,000, more preferably 1,000 to 50,000. When Mw is in the above range, good alignment and stability of the liquid crystal display element can be ensured.

[(Meth) acrylic polymer]

The (meth) acrylic polymer constituting the polymer component [A] is not particularly limited as long as it has a group containing a polymerizable double bond and / or a photo-orientable group. And the like.

(M1) A polymer is synthesized by, for example, radical polymerization in the presence of a (meth) acrylic compound having an epoxy group in the presence of a suitable organic solvent (hereinafter also referred to as "organic solvent (b1)") (A) and / or a carbonic acid compound which gives a photo-aligning group in a suitable organic solvent (hereinafter also referred to as "organic solvent (b2)"), preferably in the presence of a catalyst

(M2) A process for producing a copolymer by copolymerizing (meth) acrylic acid and a polymerizable compound imparting a photo-orienting group in the presence of an appropriate organic solvent (b1) and a polymerization initiator, for example, by radical polymerization, (B) in an appropriate organic solvent (b2), preferably in the presence of a catalyst

Examples of the (meth) acrylic compound having an epoxy group include the same compounds exemplified as the unsaturated compound (b).

As the carbonic acid compound which imparts the photo-orientable group, a carbonic acid compound among the compounds having photo-orientable groups described in [photo-orientable group] can be applied.

Examples of the polymerizable compound which imparts the photo-orientable group include a compound having a photo-orientable group and a polymerizable double bond.

Examples of the organic solvent (b1) include an alcohol solvent, an ether solvent, a ketone organic solvent, an amide solvent, an ester organic solvent and a hydrocarbon solvent. These organic solvents (b1) may be used alone or in combination of two or more. Among them, an alcohol solvent and an ether solvent are preferable, a solvent in which a polyhydric alcohol is partially etherified is more preferable, diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate are more preferable, and diethylene glycol methyl ethyl Ether is particularly preferred. These organic solvents (b1) may be used alone or in combination of two or more.

As the polymerization initiator, for example,

Azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethyl Azo compounds such as valeronitrile);

Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis (t-butylperoxy) cyclohexane;

Hydrogen peroxide;

And a redox-type initiator comprising these peroxides and a reducing agent.

Of these, azo compounds are preferable, and 2,2'-azobis (isobutyronitrile) is more preferable. These polymerization initiators may be used alone or in combination of two or more.

Examples of the organic solvent (b2) include solvents similar to those exemplified as the organic solvent (b1). Among them, an ester-based organic solvent is preferable, and propylene glycol monomethyl ether acetate is more preferable. These organic solvents (b2) may be used alone or in combination of two or more.

As the catalyst, for example,

Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine;

2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) 1- (2-cyanoethyl) -2-n-octylimidazole, 1- (2-cyanoethyl) 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- (2-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate (2- cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s- Triazine, 2,4-di Methyl-imidazolyl (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl (1 ')] ethyl-s-triazine;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenphosphate;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor N-butylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetraphenylphosphonium tetraphenylborate Quaternary phosphonium salts such as tetra-n-butylphosphonium tetrafluoroborate and tetra-n-butylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and their organic acid salts;

Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride and tetrabutylammonium chloride;

Boron compounds such as boron trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersion type latent catalyst such as dicyandiamide or an amine addition type accelerator such as an adduct of an amine and an epoxy resin;

A microcapsule type latent catalyst in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent catalyst;

Potential catalysts such as high temperature dissociation type thermal cationic polymerization latent catalysts such as Lewis acid salts and Bronsted acid salts, and the like.

These catalysts may be used alone or in combination of two or more.

Among these catalysts, a quaternary ammonium salt is preferable, and tetrabutylammonium bromide is more preferable.

The amount of the catalyst to be used is preferably 100 parts by mass or less, more preferably 0.01 parts by mass to 100 parts by mass, further preferably 0.1 parts by mass to 20 parts by mass, per 100 parts by mass of the polymer.

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 0.1 hour to 50 hours, more preferably 0.5 hours to 20 hours.

When the polymer constituting the polymer component is a (meth) acrylic polymer, the number average molecular weight (Mn) in terms of polystyrene by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and more preferably 1,000 to 50,000 Is more preferable. When Mn is in the above range, it is possible to ensure good optical alignment and stability of the liquid crystal alignment layer formed of the liquid crystal aligning agent.

[Other Polymers]

The other polymer is not particularly limited as long as it has a group containing a polymerizable double bond and / or a photo-orientable group, except for the polysiloxane and the (meth) acrylic polymer, but can be produced, for example, from the corresponding epoxy group- . &Lt; / RTI &gt;

The other polymer can be synthesized by a method of adding an epoxy group-containing compound to an epoxy group in a suitable organic solvent, preferably in the presence of a catalyst, by adding the unsaturated compound (a) and / or a carbonic acid compound giving a photo- have.

The epoxy group-containing compound is not particularly limited as long as it has a group containing a polymerizable double bond and / or an epoxy group capable of adding a photo-aligning group, and examples thereof include polymers having a structural unit represented by the following formula have.

Examples of commercial products of the polymer having the structural unit represented by the above formula include EHPE3150 (manufactured by Daicel), JP200 (manufactured by Nippon Soda Co., Ltd.) and HP7200 (manufactured by DIC).

Examples of the organic solvent include the same solvents as those exemplified as the organic solvent (b1). Among them, an ester-based organic solvent is preferable, and propylene glycol monomethyl ether acetate is more preferable. These organic solvents may be used alone or in combination of two or more.

As the catalyst, for example, there can be mentioned the same catalyst as the catalyst exemplified in the synthesis method of [(meth) acrylic polymer]. Of these, quaternary ammonium salts are preferred, and tetrabutylammonium bromide is more preferred.

The amount of the catalyst to be used is preferably 100 parts by mass or less, more preferably 0.01 parts by mass to 100 parts by mass, further preferably 0.1 parts by mass to 20 parts by mass, per 100 parts by mass of the polymer.

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 0.1 hour to 50 hours, more preferably 0.5 hours to 20 hours.

The content of the [A] component is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total solid content of the liquid crystal aligning agent.

<[B] Metal chelate compound>

The metal chelate compound [B] is a component that promotes the cross-linking reaction between the molecules of the component [A] and forms a liquid crystal alignment film having a high hardness even at a low temperature and a short time of heat treatment. The liquid crystal aligning agent preferably contains a [B] metal chelate compound.

Examples of the metal chelate compound [B] include a zirconium compound, a titanium compound, and an aluminum compound.

Examples of the zirconium compound, the titanium compound and the aluminum compound include compounds represented by the following formulas (2-1) to (2-4).

In the formulas (2-1) to (2-3), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group, Or an alkoxy group. R ³ , R ⁶ and R ⁹ are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group or an alkoxy group. R ^A is a hydrogen atom or a methyl group. p and p 'are each independently an integer of 0 to 3; p "is an integer of 0~2. R ¹ ~R ^9, if a plurality of each, a plurality of R ¹ ~R ⁹ are, respectively, may be the same or different.

In the formula (2-4), R ^B is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, a cycloalkyl group or an alkoxy group. Ar is an arylene group. When R ^B and Ar are respectively plural, plural R ^B and Ar may be the same or different. R ^c is an alkyl group having 1 to 6 carbon atoms, an aryl group, a cycloalkyl group or an alkoxy group. p '&quot; is an integer of 0 to 2; When there are a plurality of R ^c , a plurality of R ^c may be the same or different.

Examples of the alkyl group having 1 to 6 carbon atoms include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group and an n-pentyl group. Examples of the alkoxy group having 1 to 16 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a n-butoxy group, a sec-butoxy group, Time and so on. Examples of the arylene group include a phenylene group, a tolylene group, a xylene group and a naphthylene group. Examples of the cycloalkyl group include a cyclohexyl group and the like.

Examples of the aluminum compound include diisopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (Ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum, and compounds represented by the following formulas.

Examples of the zirconium compound include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis -Propyl acetoacetate) zirconium, tetrakis (acetylacetonate) zirconium, tetrakis (ethylacetoacetate) zirconium and the like.

Examples of the titanium compound include titanium compounds such as diisopropoxybis (ethylacetoacetate) titanium and diisopropoxybis (acetylacetonate) titanium.

Among these metal chelate compounds, aluminum compounds are preferred, diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum and tris (ethyl acetoacetate) aluminum are more preferable, tris (acetylacetonate) Aluminum is more preferable.

These [B] metal chelate compounds may be used alone or in combination of two or more. As the [B] metal chelate compound, a partial hydrolyzate of these metal chelate compounds may also be used.

The content of the metal chelate compound [B] is preferably 0.1 part by mass to 30 parts by mass, more preferably 0.5 part by mass to 15 parts by mass, per 100 parts by mass of the component [A]. By setting the content of the metal chelate compound in the above range, it is possible to promote the crosslinking reaction and make it possible to manufacture a liquid crystal alignment film even at a low temperature and a short time of heat treatment, and to preserve (maintain) the storage stability well.

[Curing accelerator]

The curing accelerator is a component which can be used for a cross-linking reaction between molecules of the component [A], such as when the molecule of the component [A] has an epoxy group, and can accelerate the crosslinking. Examples of the curing accelerator include a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, etc., a carboxylic acid anhydride, and an aromatic sulfonium salt. Among them, a phenol group, a silanol group, a compound having a carboxy group, a carbonic acid anhydride, and an aromatic sulfonium salt are preferable, and a compound having a phenol group, a silanol group and an aromatic sulfonium salt are more preferable, and a compound having a silanol group, Is particularly preferred.

Examples of the compound having a phenol group include compounds represented by the following formulas.

In the above formula, n ¹ and m ¹ are each independently an integer of 1 to 10.

Examples of the compound having a silanol group include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl ) Benzene, and a compound represented by the following formula (3).

In the formula (3), R ¹⁰ is an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, a halogen atom, -NO ₂ , -CN, -COOR ¹² or -SO ₂ OR ¹² . R ¹² is an alkyl group having 1 to 4 carbon atoms. R ¹¹ is an alkyl group having 1 to 4 carbon atoms or an alicyclic group. l and n ² are, each independently, an integer from 1 to 3. m ² is an integer of 0 to ² . However, l + n ² + m ² = 4. v is an integer of 0 to 5; When there are a plurality of R ¹⁰ and R ¹¹ each, a plurality of R ¹⁰ and R ¹¹ may be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹⁰ to R ¹² include a methyl group, an ethyl group and a propyl group.

The compound having a silanol group is preferably a compound represented by the formula (3), a compound wherein n ² is 2 or 3 and R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, a fluorine atom or -CN which may be substituted with a fluorine atom, v is 0, the compound (for example, the following formulas (3-1) to (3-8), compounds represented by) more preferably, n is 3 and ² may be substituted with a fluorine atom as R ¹⁰ good having 1 to 4 carbon atoms (3-1) and (3-2) shown below are more preferable, and compounds represented by the following formulas (3-1) and (3-2) Are particularly preferred.

Examples of the compound having a silanol group include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethylisobutoxysilane, trimethyl-1- But are not limited to, methyl propoxysilane, trimethyl butoxy silane, dimethyl diethoxy silane, diethyl diethoxy silane, methyl triethoxysilane, ethyl triethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, But are not limited to, diphenyldimethoxysilane, diphenylmethylethoxysilane, methylphenyldiethoxysilane, methyldimethoxysilane, trimethoxysilane, triethoxysilane, dimethylethoxysilane, diethoxysilane, tetramethoxysilane, Dimethylvinylethoxysilane, ethyltrimethoxysilane, methyldiethoxysilane, butyltrimethoxysilane, trimethylphenoxysilane, trimethyl-3-hyde Methyl-2-hydroxyphenoxytrisilane, phenylmethyldimethoxysilane, trimethylcyclohexyloxysilane, allyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, hexyloxytrimethylsilane , Propyltriethoxysilane, hexyltrimethoxysilane, dimethylphenylethoxysilane, tripropylmethoxysilane, methyltripropoxysilane, octyloxytrimethoxysilane, benzyltriethoxysilane, diphenylvinylethoxysilane , Diphenyldiethoxysilane, triphenylethoxysilane, tetraphenoxysilane, 1,2-bis (trimethylsiloxy) benzene, 1,3-bis (trimethylsiloxy) benzene, 1,4- Cis) benzene, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, and the like.

Further, in the compound having a phenol group and the compound having a silanol group, the phenol group and the silanol group may be protected with, for example, a protecting group represented by the following formula. Thus, the storage stability at room temperature can be improved while maintaining the catalytic activity.

As the aromatic sulfonium salt, for example,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2. 1] hepto-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 10-camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4 -Cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 10-camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfate 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenylsulfonium trifluoromethanesulfonate, 4- Octylsulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoro Ethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 10-camphorsulfonate, triphenylphosphonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) -hexane -1-sulfonate, and the like.

The content of the curing accelerator is preferably 0.5 part by mass to 70 parts by mass, more preferably 1 part by mass to 60 parts by mass, further preferably 2 parts by mass to 50 parts by mass, per 100 parts by mass of the component [A]. When the content of the curing accelerator is within the above range, curing of the liquid crystal alignment film can be effectively promoted.

[Surfactants]

The surfactant is a component that improves the coatability of the liquid crystal aligning agent to the substrate. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. These surfactants may be used alone or in combination of two or more.

The content of the surfactant is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the liquid crystal aligning agent.

&Lt; Preparation method of liquid crystal aligning agent >

The liquid crystal aligning agent is prepared as a composition in a solution state in which the component [A] as an essential component and, if necessary, other components are mixed in a predetermined ratio, preferably each component is dissolved in an organic solvent. The composition in the solution state may be prepared by filtration with a filter having a pore diameter of about 1 탆 after mixing the components.

It is preferable that the organic solvent does not react with the [A] component and other components contained as required. Examples of the organic solvent include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent and a hydrocarbon-based solvent. These organic solvents may be used alone or in combination of two or more.

As the alcoholic solvent, for example,

As the monoalcohol-based solvent, it is preferable to use at least one solvent selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, Heptanol, sec-heptanol, 3-heptanol, n-octanol, sec-hexanol, sec-hexanol, sec- Sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-tetradecyl alcohol, sec-octadecanol, sec-octadecyl alcohol, Heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like;

Examples of polyhydric alcohol solvents include polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl- , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;

Examples of the polyhydric alcohol partial ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2- Diethyleneglycol monoethyl ether, diethyleneglycol monopropyl ether, diethyleneglycol monobutyl ether, diethyleneglycol monohexyl ether, propyleneglycol monomethyl ether, propyleneglycol monoethyl ether, diethyleneglycol monomethylether, diethyleneglycol monomethylether, , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol ethyl methyl ether and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethyl nonane, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, Acetonyl acetone, acetophenone, and the like.

Examples of the amide solvent include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, Amide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like.

Examples of the ester solvents include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, Ethyl acetate, ethyl acetate, ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, diacetic acid diacetate, diethyl acetate, and the like. Ethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid propylene glycol monoethyl ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol mono Butyl Butyl acetate, diethyl oxalate, di-n-propyl acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, Butyl, methyl lactate, ethyl lactate, n-butyl lactate, diethyl lactate, dimethyl dimethyl phthalate, and diethyl phthalate.

As the hydrocarbon-based solvent, for example,

Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, Methylcyclohexane and the like;

Examples of the aromatic hydrocarbon solvent include aliphatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, -I-propylbenzene, and n-amylnaphthalene.

Among these organic solvents, an alcohol solvent, an ether solvent, a ketone solvent and an ester solvent are preferable. As the alcohol solvent, propylene glycol monomethyl ether is more preferable. As the ether solvent, diethylene glycol ethyl methyl ether Methyl ethyl ketone, cyclopentanone and cyclohexanone are more preferable as the ketone solvent, and examples of the ester solvent include ethyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, Ethyl acetate, and propylene glycol monomethyl ether acetate are more preferable.

The ratio of the solid content of the liquid crystal aligning agent, that is, the mass of all the components other than the solvent in the liquid crystal aligning agent, to the total mass of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., but is preferably 0.2 mass% % Is preferable. When the solid concentration is less than 0.2 mass%, the film thickness of the liquid crystal alignment film formed with the liquid crystal aligning agent becomes too small and a good liquid crystal alignment film may not be obtained. On the other hand, when the solid concentration exceeds 10% by mass, the film thickness of the coating film becomes excessively large, and a good liquid crystal alignment film may not be obtained. In addition, the viscosity of the liquid crystal aligning agent may increase and coating properties may be insufficient. The preferable range of the solid content concentration differs depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is preferably 1.5% by mass to 4.5% by mass. In the case of the printing method, it is preferable that the solid concentration is set in the range of 3 mass% to 9 mass%, and the solution viscosity is accordingly set in the range of 0.8 mPa · s to 50 mPa · s. In the case of the ink-jet method, it is preferable that the solid concentration is in the range of 1% by mass to 5% by mass, and the solution viscosity is accordingly set in the range of 0.8 mPa · s to 15 mPa · s.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film is formed of the liquid crystal aligning agent. Since the liquid crystal alignment film is formed of the liquid crystal aligning agent, the liquid crystal alignment film exhibits excellent liquid crystal alignability and is excellent in adhesion with the liquid crystal layer.

<Retardation film>

The retardation film includes the liquid crystal alignment film. Since the retardation film has the liquid crystal alignment film, the retardation film exhibits good liquid crystal alignability and is excellent in adhesion between the liquid crystal alignment film and the liquid crystal layer. Therefore, such a retardation film can be suitably used for a liquid crystal display element, particularly a liquid crystal display element for 3D image.

&Lt; Production method of retardation film >

The production method of the retardation film has the following steps.

The method for producing the retardation film includes:

(1) a step of forming a coating film on the substrate (hereinafter also referred to as &quot; step (1) &quot;) using the liquid crystal aligning agent,

(2) a step of forming a liquid crystal alignment film by irradiation of the coating film with radiation (hereinafter also referred to as &quot; process (2) &quot;),

(3) a step of forming a polymerizable liquid crystal film on the liquid crystal alignment film (hereinafter also referred to as &quot; step (3) &quot;) using a polymerizable liquid crystal,

(4) a step of curing the polymerizable liquid crystal film to form a liquid crystal layer (hereinafter also referred to as &quot; step (4) &quot;).

According to this production method, it is possible to produce a retardation film that exhibits good liquid crystal alignability and is excellent in adhesion between the liquid crystal alignment film and the liquid crystal layer. Hereinafter, each process will be described in detail.

[Step (1)]

In this step, a coating film is formed on the substrate by using the liquid crystal aligning agent. Examples of the application method include a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber doctor coater method, an offset gravure coater method, Three reverse roll coater methods, a four reverse roll coater method, a slot die method, an air doctor coater method, a forward rotation roll coater method, a blade coater method, a knife coater method, a reverse coater method using a small diameter gravure roll, , An impregnation coater method, an MB coater method, and an MB reverse coater method. Next, the coated surface is heat-treated to form a coated film. The temperature of the heat treatment is preferably 40 to 150 占 폚, more preferably 100 to 140 占 폚. The time for the heat treatment is preferably 0.1 minute to 15 minutes, more preferably 1 minute to 10 minutes. The film thickness of the coating film is preferably 1 nm to 1,000 nm, more preferably 5 nm to 500 nm.

Examples of the substrate include plastic substrates such as triacetylcellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, And a transparent substrate. In particular, TAC is generally used as a protective layer of a polarizing film which has an important function in an LCD. In most cases, the retardation film is used in combination with a polarizing film. It is necessary that the retardation film is precisely controlled to be bonded at an angle capable of exhibiting a desired optical characteristic with respect to the polarization axis of the polarizing film. Therefore, it is possible to form a liquid crystal alignment film capable of aligning the liquid crystal in an arbitrary direction on the TAC film by the photo alignment method, and to form a retardation film formed by applying and curing a polymerizable liquid crystal so as to exhibit desired optical properties , It is possible to omit the step of bonding the conventional polarizing film and the retardation film, thereby contributing to improvement of productivity. In addition, it contributes to the miniaturization and lightening of LCD materials, and can be applied to flexible displays and the like. However, since the TAC film is characterized by poor solvent resistance, the solvent that can be used for forming a photo alignment film is limited, and a solvent having high solubility such as NMP can not be used. In addition, the TAC film has a low heat resistance and is characterized in that it can not be processed at a high temperature for forming a photo alignment film.

The liquid crystal aligning agent can be used as a liquid crystal alignment film, for example, on an LCD component such as a color filter, on an optical film including a polarizing plate and a retardation film, and through a step (2) described below. Further, the liquid crystal aligning agent may be overlaid on the retardation film produced using the liquid crystal aligning agent, and the liquid crystal aligning agent may be used as a liquid crystal alignment film through the same process.

In applying the liquid crystal aligning agent, a functional silane compound, titanate, or the like may be previously coated on the substrate in order to further improve adhesion between the substrate and the coating film.

[Step (2)]

In this step, a liquid crystal alignment film is formed by irradiation of the coating film with radiation. Examples of the radiation include ultraviolet rays including visible light having a wavelength of 150 nm to 800 nm, visible rays, and the like. Of these, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferred. The radiation may be polarized light or unpolarized light. In the case of polarized light, it may be linearly polarized light or partially polarized light. In the present specification, &quot; unpolarized light &quot; means that some polarized light is included, but is included in &quot; unpolarized light &quot;

In the case of using radiation that is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed in an oblique direction to give a pretilt angle, or may be performed in combination good. In the case of irradiating non-polarized radiation, the irradiation direction needs to be an oblique direction. In the present specification, the term "pretilt angle" refers to the angle of inclination of the liquid crystal molecules from a direction parallel to the substrate surface.

Examples of the light source to be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). The linearly polarized light or the partially polarized ultraviolet light is obtained by a means for using the light source together with, for example, a filter, a diffraction grating or the like.

The dose of radiation is preferably from 0.1 mJ / cm 2 to 1,000 mJ / cm 2, more preferably from 1 mJ / cm 2 to 500 mJ / cm 2, and further preferably from 2 mJ / cm 2 to 200 mJ / cm 2. When a liquid crystal aligning ability is imparted to a coating film formed by a conventionally known liquid crystal aligning agent by a photo alignment method, a radiation dose of 1,000 mJ / cm 2 or more is required. When the liquid crystal aligning agent is used, / Cm &lt; 2 &gt;, and furthermore 200 mJ / cm &lt; 2 &gt; or less, good liquid crystal aligning ability can be imparted, contributing to reduction of manufacturing cost.

[Step (3)]

In this step, a polymerizable liquid crystal film is formed on the liquid crystal alignment film using a polymerizable liquid crystal. Examples of the method of applying the polymerizable liquid crystal include a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an ink jet method.

The polymerizable liquid crystal is not particularly limited as long as it is a liquid crystal compound which can be polymerized by heating and / or irradiation with radiation. For example, a nematic liquid crystal compound as described in UV curable liquid crystal and its application (see Liquid Crystal 3, No. 1, 1999, pages 34 to 42) may be used. A mixture may be used. In addition, a known photopolymerization initiator or a thermal polymerization initiator may be contained. These polymerizable liquid crystal compounds and mixtures thereof can be used by dissolving them in a suitable solvent. Further, by adding a chiral agent or the like, it is possible to use a liquid crystal in which the twisted nematic alignment is twisted in the direction perpendicular to the substrate, a cholesteric liquid crystal, or a discotic liquid crystal.

[Step (4)]

In this step, the solvent contained in the polymerizable liquid crystal is dried by heating and / or irradiation with radiation, and the polymerizable liquid crystal film is cured by polymerization to form a liquid crystal layer. The polymerization may be carried out under air or in an atmosphere of an inert gas such as nitrogen, and suitable conditions may be selected depending on the polymerizable group of the polymerizable liquid crystal to be used and the initiator. The thus obtained film can immobilize the liquid crystal layer in an intended orientation state and can be used as a retardation film.

As the temperature for heating the polymerizable liquid crystal, a temperature at which good orientation can be obtained is selected. For example, in the case of using the mercury-producing polymerizable liquid crystal, RMS03-013C, the heating temperature is selected in the range of 40 占 폚 to 80 占 폚.

Examples of the radiation when irradiating with radiation include ultraviolet rays of non-deflection. The irradiation dose of the radiation is preferably 50 mJ / cm 2 to 10,000 mJ / cm 2, more preferably 100 mJ / cm 2 to 5,000 mJ / cm 2.

As the film thickness of the liquid crystal layer, the film thickness at which desired optical characteristics are obtained is selected. For example, in the case of producing a 1/2 wave plate in a visible light having a wavelength of 540 nm, a film thickness such that the retardation of the formed retardation film becomes 240 nm to 300 nm is selected, If the film is a 1/4 wavelength plate, a film thickness such that the retardation becomes 120 nm to 150 nm is selected. The film thickness at which the aimed retardation is obtained differs depending on the optical characteristics of the polymerizable liquid crystal used. For example, when a polymerizable liquid crystal (RMS03-013C) produced by Merck is used, the film thickness for producing a 1/4 wavelength plate is selected in the range of 0.6 탆 to 1.5 탆.

<Liquid crystal display element>

The liquid crystal display element includes the retardation film. This liquid crystal display element is constituted by a liquid crystal cell, a polarizing plate, and the like which will be described later. Since the liquid crystal display element has the phase retardation film, the liquid crystal display element is excellent in liquid crystal alignability and the like.

The driving method of the liquid crystal display of the present invention is not particularly limited and the present invention can be applied to various known methods such as TN, STN, IPS, FFS, VA (including VA-MVA method and VA-PVA method) And the retardation film formed of the liquid crystal aligning agent. In general, a liquid crystal display element is provided with a pair of substrates on which a transparent electrode and a liquid crystal alignment film are laminated in this order, and the pair of substrates is disposed inside to face each other, and between the pair of substrates, And the periphery is sealed with a sealant.

<Manufacturing Method of Liquid Crystal Display Element>

Such a liquid crystal display element can be produced, for example, as follows. Two substrates on which the liquid crystal alignment film is formed are prepared, and a liquid crystal is arranged between the two substrates to manufacture a liquid crystal cell. To produce a liquid crystal cell, for example, the following two methods can be mentioned.

In a first method, two substrates are opposed to each other with an interval (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and peripheral portions of the two substrates are bonded using a sealant, The polymerizable liquid crystal is injected and filled in the cell gap defined by the liquid crystal cell, cured, and then the injection hole is sealed, whereby the liquid crystal cell can be manufactured.

The second method is a so-called ODF (One Drop Fill) method. For example, an ultraviolet curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and furthermore, the polymerizable liquid crystal is dropped on the liquid crystal alignment film surface, And then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.

In either case, it is preferable that the liquid crystal using the liquid crystal cell is heated to a temperature at which it takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation at the time of injection. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain the liquid crystal display element.

As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

As the polymerizable liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal and the like can be used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, it is preferable to have a positive dielectric anisotropy for forming a nematic liquid crystal. Examples of such polymerizable liquid crystals include biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane- Liquid crystal, quartz liquid crystal, and the like are used. Examples of the polymerizable liquid crystal include cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (manufactured by Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, or the like may be further added to the composition.

On the other hand, in the case of the vertical alignment type liquid crystal cell, it is preferable to have a negative dielectric anisotropy for forming a nematic liquid crystal. As such a polymerizable liquid crystal, for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a hepta base-based liquid crystal, an agar watch liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal and the like are used.

The polarizing plate used for the outside of the liquid crystal cell is not particularly limited, but a polarizing plate in which a polarizing film called &quot; H film &quot;, in which a polyvinyl alcohol film is oriented by stretching while iodine is absorbed is sandwiched by a cellulose acetate protective film or a polarizing plate And the like.

<Polymer>

The polymer is a polymer having a group containing a photo-alignable group and a polymerizable double bond. Since such a polymer has such groups in the same molecule, it can be suitably used, for example, as the [A] component of the liquid crystal aligning agent as described above.

The photo-orientable group is preferably a group containing a cinnamic acid structure. When the photo-orientable group is a group including a cinnamic acid structure, the liquid crystal alignment layer formed of the liquid crystal aligning agent has excellent photo-alignment property.

Further, the polymer is the same as the polymer having a group having a photo-orienting group and a polymerizable double bond in the same molecule in the description of the above-mentioned < [A] polymer component > .

(Example)

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. A method of measuring the physical property values is described below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)] [

Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.

Column: Toso Production TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

Standard material: monodisperse polystyrene

[Epoxy equivalent]

Was measured according to JIS C2105 &quot; hydrochloric acid-methyl ethyl ketone method &quot;.

[ ¹ H-NMR analysis]

^{The 1} H-NMR analysis was carried out using the magnetic resonance apparatus (JNM-ECX400P, manufactured by Nippon Denshi Co., Ltd.) under the conditions of measurement frequency: 400 MHz, measurement solvent: chloroform-d ₃ or DMSO-d ₆ .

&Lt; Synthesis of Component [A] >

(PA) having a group containing a polymerizable double bond and / or a photo-aligning group (hereinafter also referred to as a &quot; functional group &quot;) may be synthesized by synthesizing a cinnamic acid derivative and a polyorganosiloxane, Synthesized. Further, poly (meth) acrylates having a functional group and poly (meth) acrylates having no functional group were synthesized and used as poly (meth) acrylate (PB). The component (A) was prepared (synthesized) by using the polyorganosiloxane (PA) and the poly (meth) acrylate (PB). Further, by repeating the synthesis described below as necessary, the required amount of the compound used in each of the synthesis examples and examples was secured.

[Synthesis of cinnamic acid derivatives]

[Synthesis Example 1] (Synthesis of cinnamic acid derivative (C-1)

In a 500 mL three-necked flask equipped with a cooling tube, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were mixed. Then, 7 g of acrylic acid was added to the mixed solution with a cylinder, and the mixture was stirred and further heated and stirred at 120 캜 for 3 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Subsequently, the precipitate was separated by filtration, and the filtrate was poured into 300 mL of a 1N hydrochloric acid aqueous solution to recover the precipitate. These precipitates were recrystallized from a 1: 1 (by mass) solution of ethyl acetate and hexane to obtain 8.4 g of the cinnamic acid derivative (C-1) represented by the following formula.

[Synthesis Example 2] (Synthesis of cinnamic acid derivative (C-2)

In a 500 ml three-necked flask equipped with a condenser tube, 19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, Were mixed. Then, 7 g of acrylic acid was added to the mixed solution with a cylinder, and the mixture was stirred and further heated and stirred at 120 캜 for 3 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Subsequently, the precipitate was separated by filtration, and the filtrate was poured into 300 mL of a 1N hydrochloric acid aqueous solution to recover the precipitate. These precipitates were recrystallized from a 1: 1 (by mass) solution of ethyl acetate and hexane to obtain 10.2 g of the cinnamic acid derivative (C-2) represented by the following formula.

[Synthesis Example 3] (Synthesis of cinnamic acid derivative (C-3)) [

In a 500 mL three-necked flask equipped with a cooling tube, 20.1 g of p-bromobenzoic acid, 0.23 g of palladium acetate, 1.22 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were mixed. Then, 10.8 ml of methyl acrylate was added to the mixed solution, and the mixture was stirred with heating at 110 DEG C for 5 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Then, the reaction solution was further diluted with 1 L of ethyl acetate, and washed with 500 mL of water. This solution was concentrated and recrystallized with ethanol to obtain 15.2 g of the cinnamic acid derivative (C-3) represented by the following formula.

[Synthesis Example 4] (Synthesis of cinnamic acid derivative (C-4)

13.5 g of 5-bromo-2-methoxyphenol, 20 g of ethyl 6-bromohexanoate, 10.1 g of potassium carbonate and 120 mL of dimethylacetamide were mixed in a 500 mL three-necked flask equipped with a cooling tube. This mixed solution was heated and stirred at 100 占 폚 for 6 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Then, the reaction solution was further diluted with 250 mL of ethyl acetate and washed with 375 mL of water. This reaction solution was concentrated, 35 mL of a 4N aqueous sodium hydroxide solution was added, and further 35 mL of ethanol was added. This mixed solution was heated and stirred at 60 占 폚 for 1 hour. After the reaction solution was allowed to cool to room temperature, 250 mL of ethyl acetate was added, and the mixture was washed with 125 mL of 1N hydrochloric acid aqueous solution and further washed with 375 mL of water. This solution was concentrated and recrystallized from a 1: 1 (by mass) solution of ethyl acetate and hexane to obtain an intermediate compound.

Thereafter, 31.7 g of the intermediate compound, 0.23 g of palladium acetate, 1.22 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were mixed in a 500 mL three-necked flask equipped with a cooling tube . Then, 10.8 ml of methyl acrylate was added to the mixed solution, and the mixture was stirred with heating at 110 DEG C for 5 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Then, the reaction solution was further diluted with 1 L of ethyl acetate, and washed with 500 mL of water. This solution was concentrated and recrystallized with ethanol to obtain 17.6 g of the cinnamic acid derivative (C-4) represented by the following formula.

[Synthesis Example 5] (Synthesis of cinnamic acid derivative (C-5)) [

In a 500 mL three-necked flask equipped with a cooling tube, 17.6 g of the cinnamic acid derivative (C-4) obtained in Synthesis Example 4, 7.88 g of glycidyl methacrylate, 0.78 g of tetrabutylammonium bromide and 0.35 g of propylene glycol monomethyl ether acetate Were mixed. Subsequently, this mixed solution was further heated and stirred at 90 占 폚 for 7 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. The reaction solution was washed with 300 mL of water and then concentrated to obtain 56.6 g of a solution containing the cinnamic acid derivative (C-5) represented by the following formula.

[Synthesis of polyorganosiloxane]

[Synthesis Example 6] (Synthesis of polyorganosiloxane (POS-1)

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, And mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane (POS-1) As a viscous transparent liquid.

The polyorganosiloxane (POS-1) was subjected to ¹ H-NMR analysis. As a result, a peak based on the oxiranyl group was obtained near the chemical shift (?) = 3.2 ppm as the theoretical intensity, It was confirmed that this did not happen.

The polyorganosiloxane (POS-1) had an Mw of 2,200 and an epoxy equivalent of 186.

[Synthesis Example 7] (Synthesis of polyorganosiloxane (POS-2)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube, 80.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 80.0 g of 3- (methacryloyloxy) propyltrimethoxysilane , 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed and mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane (POS-2) As a viscous transparent liquid. As a result of ¹ H-NMR analysis in the same manner as in Synthesis Example 6, it was confirmed that a side reaction of the epoxy group did not occur during the reaction. The polyorganosiloxane (POS-2) had an Mw of 2,400 and an epoxy equivalent of 184. Further, the polyorganosiloxane (POS-2) has a group containing a polymerizable double bond derived from 3- (methacryloyloxy) propyltrimethoxysilane.

[Synthesis Example 8] (Synthesis of polyorganosiloxane (POS-3)

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 70.5 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol, Were added and mixed at room temperature. Subsequently, 70.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 2 hours while stirring under reflux. Triethylamine and water were distilled off by repeating the operation of concentrating the reaction solution and diluting with butyl acetate twice to obtain a polymer solution containing polyorganosiloxane (POS-3). As a result of ¹ H-NMR analysis in the same manner as in Synthesis Example 6, it was confirmed that a side reaction of the epoxy group did not occur during the reaction. The polyorganosiloxane (POS-3) had an Mw of 11,000 and an epoxy equivalent of 182.

[Synthesis of polyorganosiloxane (PA)

[Synthesis Example 9] (Synthesis of polyorganosiloxane (PA-1)

9.3 g of the polyorganosiloxane (POS-1) having an epoxy group obtained in Synthesis Example 6, 26 g of methyl isobutyl ketone, 3 g of the cinnamic acid derivative (C-1) obtained in Synthesis Example 1 and 3 g of tetrabutyl 0.93 g of ammonium bromide was added, and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, the mixture was diluted with 100 g of butyl acetate and the mixture was washed three times with water. This solution was concentrated and diluted with butyl acetate was repeated twice to finally obtain a solution containing a polyorganosiloxane (PA-1) having a photo-aligning group. The weight average molecular weight Mw of the polyorganosiloxane (PA-1) was 3,500.

[Examples 1 to 5 and Synthesis Examples 10 to 12] (Synthesis of polyorganosiloxanes (PA-2) to (PA-8)

(PA-2) to (PA-2) were obtained in the same manner as in Synthesis Example 9, except that the types and blending amounts of the compound giving photo-aligning group and the group giving polymerizable double bond- (PA-9) was synthesized. In Table 1, "-" indicates that the corresponding components are not blended. In Table 1, M-1 to M-3 each represent an acryloyl group-containing carboxylic acid, M-1 is Aronix M-5300 (manufactured by Toagosei Co.) (Manufactured by Kyoeisha Kagaku), and M-3 represents Aronix M-510 (manufactured by Toagosei Co., Ltd.).

[Synthesis of poly (meth) acrylate (PB)] [

[Synthesis Example 13] (Synthesis of poly (meth) acrylate (PB-1)

In a flask equipped with a cooling tube and a stirrer, 3 parts by mass of 2,2'-azobis (isobutyronitrile) as a polymerization initiator, 1 part by mass of 2,4-diphenyl-4-methyl- , And 180 parts by mass of diethylene glycol methyl ethyl ether as a solvent. Subsequently, 30 parts by mass of glycidyl methacrylate, 50 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, and 20 parts by mass of tetrahydrofurfuryl methacrylate were added, and after nitrogen replacement, stirring was gently started . The solution temperature was raised to 80 占 폚, and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate (PB-1). The solid concentration of the obtained polymer solution was 33.1 mass%. The Mn of the obtained polymer was 7,000.

[Synthesis Example 14] (Synthesis of poly (meth) acrylate (PB-2)

A flask equipped with a cooling tube and a stirrer was charged with 1 part by mass of 2,2'-azobis (isobutyronitrile) as a polymerization initiator and 180 parts by mass of diethylene glycol methyl ethyl ether as a solvent. Subsequently, 70 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate and 30 parts by mass of 3-methyl-3-oxetanylmethyl methacrylate were added and replaced with nitrogen, and stirring was started gently. The solution temperature was raised to 80 占 폚 and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate (PB-2). The solid concentration of the obtained polymer solution was 32.8 mass%. The Mn of the obtained polymer was 16,000.

[Synthesis Example 15] (Synthesis of poly (meth) acrylate (PB-3)

1 part by mass of 2,2'-azobis (isobutyronitrile) as a polymerization initiator and 270 parts by mass of diethylene glycol methyl ethyl ether as a solvent were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 100 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate was added, and after nitrogen replacement, stirring was gently started. The solution temperature was raised to 80 占 폚 and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate (PB-3). The solid concentration of the obtained polymer solution was 32.8 mass%. The Mn of the obtained polymer was 14,000.

[Synthesis Example 16] (Synthesis of poly (meth) acrylate (PB-4)

100 parts by mass of the poly (meth) acrylate (PB-2) obtained in Synthesis Example 14, 20 parts by mass of acryloyl group-containing carbonic acid (Aronix M-5300, Toagosei Co.), 10 parts by mass of tetrabutylammonium bromide And 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and the mixture was stirred at 90 占 폚 for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated twice to finally obtain a polymer solution containing poly (meth) acrylate (PB-4).

[Synthesis Example 17] (Synthesis of poly (meth) acrylate (PB-5)

100 parts by mass of the poly (meth) acrylate (PB-2) obtained in Synthesis Example 14, 20 parts by mass of acryloyl group-containing carbonic acid (Aronix M-5300, Toagosei Co.), 10 parts by mass of tetrabutylammonium bromide And 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent were added thereto, and the mixture was stirred at 90 占 폚 for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated twice to finally obtain a polymer solution containing poly (meth) acrylate (PB-5).

[Synthesis Example 18] (Synthesis of poly (meth) acrylate (PB-6)

100 parts by mass of the poly (meth) acrylate (PB-2) obtained in Synthesis Example 14, 20 parts by mass of methacrylic acid, 10 parts by mass of tetrabutylammonium bromide as a catalyst, and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent, And the mixture was stirred under nitrogen atmosphere at 90 占 폚 for 12 hours. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated twice to finally obtain a polymer solution containing poly (meth) acrylate (PB-6).

[Example 6] (Synthesis of poly (meth) acrylate (PB-7)

100 parts by mass of the poly (meth) acrylate (PB-3) obtained in Synthesis Example 15, 20 parts by mass of an acryloyl group-containing carbonic acid (Aronix M-5300, Toagosei), a cinnamic acid derivative C-3), 10 parts by mass of tetrabutylammonium bromide as a catalyst and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent were placed and stirred at 90 ° C for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated twice to finally obtain a polymer solution containing poly (meth) acrylate (PB-7).

[Example 7] (Synthesis of poly (meth) acrylate (PB-8)) [

5 parts by mass of 2,2'-azobis (isobutyronitrile) as a polymerization initiator and 270 parts by mass of diethylene glycol methyl ethyl ether as a solvent were placed in a flask equipped with a cooling tube and a stirrer. 80 parts by mass of the cinnamic acid derivative (C-5) obtained in Synthetic Example 5 and 20 parts by mass of methacrylic acid were charged, and after nitrogen replacement, stirring was gently started. The solution temperature was raised to 80 占 폚, and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate. Subsequently, 100 parts by mass of the obtained poly (meth) acrylate, 20 parts by mass of glycidyl methacrylate, 10 parts by mass of tetrabutylammonium bromide as a catalyst, and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent were placed, C &lt; / RTI &gt; for 12 hours. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated twice to finally obtain a polymer solution containing poly (meth) acrylate (PB-8).

[Synthesis of other polymer (PC)

[Example 8] (Synthesis of other polymer (PC-1)) [

100 parts by mass of EHPE3150 (Daicel Corporation) having a structural unit represented by the following formula, 25 parts by mass of the cinnamic acid derivative (C-5) obtained in Synthetic Example 5, 10 parts by mass of acryloyl group-containing carbonic acid (Aronix M- , 10 parts by mass of tetrabutylammonium bromide as a catalyst and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent were placed and stirred at 90 占 폚 for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated two times to finally obtain a polymer solution containing the polymer (PC-1).

[Example 9] (Synthesis of other polymer (PC-2)) [

100 parts by mass of JP200 (Nippon Soda Co., Ltd.) having a structural unit represented by the following formula, 25 parts by mass of the cinnamic acid derivative (C-5) obtained in Synthetic Example 5, 10 parts by mass of acryloyl group-containing carbonic acid (Aronix M- 10 parts by mass of tetrabutylammonium bromide as a catalyst and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent were placed and stirred at 90 占 폚 for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated two times to finally obtain a polymer solution containing the polymer (PC-2).

[Example 10] (Synthesis of other polymer (PC-3)) [

100 parts by mass of HP7200 (DIC Corporation) having structural units represented by the following formulas, 25 parts by mass of the cinnamic acid derivative (C-5) obtained in Synthetic Example 5, 100 parts by mass of acryloyl group-containing carbonic acid (Aronix M- 10 parts by mass of tetrabutylammonium bromide as a catalyst and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent were placed and stirred at 90 占 폚 for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was subjected to three times water washing. This solution was concentrated and diluted with butyl acetate was repeated two times to finally obtain a polymer solution containing the polymer (PC-3).

&Lt; Preparation of liquid crystal aligning agent &

[B] Metal chelate compounds, curing accelerators and solvents used for the preparation of liquid crystal aligning agents are shown below.

[[B] metal chelate compound]

B-1: Tris (acetylacetonate) aluminum (aluminum chelate A (W), manufactured by Kawaken Fine Chemicals)

[Curing accelerator]

K-1: tri (p-tolyl) silanol

K-2: San-Aid SI-60 (SANSHIN KAGAKU KOGYO Co., Ltd.)

[menstruum]

BA: n-butyl acetate

IBA: isobutyl acetate

MEK: methyl ethyl ketone

PGMEA: Propylene glycol monomethyl ether acetate

EA: Ethyl acetate

EAA: ethyl acetoacetate

EDM: diethylene glycol ethyl methyl ether

CHN: cyclohexanone

CPN: cyclopentanone

PGME: Propylene glycol monomethyl ether

[Example 11]

(PA-1) obtained in Synthesis Example 9, as the component (A), in an amount corresponding to 15 parts by mass in terms of (PA-1) (B-1) as a metal chelate compound and 40 parts by mass of (K-1) as a curing accelerator were mixed in an amount corresponding to 85 parts by mass of the (PB-6) BA, MEK and PGMEA (mass ratio of each solvent: 65:25:10) as a solvent were added to obtain a solution having a solid concentration of 2.5% by mass. Subsequently, this obtained solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (A-1).

[Examples 12 to 22 and Comparative Examples 1 to 3]

(A-2) to (A-12) and (a-1) to (a-2) were obtained by operating in the same manner as in Example 11, 3) was prepared. In Table 2, &quot; - &quot; indicates that the corresponding components are not blended.

&Lt; Formation of liquid crystal alignment film and production of retardation film &

[Example 23]

A liquid crystal aligning agent (A-1) prepared in Example 11 was coated on one surface of a TAC film as a substrate using a bar coater and baked at 120 DEG C for 2 minutes in an oven to form a 100 nm thick coating film. Subsequently, a 10 mJ / cm 2 polarized ultraviolet ray including a bright line of 313 nm was vertically irradiated from the substrate normal to the surface of the coating film using an Hg-Xe lamp and a Glane Taylor prism to form a liquid crystal alignment film Quot; polarized ultraviolet ray irradiation A &quot;). Subsequently, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered with a filter having a pore size of 0.2 mu m, and then a polymerizable liquid crystal film was formed on the liquid crystal alignment film using a bar coater. After baking in one oven for one minute, 1,000 mJ / cm 2 of unpolarized ultraviolet light including a bright line of 365 nm was irradiated to the polymerizable liquid crystal film by using a He-Xe lamp to produce a retardation film.

[Examples 24 to 34 and Comparative Examples 4 to 6]

(A-2) to (A-12) and (a-1) to (a-3) were used as the liquid crystal aligning agent and Example 31 was a liquid crystal alignment film 23, the retardation films of Examples 24 to 34 and Comparative Examples 4 to 6 were produced.

<Evaluation>

The retardation films prepared above were evaluated by the following method. The evaluation results are shown in Table 3.

[Liquid crystal alignment property (1)]

For each of the retardation films, the alignment properties were observed by visual observation under a cross-nicol and a polarizing microscope. The liquid crystal alignability (1) is excellent (good) "A" when the naked eye has good orientation and the liquid crystal orientation is good when viewed from the naked eye. However, when the polarized light microscope is used, When the abnormal domain was observed, the liquid crystal alignability (1) was evaluated as good "B", and when the liquid crystal alignability was visually observed, the liquid crystal alignability (1) was evaluated as bad "C".

[Liquid crystal alignment property (2)]

Each of the retardation films was produced in the same manner as in Examples 23 to 34 and Comparative Examples 4 to 6 except that the conditions of the polarizing ultraviolet irradiation A were changed to 100 mJ / cm 2, and evaluation methods of the liquid crystal alignability (1) To evaluate the liquid crystal alignment properties.

[Adhesion]

Using an equal interval spacer with a guide, an incision was made at intervals of 1 mm on each retardation film with a cutter knife to form a grid pattern of 10 10. Subsequently, the cellophane tape was brought into close contact with the grid pattern, and then the cellophane tape was peeled from the grid pattern. When the cut-out portion of the grid pattern after peeling the cellophane tape was observed and no peeling was observed along the cut-off line or the intersection of the grid pattern, the adhesion was evaluated as good "A" Quot; B &quot; when the number of the grid patterns is less than 15%, and the defective &quot; C &quot;

As is evident from the results in Table 3, the retardation film of the Examples had good adhesion, and when the polarizing ultraviolet radiation dose was increased to at least 100 mJ / cm 2 (see evaluation results of liquid crystal alignability (2)), In contrast, in the comparative example, when the irradiation amount of the polarized ultraviolet ray was increased to 100 mJ / cm 2, the liquid crystal alignability was poor or the adhesion was poor.

Since the liquid crystal aligning agent and the polymer of the present invention have a group containing a photo-aligning group and a polymerizable double bond in a component such as a polymer, a liquid crystal alignment film exhibiting good liquid crystal alignability and excellent adhesion to the liquid crystal layer is formed . Therefore, the present invention can provide a retardation film having a liquid crystal alignment film that exhibits good liquid crystal alignability and excellent adhesion to the liquid crystal layer, a method for producing the same, and a liquid crystal display device comprising the retardation film.

Claims (13)

A liquid crystal composition comprising a polyorganosiloxane having at least one of a group containing a polymerizable double bond and a photo-aligning group, a liquid crystal containing a poly (meth) acrylate having at least one of a group containing a polymerizable double bond and a photo- (Wherein the liquid crystal aligning agent has at least one group each containing a polymerizable double bond and at least one photo-orientable group). delete delete The method according to claim 1,
Wherein the photo-orientable group is a group containing a cinnamic acid structure. The method according to claim 1,
Wherein the group containing the polymerizable double bond is a (meth) acryloyl group. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1, 4 and 5. A retardation film comprising the liquid crystal alignment film according to claim 6. 8. The method of claim 7,
A retardation film used in a liquid crystal display device. A liquid crystal display element comprising the retardation film according to claim 8. A method for manufacturing a liquid crystal display device, comprising the steps of forming a coating film on a substrate using the liquid crystal aligning agent according to any one of claims 1, 4, and 5,
A step of forming a liquid crystal alignment film by irradiation of the coating film with radiation,
A step of forming a polymerizable liquid crystal film on the liquid crystal alignment film using a polymerizable liquid crystal,
And a step of curing the polymerizable liquid crystal film to form a liquid crystal layer. delete delete delete