JP2014026261A - Liquid crystal aligning agent, liquid crystal aligned layer, retardation film, method for manufacturing retardation film, liquid crystal display element, and polymer - Google Patents

Abstract

A liquid crystal alignment agent capable of forming a liquid crystal alignment film exhibiting good liquid crystal alignment properties and excellent adhesion to a liquid crystal layer, a liquid crystal alignment film formed from the liquid crystal alignment agent, and a position including the liquid crystal alignment film It aims at providing the polymer which is a suitable component of a phase difference film, its manufacturing method, a liquid crystal display element provided with the said phase difference film, and the said liquid crystal aligning agent.
The liquid crystal aligning agent of the present invention contains [A] a component having a photoalignable 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-alignment 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 alignment agent. The retardation film of the present invention includes the liquid crystal alignment film. The retardation film is preferably used for a liquid crystal display element. The liquid crystal display element of the present invention includes the retardation film.
[Selection figure] None

Description

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

  Liquid crystal displays (LCDs) are widely used for televisions and various monitors. Examples of LCD display elements include STN (Super Twisted Nematic), TN (Twisted Nematic), IPS (In Plane Switching), VA (Vertically Aligned), and PSA (Polymer Sustained). (See Japanese Patent Laid-Open Nos. 56-91277 and 1-120528). Various optical materials are used for the liquid crystal display element. For example, the retardation film provided in the liquid crystal display element changes in display color and contrast ratio depending on the purpose of eliminating the coloring of the display image and the viewing angle. Is used for the purpose of eliminating the viewing angle dependency (refer to Japanese Patent Laid-Open Nos. 4-229828 and 4-258923).

  As a method for producing the retardation film, a roll-to-roll method is known in which a retardation film is continuously produced on a long base film (see JP 2000-86786 A). In this roll-to-roll method, a liquid crystal alignment film is formed on a substrate film using a liquid crystal alignment agent, and then a polymerizable liquid crystal is applied on the formed liquid crystal alignment film, and the polymerizable liquid crystal is applied by light irradiation. Curing is performed to form a liquid crystal layer.

  However, when a 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, and is included in, for example, the production by the roll-to-roll method. The liquid crystal layer may be peeled off in the step of winding the retardation film.

JP 56-91277 A JP-A-1-120528 JP-A-4-229828 JP-A-4-258923 JP 2000-86786 A

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

The invention made to solve the above problems is
[A] A liquid crystal aligning agent containing a component having a photoalignable group and a group containing a polymerizable double bond in the same or different molecules (hereinafter also referred to as “[A] component”).

Another invention made to solve the above problems is as follows:
A liquid crystal alignment film formed from the liquid crystal alignment agent;
Retardation film comprising the liquid crystal alignment film,
A liquid crystal display device comprising the retardation film, and a polymer having a photo-alignable group and a group containing a polymerizable double bond.

Another invention made to solve the above problems is as follows:
(1) A step of forming a coating film on a substrate using the liquid crystal aligning agent,
(2) A step of forming a liquid crystal alignment film by irradiating the coating film with radiation,
(3) A step of forming a polymerizable liquid crystal film on the liquid crystal alignment film using a polymerizable liquid crystal, and (4) a retardation film having a step of curing the polymerizable liquid crystal film to form a liquid crystal layer. Is the method.

  Here, the polymerizable double bond refers to a double bond that can easily form a radical and perform a growth reaction. Examples of the polymerizable double bond include a terminal double bond.

  Since the liquid crystal aligning agent and polymer of the present invention have a photo-alignable group and a group containing a polymerizable double bond in a component such as a polymer, the liquid crystal aligning agent and the polymer exhibit good liquid crystal alignment and are in close contact with the liquid crystal layer. A liquid crystal alignment film having excellent properties can be formed. Therefore, the present invention provides a retardation film including a liquid crystal alignment film that exhibits good liquid crystal alignment and excellent adhesion to a liquid crystal layer, a method for producing the same, and a liquid crystal display element including the retardation film. Can contribute to quality improvement.

<Liquid crystal aligning agent>
The liquid crystal aligning agent contains the [A] component. In addition, the liquid crystal aligning agent may contain optional components such as [B] metal chelate compound, curing accelerator, and surfactant, as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] component>
The component [A] is a component having a photoalignable group and a group containing a polymerizable double bond in the same or different molecules. The liquid crystal aligning film formed from the said liquid crystal aligning agent because the said liquid crystal aligning agent contains a [A] component shows favorable liquid crystal aligning property, and is excellent in adhesiveness with a liquid crystal layer. This is considered to be because the interaction between the liquid crystal alignment film and the liquid crystal layer is strengthened by forming a cross-linked structure by the polymerizable double bond contained in the molecule.

  As the component (A), (1) one having a photo-alignable group and a group containing a polymerizable double bond in the same molecule, (2) a group containing a polymerizable double bond in a different molecule and photo-alignment And those having a group separately.

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

[Group containing 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 said liquid crystal aligning agent can improve the adhesiveness of a liquid crystal aligning film and a liquid-crystal layer because [A] component has group containing a polymerizable double bond.

  The polymerizable double bond is preferably a carbon-carbon double bond. Examples of the group containing a carbon-carbon double bond include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

  When the component [A] is a polymer component, examples of the group containing a polymerizable double bond include a reaction for adding a carboxy group to an epoxy group (hereinafter also referred to as “addition reaction”), and an isocyanate group for a hydroxy group. It can be introduced into the polymer component [A] by utilizing a reaction added to an amino group, a carboxy group or a thiol group. Each of the above groups used for the addition reaction may be on the polymer side or on the compound side to be added to the polymer. In addition, a reaction of adding a hydroxy group to —COCl can be used, but in this case, from the viewpoint of ease of introduction, the hydroxy group is on the polymer side, and —COCl is on the compound side to be added to the polymer. Is preferred. When utilizing these addition reactions, the compound added to the polymer usually has a group containing the polymerizable double bond. Among these, 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 carboxy group and a compound having an epoxy group, which are used for the addition reaction upon introduction of a group containing a polymerizable double bond, will be described.

  Examples of the compound having a polymerizable double bond and a carboxy group (including a polyvalent carboxylic acid anhydride having a polymerizable double bond) (hereinafter also referred to as “unsaturated compound (a)”) include (meth) Acrylic acid, (meth) acrylic acid ω-carboxypolycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid Unsaturated carboxylic acids such as itaconic acid; unsaturated polycarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride, etc. Can be mentioned. Among these, (meth) acrylic acid and (meth) acrylic acid ω-carboxypolycaprolactone are preferable.

  Examples of commercially available unsaturated compounds (a) include Aronix M-510, Aronix M-5300 (manufactured by Toagosei Co., Ltd.), and light ester HOMS (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the compound having a polymerizable double bond and an epoxy group (excluding the unsaturated compound (a)) (hereinafter also referred to as “unsaturated compound (b)”) include, for example, glycidyl (meth) acrylate, α- Glycidyl ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl α-ethyl acrylate, (meth) 3,4-epoxycyclohexylmethyl acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, α-ethyl acrylate 6,7-epoxyheptyl, acrylic acid Examples include 4-hydroxybutyl glycidyl ether. Of these, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, and 4-hydroxybutyl glycidyl ether acrylate are preferred.

  In the case where polysiloxane is contained as the polymer component [A], the group containing a polymer double bond can be introduced by a silane compound having a group containing a polymerizable double bond described later.

  You may use the compound which gives the group containing the said polymeric double bond individually or in combination of 2 or more types. Moreover, these compounds can also be used as one of [A] component as it is.

  When the component [A] is a non-polymer component, the group containing a polymerizable double bond is, for example, a non-polymer compound having a carboxy group as in the case where the component [A] is a polymer component. The epoxy group can be introduced into the [A] non-polymer component by utilizing a reaction of adding an isocyanate group to a hydroxy group, an amino group, a carboxy group, or a thiol group. Each of the above-described groups subjected to the addition reaction may be on the non-polymer compound side or on the compound side to be added to the non-polymer compound. In addition, a reaction of adding a hydroxy group to —COCl can be used. In this case, from the viewpoint of ease of introduction, a compound in which a hydroxy group is added to the non-polymer compound side and —COCl is added to the non-polymer compound. Preferably it is on the side. When utilizing these addition reactions, the compound added to the non-polymerizable compound usually has a group containing the polymerizable double bond. Among these, 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 for the addition reaction upon introduction of a group containing a polymerizable double bond include those represented by the following formula.

  Examples of commercially available compounds having an epoxy group represented by the above formula include TETRAD-X (manufactured by Mitsubishi Gas Chemical), Celoxide 2021P (manufactured by Daicel), EX-850L (manufactured by Nagase ChemteX), TETRAD-C ( Mitsubishi Gas Chemical).

[Photo-alignment group]
The photo-alignment group is a functional group that can impart anisotropy to the film by light irradiation. This anisotropy is imparted by a photoisomerization reaction or a photodimerization reaction. When the [A] component of the liquid crystal aligning agent has a photo-alignment group, photo-alignment can be imparted to the formed liquid crystal alignment film.

  As the photoalignable group, groups derived from various compounds exhibiting photoalignment can be employed. For example, a group containing 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 cinnamic acid structure, a group containing a chalcone structure containing a chalcone 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, a coumarin or a derivative thereof as a basic skeleton Examples thereof include a group containing a coumarin structure and a group containing a polyimide structure containing polyimide or a derivative thereof as a basic skeleton. Among these, a group including a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable from the viewpoint of excellent photoalignment and ease of introduction of the above group. In the liquid crystal alignment film, the photo-alignment group is a group including a cinnamic acid structure, and thus exhibits good photo-alignment by irradiation with polarized ultraviolet rays.

  The structure of the group containing 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 preferred.

  The method for synthesizing the cinnamic acid and cinnamic acid derivative is not particularly limited, and can be performed by combining known methods. As a typical synthesis method, for example, a method of reacting a compound having a benzene ring skeleton substituted with a halogen atom with acrylic acid or a derivative thereof in the presence of a transition metal catalyst under basic conditions; And a method of reacting cinnamic acid in which a hydrogen atom of a benzene ring is substituted with a halogen atom and a compound having a benzene ring skeleton substituted with a halogen atom in the presence of a transition metal catalyst.

  In addition, although it is preferable to use the compound which gives a photo-alignment group as a raw material of the below-mentioned [A] polymer component or [A] non-polymer component, it can also be used as it is as one of [A] components. In these cases, the compound that gives the photo-alignment group may be used alone or in combination of two or more.

  Examples of the raw material for the non-polymer component that gives the photo-alignment group include the same compounds as those having an epoxy group used when introducing a group containing a polymerizable double bond into the non-polymer compound. it can.

<[A] Polymer component>
[A] The polymer component is a polymer component having a photoalignable group and a group containing a polymerizable double bond in the same or different polymers. [A] The polymer component 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 a mixture thereof is more preferable. In particular, the polysiloxane having a photo-alignment group exhibits excellent photo-alignment, and the (meth) acrylic polymer can enhance the adhesion with the liquid crystal layer. “A” The polymer component may be other polymers such as polyether, vinyl polymer, aromatic ring-containing polymer (hereinafter, these are collectively referred to as “other polymers”). Hereinafter, the polysiloxane having the specific group, the (meth) acrylic polymer, and other polymers will be described.

[Polysiloxane]
[A] The polysiloxane constituting the polymer component is not particularly limited as long as it has a group containing a polymerizable double bond and / or a photoalignment group.
(P1) a silane compound containing an epoxy group (hereinafter also referred to as “silane compound (a)”) and a silane compound having a group containing a polymerizable double bond (hereinafter also referred to as “silane compound (b)”); A silane compound (hereinafter also referred to as “silane compound (c)”) that is different from both the silane compound (a) and the silane compound (b), if necessary, in an appropriate organic solvent in the presence of water and a catalyst. A method of reacting a carboxylic acid compound that undergoes hydrolytic condensation and further gives a photo-alignment group,
(P2) The silane compound (a) and, if necessary, the silane compound (b) or the silane compound (c) are hydrolyzed and condensed in an appropriate organic solvent in the presence of water and a catalyst, and then further polymerized. It can be synthesized by a method of reacting a carboxylic acid compound that gives a group containing an ionic double bond and / or a carboxylic acid compound that gives a photo-alignment group. 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-glycidyloxypropylmethyldiethoxysilane, 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, and 3- (methacryloyloxy) propyl. Examples include methyldiethoxysilane. Of these, 3- (methacryloyloxy) propyltrimethoxysilane is preferred.

As the silane compound (c), for example,
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane and the like;
Methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert -Butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, hexamethylenebi (Trimethoxysilane), 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane and the like;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, etc .;
Examples include trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane.
Of these, tetramethoxysilane and tetraethoxysilane are preferred.

  The carboxylic acid compound that gives a group containing a polymerizable double bond and the carboxylic acid compound that gives a photo-alignable group are unsaturated compounds (a) and [photo-alignment] of [group containing a polymerizable double bond], respectively. Among the compounds having a photoalignable group described in the section “Group”, a carboxylic acid compound can be applied.

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

  As reaction temperature at the time of synthesize | combining polysiloxane, 0 to 100 degreeC is preferable and 15 to 90 degreeC is more preferable. The reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 8 hours.

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

[(Meth) acrylic polymer]
[A] The (meth) acrylic polymer constituting the polymer component is not particularly limited as long as it has a group containing a polymerizable double bond and / or a photoalignment group. For example, the following method (M1) or ( M2) or the like.
(M1) A polymer is synthesized by, for example, radical polymerization 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)”) and a polymerization initiator. Then, the polymer is converted into the unsaturated compound (a) and / or photo-alignment group in a suitable organic solvent (hereinafter also referred to as “organic solvent (b2)”), preferably in the presence of a catalyst. (M2) (Meth) acrylic acid and a polymerizable compound giving a photoalignable group are subjected to radical polymerization, for example, in the presence of a suitable organic solvent (b1) and a polymerization initiator. A method of reacting the copolymer with the unsaturated compound (b) in a suitable organic solvent (b2), preferably in the presence of a catalyst.

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

  As the carboxylic acid compound that gives the photo-alignment group, a carboxylic acid compound among the compounds having the photo-alignment group described in the section [Photo-alignment group] can be used.

  Examples of the polymerizable compound that gives the photoalignable group include compounds having a photoalignable group and a polymerizable double bond.

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

As the polymerization initiator, for example,
2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. An azo compound;
Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis (t-butylperoxy) cyclohexane;
hydrogen peroxide;
Examples thereof include a redox initiator composed of 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 the same solvents as those exemplified as the organic solvent (b1). Of these, ester organic solvents are 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.

Examples of the catalyst include:
Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methyl] An imidazole compound such as an isocyanuric acid adduct of Louis-imidazolyl- (1 ′)] ethyl-s-triazine;
Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra Phenylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate Quaternary phosphonium salts bets like;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent catalyst such as dicyandiamide or amine addition accelerator such as adduct of amine and epoxy resin;
A microcapsule type latent catalyst in which the 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;
Examples include latent catalysts such as high temperature dissociation type thermal cationic polymerization latent catalysts such as Lewis acid salts and Bronsted acid salts.
These catalysts may be used alone or in combination of two or more.

  Of these catalysts, quaternary ammonium salts are preferred, and tetrabutylammonium bromide is more preferred.

  As the usage-amount of the said catalyst, 100 mass parts or less are preferable with respect to 100 mass parts of polymers, 0.01 mass part-100 mass parts are more preferable, 0.1 mass part-20 mass parts are more preferable.

  As reaction temperature, 0 degreeC-200 degreeC are preferable, and 50 degreeC-150 degreeC is more preferable. As reaction time, 0.1 hour-50 hours are preferable, and 0.5 hour-20 hours are more preferable.

  [A] 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 from 250 to 500,000, more preferably from 500 to 100,000. More preferred is 1,000 to 50,000. When Mn is in the above range, it is possible to ensure good photo-alignment and stability of the liquid crystal alignment film formed from 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 photoalignment group, except for polysiloxane and (meth) acrylic polymer. For example, from the corresponding epoxy-containing compound, It can be synthesized by the following method.

  The other polymer may convert the epoxy group-containing compound into an epoxy group by providing the unsaturated compound (a) and / or the carboxylic acid compound that provides the photoalignable group in an appropriate organic solvent, preferably in the presence of a catalyst. It can be synthesized by the method of adding.

  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 to which a photoalignable group can be added. For example, a polymer having a structural unit represented by the following formula Etc.

  As a commercial item of the polymer which has a structural unit represented by the said formula, EHPE3150 (made by Daicel), JP200 (made by Nippon Soda), HP7200 (made by DIC) etc. are mentioned, for example.

  As said organic solvent, the solvent similar to the solvent illustrated as said organic solvent (b1) etc. are mentioned, for example. Of these, ester organic solvents are 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 said catalyst, the catalyst similar to the catalyst illustrated in the synthesis method of [(meth) acrylic polymer] is mentioned, for example. Of these, quaternary ammonium salts are preferred, and tetrabutylammonium bromide is more preferred.

  As the usage-amount of the said catalyst, 100 mass parts or less are preferable with respect to 100 mass parts of polymers, 0.01 mass part-100 mass parts are more preferable, 0.1 mass part-20 mass parts are more preferable.

  As reaction temperature, 0 degreeC-200 degreeC are preferable, and 50 degreeC-150 degreeC is more preferable. As reaction time, 0.1 hour-50 hours are preferable, and 0.5 hour-20 hours are more preferable.

  As content of [A] component, 50 mass% or more is preferable with respect to the total solid of the said liquid crystal aligning agent, and 60 mass% or more is more preferable.

<[B] Metal chelate compound>
[B] The metal chelate compound 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 by heat treatment at a low temperature for a short time. The liquid crystal aligning agent preferably contains a [B] metal chelate compound.

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

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

In the above formula ^{(2-1) ~ (2-3),} R 1, R 2, R 4, R 5, R 7 and ^{R 8} are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group , A cycloalkyl 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. When R ¹ to R ⁹ are a plurality of each of the plurality of ^R 1 to R ⁹ may each be the same or different.
In the above formula (2-4), R ^B represents 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. If R ^B and Ar is a plurality each of a plurality of R ^B and Ar may each 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 '''is an integer of 0-2. If R ^C is plural, the 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, an n-butoxy group, a sec-butoxy group, a t-butoxy group, and a lauryloxy group. Can be mentioned. Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group. As said cycloalkyl group, a cyclohexyl group etc. are mentioned, for example.

  Examples of the aluminum compound include diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, and tris (ethylacetoacetate). Examples include aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum, and a compound represented by the following formula.

  Examples of the zirconium compound include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-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 [B] metal chelate compounds, aluminum compounds are preferable, diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonate) aluminum, and tris (ethylacetoacetate) aluminum are more preferable, and tris (acetylacetonate). More preferred is aluminum.

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

  [B] The content of the metal chelate compound is preferably 0.1 parts by mass to 30 parts by mass and more preferably 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the component [A]. [B] By setting the content of the metal chelate compound within the above range, the cross-linking reaction is promoted, and a liquid crystal alignment film can be produced even with low-temperature and short-time heat treatment, and excellent storage stability is maintained. can do.

[Curing accelerator]
The curing accelerator is a component that can be used for a cross-linking reaction between the molecules of the [A] component in the case where the molecule of the [A] component has an epoxy group, and can promote the cross-linking. Examples of the curing accelerator include compounds having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxy group, a carboxylic acid anhydride, and an aromatic sulfonium salt. Among these, a compound having a phenol group, a silanol group or a carboxy group, a carboxylic acid anhydride or an aromatic sulfonium salt is preferable, a compound having a phenol group or a silanol group or an aromatic sulfonium salt is more preferable, and a silanol group is included. Particularly preferred are compounds and aromatic sulfonium salts.

  As a compound which has the said phenol group, the compound etc. which are represented by a following formula are mentioned, for example.

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, Examples include silanol compounds such as the compound represented by (3).

In the above formula ^{(3), R 10} is an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, halogen _atom, -NO 2, -CN, is -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 of 1 to 3. m ² is an integer of 0-2. However, l + n ² + m ² = 4. v is an integer of 0-5. If R ¹⁰ and ^{R 11} are a plurality of each of the plurality of ^{R 10} and ^{R 11} may each be the same or different.

The alkyl group having 1 to 4 carbon atoms represented by ^R 10 ^{to R 12,} for example a methyl group, an ethyl group, a propyl group.

The compound having the silanol group is preferably a compound represented by the above formula (3), and n ² is 2 or 3, and R ¹⁰ may be substituted with a fluorine atom as a C 1-4 alkyl group. , A fluorine atom or -CN, or a compound in which v is 0 (for example, compounds represented by the following formulas (3-1) to (3-8)), n ² is 3, and R ¹⁰ is a compound having 1 to 4 carbon atoms optionally substituted with a fluorine atom or a compound in which v is 0 (for example, compounds represented by the following formulas (3-1) to (3-4)) ) Is more preferable, and compounds represented by the following formulas (3-1) and (3-2) are particularly preferable.

  Examples of the compound having a silanol group include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethylisobutoxysilane, trimethyl-1-methylpropoxysilane, and trimethylbutoxy. Silane, dimethyldiethoxysilane, diethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenylmethylethoxysilane, methylphenyldiethoxysilane , Methyldimethoxysilane, trimethoxysilane, triethoxysilane, dimethylethoxysilane, diethoxysilane, Tramethoxysilane, vinyltrimethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, ethyltrimethoxysilane, methyldiethoxysilane, butyltrimethoxysilane, trimethylphenoxysilane, trimethyl-3-hydroxyphenoxysilane, methyl-2- Hydroxyphenoxytrisilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, trimethylcyclohexyloxysilane, allyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, hexyltrimethoxysilane, Dimethylphenylethoxysilane, tripropylmethoxysilane, methyltripropoxysilane, octyloxytrimethoxy Lan, phenyltriethoxysilane, benzyltriethoxysilane, diphenyldimethoxysilane, diphenylvinylethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, tetraphenoxysilane, 1,2-bis (trimethylsiloxy) benzene, 1,3- Examples thereof include hydrolysis condensates such as bis (trimethylsiloxy) benzene, 1,4-bis (trimethylsiloxy) benzene, 1,3-dimethoxytetramethyldisiloxane, and 1,3-diethoxytetramethyldisiloxane.

  In addition, the compound which has the said phenol group and the compound which has a silanol group may protect a phenol group and a silanol group with the protective group represented by a following formula, for example. Thereby, the storage stability at room temperature can be improved while maintaining the catalytic activity.

As an aromatic sulfonium salt, for example,
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1, 1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 10-camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium persulfonate Fluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bisic [2.2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 10-camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4- Methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl -1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 10-camphorsulfonate, triphenylphosphonate Arm 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) - hexane-1-sulfonate, and the like.

  As content of a hardening accelerator, 0.5 mass part-70 mass parts are preferable with respect to 100 mass parts of [A] component, 1 mass part-60 mass parts are more preferable, 2 mass parts-50 mass parts. Is more preferable. By making content of a hardening accelerator into the said range, hardening of a liquid crystal aligning film can be accelerated | stimulated effectively.

[Surfactant]
The surfactant is a component that improves the applicability 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.

  As content of surfactant, 10 mass parts or less are preferable with respect to 100 mass parts of the whole liquid crystal aligning agent, and 1 mass part or less is more preferable.

<Method for preparing liquid crystal aligning agent>
The liquid crystal aligning agent is prepared as a solution-like composition in which the [A] component which is an essential component and other components as necessary are mixed in a predetermined ratio, and preferably each of the above components is dissolved in an organic solvent. . The solution-like composition may be prepared by mixing each component and then filtering with a filter having a pore size of about 1 μm.

  As the organic solvent, those which do not react with the [A] component and other components contained as necessary are preferable. Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like. These organic solvents may be used alone or in combination of two or more.

As an alcohol solvent, for example,
As monoalcohol solvents, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol Call, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, diacetone alcohol and the like;
As polyhydric alcohol solvents, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2 , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;
As polyhydric alcohol partial ether solvents, 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-ethyl Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Mono butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

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

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n. -Hexylketone, di-i-butylketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and the like.

  Examples of amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide. , N-methylpropionamide, N-methylpyrrolidone and the like.

  Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate Ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, Examples include diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

Examples of the hydrocarbon solvent include
As aliphatic hydrocarbon solvents, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane , Methylcyclohexane and the like;
As aromatic hydrocarbon solvents, benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene , N-amyl naphthalene and the like.

  Among these organic solvents, alcohol solvents, ether solvents, ketone solvents, and ester solvents are preferable. As the alcohol solvent, propylene glycol monomethyl ether is more preferable. As the ether solvent, diethylene glycol ethyl methyl ether is used. More preferably, the ketone solvent is methyl ethyl ketone, cyclopentanone or cyclohexanone, and the ester solvent is ethyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, ethyl acetoacetate or acetic acid. Propylene glycol monomethyl ether is more preferred.

  The solid content concentration of the liquid crystal aligning agent, that is, the ratio of the mass of all 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, 0.2 mass%-10 mass% are preferable. If the solid content concentration is less than 0.2% by mass, the film thickness of the liquid crystal alignment film formed from the liquid crystal aligning agent may be too small to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by mass, the film thickness of the coating film may be excessive and a good liquid crystal alignment film may not be obtained. May be insufficient. The range of the preferable solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, the range of the solid content concentration in the case of the spinner method is preferably 1.5% by mass to 4.5% by mass. In the case of the printing method, the solid content concentration is preferably in the range of 3% by mass to 9% by mass, and thereby the solution viscosity is preferably in the range of 0.8 mPa · s to 50 mPa · s. In the case of the ink jet method, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, and the solution viscosity is preferably in the range of 0.8 mPa · s to 15 mPa · s.

<Liquid crystal alignment film>
The liquid crystal alignment film is formed from the liquid crystal alignment agent. Since the liquid crystal alignment film is formed from the liquid crystal aligning agent, the liquid crystal alignment film exhibits good liquid crystal alignment properties and excellent adhesion to the liquid crystal layer.

<Phase difference film>
The retardation film includes the liquid crystal alignment film. Since the retardation film includes the liquid crystal alignment film, the retardation film exhibits good liquid crystal alignment properties and excellent adhesion between the liquid crystal alignment film and the liquid crystal layer. Therefore, the retardation film can be suitably used for a liquid crystal display element, particularly a liquid crystal display element for 3D video.

<Method for producing retardation film>
The method for producing the retardation film includes the following steps.

The method for producing the retardation film is as follows:
(1) A step of forming a coating film on a substrate using the liquid crystal aligning agent (hereinafter, also referred to as “step (1)”),
(2) A step of forming a liquid crystal alignment film by irradiation of radiation to the coating film (hereinafter also referred to as “step (2)”),
(3) a step of forming a polymerizable liquid crystal film on the liquid crystal alignment film using the polymerizable liquid crystal (hereinafter also referred to as “step (3)”); and (4) a liquid crystal obtained by curing the polymerizable liquid crystal film. Step of forming a layer (hereinafter also referred to as “step (4)”)
Have

  According to the manufacturing method, a retardation film that exhibits good liquid crystal alignment and excellent adhesion between the liquid crystal alignment film and the liquid crystal layer can be manufactured. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a coating film is formed on the substrate using the liquid crystal aligning agent. Examples of the coating method include a roll coater method, a spinner method, a printing method, an inkjet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber doctor coater method, an offset gravure coater method, and a single roll kiss coater. , Reverse kiss coater method with small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method, forward rotation roll coater method, blade coater method, knife coater method And an appropriate coating method such as an impregnation coater method, an MB coater method, and an MB reverse coater method. Next, a coating film is formed by heat-treating the coated surface. As temperature of heat processing, 40 to 150 degreeC is preferable and 100 to 140 degreeC is more preferable. The heat treatment time is preferably 0.1 minute to 15 minutes, and 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 a transparent substrate including a plastic substrate such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, and polycarbonate. In particular, TAC is generally used as a protective layer for polarizing films that bear important functions in LCDs. In many cases, a retardation film is used in combination with a polarizing film. The retardation film needs to be precisely controlled and bonded to an angle at which desired optical characteristics can be exhibited with respect to the polarization axis of the polarizing film. Therefore, a liquid crystal alignment film capable of aligning liquid crystals in an arbitrary direction by a photo-alignment method is formed on a TAC film, and a polymerizable liquid crystal is applied and cured so as to exhibit desired optical characteristics. If a phase difference film can be produced, the pasting process of the conventional polarizing film and phase difference film can be omitted, and it contributes to productivity improvement. Furthermore, it contributes to reducing the size and weight of the LCD material, and can be applied to flexible displays. However, the TAC film has a feature that the solvent resistance is inferior, and the solvent that can be used for forming the photo-alignment film is limited, and a highly soluble solvent such as NMP cannot be used. In addition, the TAC film has low heat resistance and is characterized in that it cannot be processed at a high temperature to form a photo-alignment film.

  Further, the liquid crystal aligning agent can be used as a liquid crystal aligning film after being applied on an LCD component member such as a color filter, an optical film including a polarizing plate or a retardation film, and undergoing step (2) described later. . Moreover, it can also apply | coat the said liquid crystal aligning agent on the retardation film manufactured using the said liquid crystal aligning agent, and can use it as a liquid crystal aligning film through the same process.

  In applying the liquid crystal aligning agent, a functional silane compound, titanate or the like may be applied in advance on the substrate in order to further improve the 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 and visible rays containing light having a wavelength of 150 nm to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. The radiation may be polarized or non-polarized. In the case of polarized light, it may be linearly polarized light or partially polarized light. Note that “non-polarized light” in this specification is included in “non-polarized light” if it is substantially non-polarized light even if it is partially polarized light.

  When radiation using linearly polarized light or partially polarized light is used, the irradiation may be performed from a direction perpendicular to the substrate surface or from an oblique direction to give a pretilt angle. You may carry out in combination. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction. The “pretilt angle” in this specification refers to the angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

  Examples of the light source 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 can be obtained by means of using the light source in combination with a filter, a diffraction grating, or the like.

The irradiation dose of ^radiation, preferably less than ^{0.1mJ / cm 2 ~1,000mJ / cm 2} , more preferably ^{1mJ / cm 2 ~500mJ / cm 2} , more preferably ^{2mJ / cm 2 ~200mJ / cm 2} . When a liquid crystal alignment ability is imparted to a coating film formed from a conventionally known liquid crystal alignment agent by a photo-alignment method, a radiation dose of 1,000 mJ / cm ² or more is required, and the liquid crystal alignment agent is used. Even when the radiation irradiation amount in the photo-alignment method is 500 mJ / cm ² or less, and even 200 mJ / cm ² or less, good liquid crystal alignment ability can be imparted, which contributes to the 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 for applying the polymerizable liquid crystal include an appropriate application 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 that can be polymerized by heating and / or radiation irradiation. For example, it may be a nematic liquid crystal compound as described in UV curable liquid crystal and its application (see Liquid Crystal Vol. 3, No. 1, 1999, pages 34 to 42), or a mixture of a plurality of compounds. Moreover, the well-known photoinitiator or thermal polymerization initiator may be included. These polymerizable liquid crystal compounds and mixtures thereof can be used after being dissolved in an appropriate solvent. Further, a liquid crystal having twisted nematic orientation twisted in a direction perpendicular to the substrate by adding a chiral agent or the like, a cholesteric liquid crystal, or a discotic liquid crystal may be used.

[Step (4)]
In this step, the solvent contained in the polymerizable liquid crystal is dried by heating and / or radiation irradiation, and the polymerizable liquid crystal film is cured by polymerization to form a liquid crystal layer. The polymerization may be performed in the air or in an inert gas atmosphere such as nitrogen, and conditions suitable for the polymerizable group and initiator of the polymerizable liquid crystal to be used can be selected. The film thus obtained can fix the liquid crystal layer in the intended alignment state and can be used as a retardation film.

  As a temperature for heating the polymerizable liquid crystal, a temperature at which good alignment is obtained is selected. For example, when Merck polymerizable liquid crystal, RMS03-013C, is used, the heating temperature is selected in the range of 40 ° C to 80 ° C.

Examples of the radiation in the case of irradiation with radiation include non-polarized ultraviolet rays. The irradiation dose of the radiation ^is preferably ^{50mJ / cm 2 ~10,000mJ / cm 2} , 100mJ / cm 2 ~5,000mJ / cm 2 is more preferable.

  As the film thickness of the liquid crystal layer, a film thickness that provides desired optical characteristics is selected. For example, when manufacturing a half-wave plate for visible light having a wavelength of 540 nm, select a film thickness such that the retardation of the formed retardation film is 240 nm to 300 nm, for example, a quarter-wave plate. For example, the film thickness is selected such that the phase difference is 120 nm to 150 nm. The film thickness at which the desired retardation is obtained varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when a polymerizable liquid crystal (RMS03-013C) manufactured by Merck is used, the film thickness for producing a quarter wavelength plate is selected in the range of 0.6 μm to 1.5 μm.

<Liquid crystal display element>
The liquid crystal display element includes the retardation film. This liquid crystal display element is comprised by the liquid crystal cell, polarizing plate, etc. which are mentioned later. Since the liquid crystal display element includes the retardation film, the liquid crystal display element is excellent in liquid crystal orientation and the like.

  The driving method of the liquid crystal display element of the present invention is not particularly limited, and the present technology is applied to various known methods such as TN, STN, IPS, FFS, VA (including VA-MVA method, VA-PVA method, etc.). The retardation film formed from the liquid crystal aligning agent is provided. In general, a liquid crystal display element includes 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 are disposed to face each other, and a liquid crystal is interposed between the pair of substrates. And the periphery is sealed with a sealant.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element can be manufactured, for example, as follows. Two substrates on which the liquid crystal alignment film is formed are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

  In the first method, two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealant, A liquid crystal cell can be produced by injecting and filling a polymerizable liquid crystal into the cell gap defined by the substrate surface and the sealing agent, and curing the liquid crystal, and then sealing the injection hole.

  The second method is a method called an ODF (One Drop Fill) method. After applying, for example, an ultraviolet light curable sealing material to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and further dropping a polymerizable liquid crystal on the liquid crystal alignment film surface Then, the other substrate is bonded so that the liquid crystal alignment films face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent, whereby a liquid crystal cell can be produced.

  In any case, it is desirable to remove the flow alignment at the time of injection by heating to a temperature at which the liquid crystal using the liquid crystal cell takes an isotropic phase and then gradually cooling to room temperature. And the said liquid crystal display element can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

  As the sealing agent, for example, an aluminum resin 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, or the like can be used. In the case of a TN liquid crystal cell or an STN liquid crystal cell, those having positive dielectric anisotropy for forming a nematic liquid crystal are preferable. Examples of such polymerizable liquid crystal include biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, and cubane liquid crystal. Etc. are used. In addition, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (manufactured by Merck); p- A ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate can be further added and used.

  On the other hand, in the case of a vertical alignment type liquid crystal cell, a cell having negative dielectric anisotropy that forms a nematic liquid crystal is preferable. As such polymerizable liquid crystal, for example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, and phenylcyclohexane liquid crystal are used.

  The polarizing plate used outside the liquid crystal cell is not particularly limited, but is a polarizing plate in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning a polyvinyl alcohol film is sandwiched between cellulose acetate protective films, Or the polarizing plate etc. which consist of H film | membrane itself are mentioned.

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

  The photo-alignment group is preferably a group containing a cinnamic acid structure. Since the photoalignable group is a group containing a cinnamic acid structure, the liquid crystal alignment film formed from the liquid crystal aligning agent has excellent photoalignment.

  In addition, since the polymer is the same as the polymer having a group containing a photoalignable group and a polymerizable double bond in the same molecule in the description of the section of <[A] Polymer component> above, The description here is omitted.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measurement method of physical property values is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
Mw and Mn of the polymer were measured under the following conditions by gel permeation chromatography (GPC).
Column: Tosoh TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
Standard material: monodisperse polystyrene

[Epoxy equivalent]
It was measured according to JIS C2105 “hydrochloric acid-methyl ethyl ketone method”.

^[1 H-NMR analysis]
¹ H-NMR analysis was performed using a nuclear magnetic resonance apparatus (JNM-ECX400P, manufactured by JEOL Ltd.) under the conditions of measurement frequency: 400 MHz and measurement solvent: chloroform-d ₃ or DMSO-d ₆ .

<Synthesis of [A] Component>
After synthesizing a cinnamic acid derivative and a polyorganosiloxane, a polyorganosiloxane (PA) having a group containing a polymerizable double bond and / or a photo-alignment group (hereinafter also referred to as “functional group”) is used. Was synthesized. Moreover, the poly (meth) acrylate which has a functional group, and the poly (meth) acrylate which does not have a functional group were synthesize | combined and these were made into poly (meth) acrylate (PB). And [A] component was prepared (synthesis | combination) using these polyorganosiloxane (PA) and poly (meth) acrylate (PB). In addition, the required amount of the compound used by each synthesis example and an Example was ensured by repeating the below-mentioned synthesis | combination as needed.

[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 condenser, 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. Next, 7 g of acrylic acid was added to the mixed solution with a syringe and stirred, and further heated and stirred at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Next, after the precipitate was filtered off, the filtrate was poured into 300 mL of a 1N aqueous hydrochloric acid solution to collect the precipitate. By recrystallizing these precipitates with a 1: 1 (mass ratio) solution of ethyl acetate and hexane, 8.4 g of cinnamic acid derivative (C-1) represented by the following formula was obtained.

[Synthesis Example 2] (Synthesis of cinnamic acid derivative (C-2))
In a 500 mL three-necked flask equipped with a condenser, 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 and 135 mL of dimethylacetamide were mixed. did. Next, 7 g of acrylic acid was added to the mixed solution with a syringe and stirred, and further heated and stirred at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Next, after the precipitate was filtered off, the filtrate was poured into 300 mL of a 1N aqueous hydrochloric acid solution to collect the precipitate. By recrystallizing these precipitates with a 1: 1 (mass ratio) solution of ethyl acetate and hexane, 10.2 g of cinnamic acid derivative (C-2) represented by the following formula was obtained.

[Synthesis Example 3] (Synthesis of cinnamic acid derivative (C-3))
In a 500 mL three-necked flask equipped with a condenser 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. Next, 10.8 ml of methyl acrylate was added to the mixed solution with a syringe and stirred, and further heated and stirred at 110 ° C. for 5 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Next, the reaction solution was further diluted with 1 L of ethyl acetate and washed with 500 mL of water. The solution was concentrated and recrystallized with ethanol to obtain 15.2 g of cinnamic acid derivative (C-3) represented by the following formula.

[Synthesis Example 4] (Synthesis of cinnamic acid derivative (C-4))
In a 500 mL three-necked flask equipped with a condenser, 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. This mixed solution was heated and stirred at 100 ° C. for 6 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. The reaction solution was then further diluted with 250 mL of ethyl acetate and washed with 375 mL of water. The reaction solution was concentrated, 35 mL of 4N aqueous sodium hydroxide solution was added, and 35 mL of ethanol was further added. This mixed solution was heated and stirred at 60 ° C. for 1 hour. 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 aqueous hydrochloric acid and further with 375 mL of water. This solution was concentrated and recrystallized with a 1: 1 (mass ratio) 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 condenser. . Next, 10.8 ml of methyl acrylate was added to the mixed solution with a syringe and stirred, and further heated and stirred at 110 ° C. for 5 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. Next, the reaction solution was further diluted with 1 L of ethyl acetate and washed with 500 mL of water. The solution was concentrated and recrystallized with ethanol to obtain 17.6 g of 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 condenser, 17.6 g of cinnamic acid derivative (C-4) obtained in Synthesis Example 4, 7.88 g of glycidyl methacrylate, 0.78 g of tetrabutylammonium bromide and propylene glycol monomethyl ether 160 mL of acetate was mixed. Subsequently, this mixed solution was further heated and stirred at 90 ° C. for 7 hours. After confirming the completion of the reaction 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 a cinnamic acid derivative (C-5) represented by the following formula.

[Synthesis of polyorganosiloxane]
[Synthesis Example 6] (Synthesis of polyorganosiloxane (POS-1))
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. Mixed. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2% by mass aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (POS- 1) was obtained as a viscous transparent liquid.
When this polyorganosiloxane (POS-1) was subjected to ¹ H-NMR analysis, a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred.
This 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, thermometer, dropping funnel and reflux condenser, 80.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 20. 0 g, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2% by mass aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (POS- 2) was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed in the same manner as in Synthesis Example 6, it was confirmed that no side reaction of the epoxy group occurred during the reaction. This polyorganosiloxane (POS-2) had an Mw of 2,400 and an epoxy equivalent of 184. This polyorganosiloxane (POS-2) has a group containing a polymerizable double bond derived from 3- (methacryloyloxy) propyltrimethoxysilane.

[Synthesis Example 8] (Synthesis of polyorganosiloxane (POS-3))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 70.5 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol and triethylamine 8.8 g was charged and mixed at room temperature. Subsequently, 70.5 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 2 hours while stirring under reflux. The operation of concentrating the reaction solution and diluting with butyl acetate was repeated twice to distill off triethylamine and water to obtain a polymer solution containing polyorganosiloxane (POS-3). When ¹ H-NMR analysis was performed in the same manner as in Synthesis Example 6, it was confirmed that no side reaction of the epoxy group occurred during the reaction. This 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))
In a 100 mL three-necked flask, 9.3 g of polyorganosiloxane (POS-1) having an epoxy group obtained in Synthesis Example 6, 26 g of methyl isobutyl ketone, 3 g of cinnamic acid derivative (C-1) obtained in Synthesis Example 1 and tetra 0.93 g of butylammonium bromide was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, the reaction mixture was diluted with 100 g of butyl acetate and washed with water three times. The operation of concentrating this solution and diluting with butyl acetate was repeated twice to finally obtain a solution containing polyorganosiloxane (PA-1) having a photoalignment 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 polyorganosiloxane (PA-2) to (PA-8))
A polyorganosiloxane (PA--) was prepared in the same manner as in Synthesis Example 9 except that the type and amount of the compound giving a photoalignable group and the group containing a polymerizable double bond were changed as shown in Table 1 below. 2) to (PA-9) were synthesized. In addition, "-" in Table 1 indicates that the corresponding component was not blended. In Table 1, M-1 to M-3 are acryloyl group-containing carboxylic acids, M-1 is a trade name: Aronix M-5300 (manufactured by Toagosei), and M-2 is a trade name: light ester. HOMS (manufactured by Kyoeisha Chemical Co., Ltd.) and M-3 are trade names: Aronix M-510 (manufactured by Toa Gosei).

[Synthesis of poly (meth) acrylate (PB)]
[Synthesis Example 13] (Synthesis of poly (meth) acrylate (PB-1))
In a flask equipped with a condenser and a stirrer, 3 parts by mass of 2,2′-azobis (isobutyronitrile) as a polymerization initiator and 2,4-diphenyl-4-methyl-1-pentene 1 as a chain transfer agent A mass part and 180 mass parts of diethylene glycol methyl ethyl ether as a solvent were charged. 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 the atmosphere was replaced with nitrogen, stirring was started gently. The solution temperature was raised to 80 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate (PB-1). The solid content concentration of the obtained polymer solution was 33.1% by mass. Mn of the obtained polymer was 7,000.

[Synthesis Example 14] (Synthesis of poly (meth) acrylate (PB-2))
A flask equipped with a condenser 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 after nitrogen substitution, stirring was started gently. The solution temperature was raised to 80 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate (PB-2). The solid content concentration of the obtained polymer solution was 32.8% by mass. Mn of the obtained polymer was 16,000.

[Synthesis Example 15] (Synthesis of poly (meth) acrylate (PB-3))
A flask equipped with a condenser and a stirrer was charged with 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. Subsequently, 100 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate was added, and after the atmosphere was replaced with nitrogen, stirring was started gently. The solution temperature was raised to 80 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate (PB-3). The solid content concentration of the obtained polymer solution was 32.8% by mass. Mn of the obtained polymer was 14,000.

[Synthesis Example 16] (Synthesis of poly (meth) acrylate (PB-4))
100 parts by mass of poly (meth) acrylate (PB-2) obtained in Synthesis Example 14, 20 parts by mass of acryloyl group-containing carboxylic acid (Aronix M-5300, manufactured by Toagosei), 10 parts by mass of tetrabutylammonium bromide as a catalyst Then, 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent was charged and stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting 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 poly (meth) acrylate (PB-2) obtained in Synthesis Example 14, 20 parts by mass of acryloyl group-containing carboxylic acid (Aronix M-5300, manufactured by Toagosei), 10 parts by mass of tetrabutylammonium bromide as a catalyst Then, 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent was charged and stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting 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 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. The mixture was stirred and stirred at 90 ° C. for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting 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 poly (meth) acrylate (PB-3) obtained in Synthesis Example 15, 20 parts by mass of acryloyl group-containing carboxylic acid (Aronix M-5300, manufactured by Toagosei Co., Ltd.), cinnamic acid derivative obtained in Synthesis Example 3 (C-3) 50 parts by mass, 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 charged and stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting 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))
A flask equipped with a condenser and a stirrer was charged with 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. After 80 parts by mass of the cinnamic acid derivative (C-5) obtained in Synthesis Example 5 and 20 parts by mass of methacrylic acid were charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 80 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing poly (meth) acrylate. Next, 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 charged, and the temperature was 90 ° C. in a nitrogen atmosphere. For 12 hours. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting 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 cinnamic acid derivative (C-2) obtained in Synthesis Example 5, acryloyl group-containing carboxylic acid (Aronix M-5300, 10 parts by mass of Toa Gosei Co., Ltd., 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 stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting with butyl acetate was repeated twice 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 cinnamic acid derivative (C-2) obtained in Synthesis Example 5, acryloyl group-containing carboxylic acid (Aronix M-5300) , Manufactured by Toagosei Co., Ltd.), 10 parts by mass, 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 stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting with butyl acetate was repeated twice 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 a structural unit represented by the following formula, 25 parts by mass of cinnamic acid derivative (C-5) obtained in Synthesis Example 5, acryloyl group-containing carboxylic acid (Aronix M-5300, 10 parts by mass of Toa Gosei Co., Ltd., 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 stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting with butyl acetate was repeated twice to finally obtain a polymer solution containing the polymer (PC-3).

<Preparation of liquid crystal aligning agent>
The [B] metal chelate compound, curing accelerator and solvent used for the preparation of the liquid crystal aligning agent 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: Sun-Aid SI-60 (Sanshin Chemical Industry Co., Ltd.)

[solvent]
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]
[A] As a component, the solution containing (PA-1) obtained in Synthesis Example 9 was converted to (PA-1) and the amount corresponding to 15 parts by mass and obtained in Synthesis Example 18 (PB-6) In an amount equivalent to 85 parts by mass in terms of (PB-6), (B-1) 10 parts by mass as a metal chelate compound and (K-1) 40 as a curing accelerator Mass parts were mixed, and BA, MEK and PGMEA (mass ratio of each solvent: 65:25:10) as a solvent were added thereto to obtain a solution having a solid content concentration of 2.5 mass%. Subsequently, this obtained solution was filtered with a filter having a pore diameter of 1 μm to prepare a liquid crystal aligning agent (A-1).

[Examples 12 to 22 and Comparative Examples 1 to 3]
The liquid crystal aligning agents (A-2) to (A-12) and (a-1) to (a-1) to (a) are operated in the same manner as in Example 11 except that the components of the types and blending amounts shown in Table 2 below are used. a-3) was prepared. In addition, “-” in Table 2 indicates that the corresponding component was not blended.

<Formation of liquid crystal alignment film and production of retardation film>
[Example 23]
The liquid crystal aligning agent (A-1) prepared in Example 7 was applied to one surface of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C. for 2 minutes to form a coating film having a thickness of 100 nm. Formed. Next, the surface of the coating film was irradiated with polarized ultraviolet light 10 mJ / cm ² containing a 313 nm emission line perpendicularly from the substrate normal line using a Hg-Xe lamp and a Grand Taylor prism to form a liquid crystal alignment film (hereinafter referred to as this film). Polarized ultraviolet irradiation is also referred to as “polarized ultraviolet irradiation A”). Next, a polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was used, and this was filtered with a filter having a pore size of 0.2 μm. Then, a polymerizable liquid crystal film was formed on the liquid crystal alignment film using a bar coater, and a temperature of 50 ° C. baking was carried out for 1 minute at set oven, a UV 1,000 mJ / cm ² of unpolarized light including 365nm emission lines using a Hg-Xe lamp is cured by irradiating the polymerizable liquid crystal film, position A phase difference film was produced.

[Examples 24-34 and Comparative Examples 4-6]
Example 31 is the same as Example 23 except that (A-2) to (A-12) and (a-1) to (a-3) were used as liquid crystal aligning agents, and Example 31 used a polymethyl methacrylate film as a substrate. By operating in the same manner, the respective retardation films of Examples 24-34 and Comparative Examples 4-6 were produced.

<Evaluation>
About each manufactured said retardation film, it evaluated by the following method. The evaluation results are shown in Table 3.

[Liquid crystal orientation (1)]
About each phase difference film, orientation was observed with the visual observation under a cross Nicol, and a polarizing microscope. When the alignment is good visually and no abnormal domain is observed with a polarizing microscope, the liquid crystal alignment (1) is “A”. When observed, the liquid crystal orientation (1) was good “B”, and when an abnormality in the liquid crystal orientation was visually observed, the liquid crystal orientation (1) was evaluated as defective “C”.

[Liquid crystal orientation (2)]
Except having changed the conditions of the said polarized ultraviolet irradiation A into 100 mJ / cm < ² >, it operates similarly to the said Examples 15-22 and Comparative Examples 4-6, each retardation film is manufactured, The said liquid crystal aligning property (1) The liquid crystal alignment was evaluated by the same method as the evaluation method.

[Adhesion]
Using an equally spaced spacer with a guide, each retardation film was cut into 1 mm intervals with a cutter knife to form a 10 × 10 lattice pattern. Next, after the cellophane tape was adhered to the lattice pattern, the cellophane tape was peeled off from the lattice pattern. Observe the notch of the lattice pattern after peeling the cellophane tape, and if peeling is not confirmed along the notch line or at the intersection of the lattice pattern, the adhesiveness is excellent as “A” and peeling occurs. When the number of grids in the grid is less than 15% with respect to the total number of grid patterns, it was evaluated as good “B”, and when it was 15% or more, it was evaluated as defective “C”.

As is clear from the results of Table 3, the retardation films of the examples have good adhesion, and if the irradiation amount of polarized ultraviolet rays is increased to at least 100 mJ / cm ² (refer to the evaluation result of liquid crystal alignment (2)). ), The liquid crystal alignment was good, but in the comparative example, the liquid crystal alignment was poor or the adhesion was poor even when the polarized UV irradiation dose was increased to 100 mJ / cm ² . .

Since the liquid crystal aligning agent and polymer of the present invention have a photo-alignable group and a group containing a polymerizable double bond in a component such as a polymer, the liquid crystal aligning agent and the polymer exhibit good liquid crystal alignment and adhere to the liquid crystal layer. A liquid crystal alignment film having excellent properties can be formed. Therefore, the present invention provides a retardation film including a liquid crystal alignment film that exhibits good liquid crystal alignment and excellent adhesion to a liquid crystal layer, a method for producing the same, and a liquid crystal display element including the retardation film. Can do.

Claims (13)

  [A] A liquid crystal aligning agent containing a component having a photoalignable group and a group containing a polymerizable double bond in the same or different molecules.   The liquid crystal aligning agent according to claim 1, wherein the component (A) is a polymer component.   The liquid crystal aligning agent of Claim 2 in which the said polymer component contains polysiloxane, a (meth) acryl polymer, or these mixtures.   The liquid crystal aligning agent according to claim 1, wherein the photoalignable group is a group containing a cinnamic acid structure.   The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the group containing a polymerizable double bond is a (meth) acryloyl group.   The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-5.   A retardation film comprising the liquid crystal alignment film according to claim 6.   The retardation film according to claim 7, which is used for a liquid crystal display element.   A liquid crystal display device comprising the retardation film according to claim 8. A step of forming a coating film on a substrate using the liquid crystal aligning agent according to any one of claims 1 to 5,
Forming a liquid crystal alignment film by irradiating the coating film with radiation;
A method for producing a retardation film, comprising: using a polymerizable liquid crystal; forming a polymerizable liquid crystal film on the liquid crystal alignment film; and curing the polymerizable liquid crystal film to form a liquid crystal layer.   A polymer having a photoalignable group and a group containing a polymerizable double bond.   The polymer according to claim 11, wherein the photo-alignment group is a group containing a cinnamic acid structure. The polymer according to claim 11 or 12, wherein the group containing a polymerizable double bond is a (meth) acryloyl group.