JP2015026050A - Liquid crystal aligning agent, retardation film and production method of retardation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a liquid crystal alignment layer having good adhesiveness to a substrate.SOLUTION: A liquid crystal aligning agent is provided, which includes a polymer component; and in the polymer component, the following recurring units are incorporated. They are: a recurring unit (a) having a photo-aligning group; a recurring unit (b) having at least one moiety selected from a group consisting of a heterocycle having five or more members, a cyclic ketone, an aromatic ring and an alkyl chain, in a side chain of the recurring unit; and a recurring unit (c) having at least one moiety selected from a group consisting of an oxetanyl group and an oxiranyl group.

Description

  The present invention relates to a liquid crystal aligning agent, a retardation film, and a method for producing a retardation film, and more specifically, a liquid crystal aligning agent that can be suitably used to form a liquid crystal aligning film for a retardation film of a liquid crystal display element. Etc.

  Liquid crystal displays are widely used for display screens of televisions and mobile phones. Various optical materials are used for the display elements of liquid crystal displays. Among them, the retardation film eliminates the viewing angle dependency of the purpose of eliminating the coloring of the display and the change of the display color and contrast ratio depending on the visual direction. It is used for the purpose.

  In recent years, the retardation film has a liquid crystal alignment film formed on the surface of a substrate such as a TAC film, and a liquid crystal layer formed by curing a polymerizable liquid crystal on the surface of the liquid crystal alignment film. It has been known. In addition, as a means for imparting orientation to the liquid crystal alignment film in the retardation film, instead of rubbing the coating film surface in one direction with a cloth material such as rayon, a radiation sensitive material formed on the substrate surface. A photo-alignment method that imparts liquid crystal alignment ability by irradiating an organic thin film with polarized or non-polarized radiation is known. According to this photo-alignment method, it is possible to form a uniform liquid crystal alignment film while suppressing the generation of dust and static electricity during the process. In addition, there is an advantage that a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the substrate by using an appropriate photomask at the time of radiation irradiation. In recent years, various liquid crystal aligning agents for retardation films for forming a liquid crystal alignment film on a substrate using a photo-alignment method have been proposed (for example, see Patent Documents 1 and 2).

  Further, a roll-to-roll method has been proposed as a method for producing a retardation film on an industrial scale (see, for example, Patent Document 3). In this method, a film is unwound from a wound body of a long base film, a liquid crystal alignment film is formed on the unwound film, and a polymerizable liquid crystal is applied and cured on the liquid crystal alignment film. It is the method of performing the process and the process which laminates | stacks a protective film as needed in the continuous process, and collect | recovering the film after passing through these processes as a wound body.

JP 2012-37868 A JP 2012-155308 A JP 2000-86786 A

  According to the above roll-to-roll method, the retardation film can be easily produced on an industrial scale, but if the adhesion of the liquid crystal alignment film to the base film is insufficient, the film is wound after the completion of the process. The liquid crystal alignment film may be peeled off from the substrate film when it is used as a rotating body. In such a case, there arises a problem that the product yield decreases. Moreover, as a liquid crystal aligning film, not only the adhesiveness to a board | substrate but natural liquid crystal aligning property is naturally requested | required.

  The present invention has been made in view of the above problems, and provides a liquid crystal aligning agent that can form a liquid crystal aligning film having good liquid crystal alignment and adhesion with a substrate, particularly a liquid crystal aligning agent suitable for a retardation film. The main purpose is to provide.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors can solve the above problems by including a polymer having a specific side chain as the polymer component of the liquid crystal aligning agent. As a result, the present invention has been completed. Specifically, the present invention provides the following liquid crystal aligning agent, retardation film and retardation film production method.

  In one aspect, the present invention includes one or more polymers as a polymer component, and the polymer component includes a repeating unit (a) having a photo-alignment group and a 5-membered ring or more complex. A repeating unit (b) having at least one selected from the group consisting of a ring, a cyclic ketone, an aromatic ring and an alkyl chain in the side chain, and a repeating unit (c) having at least one selected from the group consisting of an oxetanyl group and an oxiranyl group And a liquid crystal aligning agent containing.

  In another aspect, the present invention provides a step of coating the liquid crystal aligning agent on a substrate to form a coating film, a step of irradiating the coating film with light, and a coating layer after the light irradiation. And a step of applying and curing a polymerizable liquid crystal. Moreover, the retardation film which has a liquid crystal aligning film formed using the said liquid crystal aligning agent is provided.

  According to the liquid crystal aligning agent of the present invention, by including the repeating unit (b) and the repeating unit (c) in the polymer component, the liquid crystal alignment is good and the adhesion to the substrate is also good. A liquid crystal alignment film can be formed. Moreover, since the retardation film of this invention comprises the liquid crystal aligning film which consists of the said liquid crystal aligning agent, while having favorable liquid crystal aligning property, the adhesiveness of a liquid crystal aligning film and a board | substrate is favorable. Therefore, even when this is stored as a wound body, the liquid crystal alignment film and the substrate are not easily peeled off, and thus a decrease in product yield can be suppressed.

  The liquid crystal aligning agent of this invention contains 1 type, or 2 or more types of polymers as a polymer component, and another component is arbitrarily mix | blended as needed. Below, each component contained in the liquid crystal aligning agent of this invention is demonstrated. In addition, the (meth) acryl in this specification is a meaning containing acryl and methacryl. The (meth) acryloxy group has a meaning including an acryloxy group and a methacryloxy group.

<Polymer component>
The polymer component in the present invention is composed of a repeating unit (a) having a photoalignable group and a 5- or more-membered heterocyclic ring, cyclic ketone, aromatic ring and alkyl chain in the same polymer or different polymers. A repeating unit (b) having at least one selected from the group in the side chain; and a repeating unit (c) having at least one selected from the group consisting of an oxetanyl group and an oxiranyl group.

[Repeating unit (a)]
The repeating unit (a) in the present invention has a photoalignment group. Here, the photo-alignment group is a functional group capable of imparting anisotropy to the film by a photoisomerization reaction, a photodimerization reaction, or a photolysis reaction by light irradiation. Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone or a derivative thereof as a basic skeleton. As a chalcone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton, etc. It is done. Among these, the photoalignable group possessed by the polymer in the present invention is preferably a group having a cinnamic acid structure in that it has high orientation ability and can be easily introduced into the polymer.

（式（ｃｎ−１）中、Ｒ^１は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基又はシアノ基である。Ｒ^２は、フェニレン基、ビフェニレン基、ターフェニレン基若しくはシクロヘキシレン基、又はこれらの基が有する水素原子の少なくとも一部が、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、当該アルコキシ基の水素原子の少なくとも一部がハロゲン原子で置換された１価の基によって置換された基又はシアノ基である。Ａ^１は、単結合、酸素原子、硫黄原子、炭素数１〜３のアルカンジイル基、−ＣＨ＝ＣＨ−、−ＮＨ−、＊^１−ＣＯＯ−、＊^１−ＯＣＯ−、＊^１−ＮＨ−ＣＯ−、＊^１−ＣＯ−ＮＨ−、＊^１−ＣＨ_２−Ｏ−または＊^１−Ｏ−ＣＨ_２−（「＊^１」はＲ^２との結合手を示す。）である。Ｒ^３は、ハロゲン原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基又はシアノ基である。ａは０又は１であり、ｂは０〜４の整数である。但し、ｂが２以上の場合、複数のＲ^３は同じでも異なっていてもよい。「＊」は結合手であることを示す。）

（式（ｃｎ−２）中、Ｒ^４は、炭素数１〜３のアルキル基である。Ｒ^５は、ハロゲン原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基又はシアノ基である。Ａ^２は、酸素原子、＊^１−ＣＯＯ−、＊^１−ＯＣＯ−、＊^１−ＮＨ−ＣＯ−又は＊^１−ＣＯ−ＮＨ−（「＊^１」はＲ^６との結合手を示す。）である。Ｒ^６は、炭素数１〜６のアルカンジイル基である。ｃは０又は１であり、ｄは０〜４の整数である。但し、ｄが２以上の場合、複数のＲ^５は同一であっても異なっていてもよい。「＊」は結合手であることを示す。） Examples of the group having a cinnamic acid structure include a monovalent group obtained by removing a hydrogen atom of a carboxyl group of cinnamic acid, or a group in which a substituent is introduced into the benzene ring of the monovalent group ( Hereinafter, these are also referred to as “order cinnamate groups”), a monovalent group in which a carboxyl group of cinnamic acid is esterified, and a divalent organic group is bonded to a benzene ring, or the monovalent group And a group in which a substituent is introduced into the benzene ring of the group (hereinafter also referred to as “reverse cinnamate group”). The forward cinnamate group can be represented by, for example, the following formula (cn-1), and the reverse cinnamate group can be represented, for example, by the following formula (cn-2).

(In formula (cn-1), R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R ² is a phenylene group or biphenylene. Group, terphenylene group or cyclohexylene group, or at least a part of hydrogen atoms of these groups is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or hydrogen of the alkoxy group A group substituted by a monovalent group in which at least a part of the atoms is substituted with a halogen atom or a cyano group, A ¹ is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group having 1 to 3 carbon atoms, ^{-CH = CH -, - NH -} , * 1 -COO -, * 1 -OCO -, * 1 -NH-CO -, * 1 -CO-NH -, * 1 -CH 2 -O- or ^{* 1} - _O-CH 2 - ( ^{"* 1"} .R ³ is a.) Showing a bond to ^{R 2} is a halogen atom, an alkyl group having 1 to 3 carbon atoms, a is .a alkoxy group or a cyano group having 1 to 3 carbon atoms 0 or 1 and b is an integer of 0 to 4. However, when b is 2 or more, a plurality of R ³ may be the same or different, and “*” indicates a bond. )

(In formula (cn-2), R ⁴ is an alkyl group having 1 to 3 carbon atoms. R ⁵ is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or cyano. A ² is an oxygen atom, * ¹ —COO—, * ¹ —OCO—, * ¹ —NH—CO— or * ¹ —CO—NH— (“* ¹ ” is a bond to R ^6. R ⁶ is an alkanediyl group having 1 to 6 carbon atoms, c is 0 or 1, and d is an integer of 0 to 4. However, when d is 2 or more, A plurality of R ⁵ may be the same or different. “*” Indicates a bond.)

（上記式中、「＊」は結合手であることを示す。）
のそれぞれで表される基などを；
上記式（ｃｎ−２）で表される基の具体例としては、例えば下記式

（上記式中、「＊」は結合手であることを示す。）
のそれぞれで表される基などを；挙げることができる。 Specific examples of the group represented by the above formula (cn-1) include, for example, the following formula

(In the above formula, “*” indicates a bond.)
A group represented by each of
Specific examples of the group represented by the above formula (cn-2) include, for example, the following formula

(In the above formula, “*” indicates a bond.)
Groups represented by each of the above; and the like.

  The content ratio of the repeating unit (a) in the polymer component is from the viewpoint of not impairing other effects while imparting sufficient photoalignment to the coating film formed using the liquid crystal aligning agent. The total amount of the repeating unit (a) with respect to all repeating units of the polymer component is preferably 0.1 to 50 mol%, more preferably 1 to 40 mol%, and 2 to 30 mol%. More preferably.

[Repeating unit (b)]
The repeating unit (b) in the present invention has at least one structure selected from the group consisting of a 5-membered or higher heterocyclic ring, a cyclic ketone, an aromatic ring, and an alkyl chain (hereinafter also referred to as “adhesion imparting structure”). Has in side chain.
The heterocyclic ring in the repeating unit (b) may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring that does not exhibit aromaticity. Examples of the heterocycle include an oxygen-containing heterocycle containing an oxygen atom in the ring skeleton, a nitrogen-containing heterocycle containing a nitrogen atom, and a sulfur-containing heterocycle containing a sulfur atom.

Here, specific examples of the aromatic heterocycle include oxygen-containing heterocycles such as furan; nitrogen-containing heterocycles such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, indole, quinoline, Examples of the sulfur-containing heterocycle include carbazole, thiazole, and purine; and examples include thiophene and benzothiophene.
Specific examples of the non-aromatic heterocyclic ring include oxygen-containing heterocyclic rings such as tetrahydrofuran, tetrahydropyran, hexamethylene oxide, dioxolane, dioxane, pyran and the like, and nitrogen-containing heterocyclic rings such as pyrrolidine. Cyclic imines such as piperidine and hexamethyleneimine; lactams such as γ-butyrolactam, δ-valerolactam, and ε-caprolactam; cyclic imides such as glutarimide as sulfur-containing heterocyclic rings such as tetrahydrothiophene, tetrahydrothiopyran, Hexamethylene sulfide and the like can be mentioned respectively.

A substituent may be bonded to the ring skeleton in the heterocyclic ring exemplified above. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).
The heterocycle of the repeating unit (b) is preferably a non-aromatic heterocycle in terms of improving the adhesion of the liquid crystal alignment film to the substrate. Among them, an oxygen-containing heterocycle or a nitrogen-containing heterocycle is preferred. Are more preferable, and cyclic ethers or lactams are particularly preferable.
The number of ring members of the heterocyclic ring is 5 or more, preferably 5 to 10, more preferably 5 to 8, and still more preferably 5 to 7.

The cyclic ketone in the repeating unit (b) preferably has 5 to 10 carbon atoms, and specific examples include cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone. Especially, it is preferable that it is C5-C8, and it is more preferable that it is C5-C7.
The aromatic ring (excluding those corresponding to a heterocyclic ring) in the repeating unit (b) preferably has 5 to 15 carbon atoms, and specifically includes a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene. Ring, fluorene ring and the like. Among the above, the aromatic ring is preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring, in terms of good solubility in the substrate and easy introduction into the polymer side chain.
A substituent may be bonded to the ring skeleton in the aromatic ring. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom.

  The alkyl chain in the repeating unit (b) preferably has 1 to 15 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group. Group, nonyl group, decyl group, dodecyl group, pentadecyl group and the like, and these may be linear or branched. Especially, it is more preferable that it is C1-C10, and it is still more preferable that it is C1-C5.

（上記式（ｂ−１）中、Ｌ^１は、単結合又は２価の連結基である。Ｘ^１０は、５員環以上の複素環、環状ケトン、芳香環又はアルキル基である。「＊」は重合体の主骨格との結合手を示す。） The adhesion-imparting structure of the repeating unit (b) may be directly bonded to the main skeleton of the polymer or may be bonded via a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -COO-, -CO-NH-, a divalent chain hydrocarbon group, and a carbon-carbon bond of the chain hydrocarbon group, A divalent group containing —O—, —CO—, —COO—, —NH— or —CO—NH—, and the like, and at least one hydrogen atom in the hydrocarbon portion of each group is a fluorine atom or It may be substituted with a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, or a hydroxyl group. That is, the repeating unit (b) is represented as a repeating unit having a group represented by the following formula (b-1).

(In the above formula (b-1), L ¹ is a single bond or a divalent linking group. X ¹⁰ is a 5-membered or higher heterocyclic ring, cyclic ketone, aromatic ring or alkyl group. "Indicates a bond with the main skeleton of the polymer.)

  The “hydrocarbon group” in the present specification may be saturated or unsaturated, and includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Further, the “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group that have only a chain structure without having a cyclic structure in the main chain. The alicyclic hydrocarbon group means a hydrocarbon group having only an alicyclic hydrocarbon structure as a ring structure and not having an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. The “aromatic hydrocarbon group” means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may have a chain structure or an alicyclic hydrocarbon structure.

As the repeating unit (b), from the group consisting of a 5-membered or higher heterocyclic ring, a cyclic ketone and an aromatic ring as the above-mentioned adhesion-providing structure in that the effect of improving the adhesion of the liquid crystal alignment film to the substrate is higher. It is preferable to have at least one selected from the side chain, more preferably at least one selected from the group consisting of a 5-membered or higher heterocyclic ring and a cyclic ketone in the side chain, and a 5-membered or higher heterocyclic ring to the side. It is particularly preferred to have in the chain.
The content ratio of the repeating unit (b) in the polymer component is a viewpoint that the effect of improving the adhesion of the liquid crystal alignment film due to the introduction of the repeating unit (b) is sufficiently obtained while other effects are not impaired. In the above, the total amount of the repeating unit (b) with respect to all repeating units of the polymer component is preferably 0.1 to 95 mol%, more preferably 1 to 60 mol%, and more preferably 5 to 40 mol. More preferably, it is made into%.

[Repeating unit (c)]
The polymer component in the present invention further has a repeating unit (c) having at least one selected from the group consisting of an oxetanyl group and an oxiranyl group. By having the group in the polymer side chain, it becomes possible to improve the adhesion of the liquid crystal alignment film to the substrate and the liquid crystal alignment.
The oxetanyl group and oxiranyl group contained in the polymer component may be directly bonded to the main skeleton of the polymer or may be bonded via a divalent linking group. As the divalent linking group, the examples of the divalent linking group described in the repeating unit (a) can be applied. In view of good low temperature curability, it is preferable to have an oxiranyl group.
The content ratio of the repeating unit (c) in the polymer component is such that the effect of improving the liquid crystal orientation and adhesion to the substrate by introducing the repeating unit (b) is obtained, and other effects are not impaired. In view of this, the total amount of the repeating unit (b) with respect to all repeating units of the polymer component is preferably 0.1 to 90 mol%, more preferably 1 to 80 mol%, and more preferably 5 to 70 More preferably, it is mol%.

In the liquid crystal aligning agent of the present invention, the repeating unit (a), the repeating unit (b) and the repeating unit (c) may have the same polymer or different polymers. May be. In order to contain all of the repeating units (a) to (c) in the polymer component of the liquid crystal aligning agent, for example, the polymer [A] having the repeating unit (a) as the polymer component, the repeating unit. A polymer [B ′] having (b) and substantially free of the repeating unit (a), having the repeating unit (c) and substantially free of the repeating unit (a) One or two or more of polymers [B ''], the above repeating unit (a), the above repeating unit (b), and the polymer [C] having the above repeating unit (c) are used. Can be done. Each of the polymer [A] and the polymer [B ′] may have the repeating unit (c), and preferably has the repeating unit (c).
For example, when the liquid crystal aligning agent of this invention contains only 1 type of polymer as a polymer component, it means that the liquid crystal aligning agent of this invention contains only the said polymer [C] as a polymer component. Moreover, when the liquid crystal aligning agent of this invention contains 2 or more types of polymers as a polymer component, as long as all the said repeating units (a)-(c) are included in a polymer component, it is multiple types. The aspect of the combination of polymers is not particularly limited. If a specific example is given, it may be a combination of a plurality of polymers having at least one of the repeating units (a) to (c), and in the combination, the repeating unit (a) and the repeating unit may be used. It may be an embodiment further containing a polymer having neither the unit (b) nor the repeating unit (c) (hereinafter also referred to as “other polymer”), or the polymer [ A combination of C] and the other polymer may be used.

As a preferable form of the liquid crystal aligning agent of the present invention, as a polymer component,
[I] An embodiment containing the polymer [A] having the repeating unit (a) and the polymer [B] having the repeating unit (b) and the repeating unit (c).
[II] An embodiment containing the polymer [C] having the repeating unit (a), the repeating unit (b) and the repeating unit (c).
[III] An embodiment containing the polymer [A], the polymer [B], and the polymer [C].
And so on. In addition, the liquid crystal aligning agent of said [I]-[III] may further contain the said other polymer as a polymer component.
Among these, the aspect of [I] or the above [II] is preferable in that the effect of improving the adhesion of the liquid crystal alignment film to the substrate and the liquid crystal orientation is high, and the aspect of [I] is preferable. Particularly preferred.

[Polymer [A]]
The polymer [A] in the present invention is a polymer having a photoalignable group. The main skeleton of the polymer [A] is, for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, (meth) acrylic polymer, polyester, polyamide, polyacetal derivative, polystyrene derivative, poly (styrene-phenylmaleimide). A skeleton formed by a derivative or the like can be given. Which of these is applied may be appropriately selected according to the use of the liquid crystal aligning agent, etc., but when used for a retardation film, at least selected from the group consisting of (meth) acrylic polymers and polyorganosiloxanes. The polyorganosiloxane is more preferable because it is preferably a single type, has good solubility in a low-boiling solvent, is easy to introduce a photoalignment group, and can have higher liquid crystal alignment. preferable.
The content ratio of the photoalignable group in the polymer [A] is preferably 0.1 to 3 mmol as the number of moles of the photoalignable group per 1 g of the polymer [A], and is preferably 0.2 to 2 More preferably, it is millimolar.

  The content ratio of the oxetanyl group and the oxiranyl group in the polymer [A] is preferably 0.01 to 1 mmol as the total amount of moles of the oxetanyl group and the oxiranyl group per 1 g of the polymer [A]. More preferably, it is 0.03 to 0.8 mmol.

  The polymer [A] preferably further has a (meth) acryloxy group. When the polymer [A] has a (meth) acryloxy group, the solubility of the polymer [A] in the solvent can be increased. The content ratio of the (meth) acryloxy group in the polymer [A] is preferably 0.1 to 5 mmol as the number of moles of (meth) acryloxy group per 1 g of the polymer [A]. More preferably, it is set to ˜4 mmol.

The polymer [A] preferably further has a hydroxyl group in that the solubility in a solvent can be improved. At this time, the content ratio of the hydroxyl group in the polymer [A] is preferably 0.01 to 2 mmol as the number of moles of hydroxyl group per 1 g of the polymer [A], preferably 0.1 to 1.5 mmol. More preferably.
The polymer [A] preferably has substantially no repeating unit (b). The “substantially free” means that the number of moles of the repeating unit (b) per gram of the polymer [A] is preferably 0.01 mmol or less, and 0.005 mmol. More preferably, it is as follows.

The method for synthesizing the polymer [A] is not particularly limited, and can be performed by appropriately combining organic chemistry methods.
[Polyorganosiloxane having photo-alignment group]
The polyorganosiloxane having a photoalignable group as the polymer [A] (hereinafter also referred to as “polyorganosiloxane [A]”) is, for example,
(A-I) A hydrolyzable silane compound (ms-1) having an oxetanyl group or an oxiranyl group, or a heavy product obtained by hydrolytic condensation of a mixture of the silane compound (ms-1) and another silane compound A method of reacting a combination (hereinafter, also referred to as “epoxy-containing polyorganosiloxane”) with a carboxylic acid (mc-1) having a photo-alignment group;
(A-II) a method of hydrolyzing and condensing a hydrolyzable silane compound (ms-2) having a photoalignable group, or a mixture of the silane compound (ms-2) and another silane compound;
And so on.

Silane compound (ms-1)
The silane compound (ms-1) is a hydrolyzable silane compound having an oxetanyl group or an oxiranyl group. Specific examples thereof include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyldimethylmethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycidoxyethyldimethylethoxysilane, 4- Glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane, 4 - Sidoxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxy Examples include silane. As the silane compound (ms-1), one of these can be used alone, or two or more can be used in combination.

Silane compound (ms-2)
The silane compound (ms-2) is a hydrolyzable silane compound having a photoalignment group. As the silane compound (ms-2), an alkoxysilane compound having a cinnamic acid structure as a photo-alignable group can be preferably used. For example, a group represented by the above formula (cn-1) or the above formula (cn- Examples thereof include alkoxysilane compounds having a group represented by 2). Examples of such alkoxysilane compounds include compounds represented by the following formulas (ms-2-1) and (ms-2-2). In addition, as a silane compound (ms-2), 1 type can be used individually or in combination of 2 or more types.

Other silane compounds The other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds, and can be appropriately selected according to the intended polymer [A]. For example, a polyorganosiloxane having a (meth) acryloxy group in the side chain can be synthesized by using a hydrolyzable silane compound (ms-3) having a (meth) acryloxy group as another silane compound. . Specific examples of the silane compound (ms-3) include, for example, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2 -(Meth) acryloxyethyltrichlorosilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltrichlorosilane, 4- (meth) Examples include acryloxybutyltrimethoxysilane and 4- (meth) acryloxybutyltriethoxysilane. As the silane compound (ms-3), one of these can be used alone or a mixture of two or more can be used.

  As other silane compounds used for the synthesis of polyorganosiloxane [A], a silane compound other than the silane compound (ms-3) (hereinafter also referred to as “silane compound (ms-4)”) is used as necessary. Can be used. Examples of such silane compound (ms-4) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyldichlorosilane, methyldimethoxysilane, Methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane , Iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane, tetraethoxy Orchids, octadecyl trichlorosilane, octadecyl trimethoxysilane, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, allyl trichlorosilane, allyl trimethoxysilane, and the like allyl triethoxysilane. As the silane compound (ms-4), one of these can be used alone, or two or more can be mixed and used.

  The hydrolysis / condensation reaction of the silane compound in the above formulas (a-I) and (a-II) is performed by using one or more silane compounds as described above and water, preferably an appropriate catalyst and an organic solvent. It can carry out by making it react in presence.

When synthesizing an epoxy-containing polyorganosiloxane by the above method (a-I), it is possible to introduce a sufficient amount of photoalignable groups into the side chain of the polymer, while the epoxy groups are in an excessive amount From the viewpoint of suppressing side reactions caused by the epoxy, the epoxy equivalent of the epoxy-containing polyorganosiloxane is preferably 80 to 10,000 g / mol, and more preferably 100 to 1,000 g / mol. Therefore, in synthesizing the epoxy-containing polyorganosiloxane by the above method (a-I), the use ratio of the silane compound (ms-1) and the other silane compound is set so that the epoxy equivalent of the obtained polyorganosiloxane is in the above range. It is preferable to adjust so that.
In addition, when the polyorganosiloxane [A] is synthesized by the above method (a-II), the ratio of the silane compound (ms-2) and the other silane compound used depends on the polymer as the polymer [A] in the present invention. It is preferable to adjust so that the concentration of the photoalignable group of the organosiloxane [A] is within the above preferable range.

In the hydrolysis / condensation reaction, the proportion of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).
Examples of the catalyst that can be used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. Specific examples of these catalysts include acids such as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acids such as toluenesulfonic acid, methanesulfonic acid, phthalic acid, malonic acid, formic acid and oxalic acid; Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc .; examples of the organic base include ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole Secondary organic amines: tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene: such as tetramethylammonium hydroxide Such as quaternary organic amines It can be mentioned, respectively.
Examples of the catalyst include alkali metal compounds or organic bases, in that side reactions such as ring opening of epoxy groups can be suppressed, hydrolysis condensation rate can be increased, and storage stability is excellent. An organic base is particularly preferable. The organic base is preferably a tertiary organic amine or a quaternary organic amine.
The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set appropriately. For example, the amount is preferably 0.01 to 3 moles relative to all silane compounds. More preferably, it is 0.05-1 times mole.

Examples of the organic solvent that can be used in the above hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Specific examples thereof include hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, I-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and tetrahydrofuran; alcohols such as 1-hexanol and 4-methyl -2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like; Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The use ratio of the organic solvent in the hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds used in the reaction. .

  The hydrolysis / condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing the solution with an organic base and water, and heating the solution in an oil bath, for example. In the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux. Moreover, it is preferable to wash | clean the organic-solvent layer fractionated from the reaction liquid with water after completion | finish of reaction. In this washing, washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2% by weight) is preferable in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to remove the solvent. In the case of the above method (a-I), an epoxy-containing polyorganosiloxane, and in the case of the above method (a-II), a polyorganosiloxane [A] having a photo-alignment group, Each can be obtained.

  In the method (a-I), the epoxy-containing polyorganosiloxane obtained by the hydrolysis / condensation reaction is then reacted with a carboxylic acid (mc-1) having a photoalignment group. Thereby, the epoxy group which epoxy-containing polyorganosiloxane has, and carboxylic acid react, and polyorganosiloxane [A] which shows photo-alignment property can be obtained. The carboxylic acid used for this reaction may be carboxylic acid (mc-1) alone, or together with carboxylic acid (mc-1), other carboxylic acids other than carboxylic acid (mc-1) are used. Also good.

Carboxylic acid (mc-1)
The carboxylic acid (mc-1) may be a compound having at least one photoalignable group and one carboxyl group, and particularly preferably a carboxylic acid having a group having a cinnamic acid structure as the photoalignable group. Can do. Examples of such a carboxylic acid (mc-1) include a carboxylic acid in which a hydrogen atom is bonded to a bond in the group represented by each of the above (cn-1) and the above formula (cn-2). Can be mentioned. More specifically, for example, a hydrogen atom is bonded to a bond in each group listed as a specific example of the above formula (cn-1) and each group listed as a specific example of the above formula (cn-2). Examples thereof include carboxylic acid.

  Note that the synthesis method of the compound in which a hydrogen atom is bonded to the bond of the group represented by each of the formula (cn-1) and the formula (cn-2) is not particularly limited, and a conventionally known method is used. They can be combined. As a typical synthesis method, for example, a method of reacting a compound having a benzene ring skeleton substituted with a halogen atom and (meth) acrylic acid or a derivative thereof in the presence of a transition metal catalyst under basic conditions; For example, a method in which 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 are reacted in the presence of a transition metal catalyst.

The other carboxylic acid used in the above reaction is a carboxylic acid having no photo-alignment group, and can be appropriately selected according to the target polymer [A]. For example, polyorganosiloxane [A] having a (meth) acryloxy group in the side chain can be synthesized by using a carboxylic acid (mc-2) having a (meth) acryloxy group as another carboxylic acid. Specific examples of the carboxylic acid (mc-2) include acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, and the like. As carboxylic acid (mc-2), 1 type selected from these can be used individually or in combination of 2 or more types.
Moreover, as other carboxylic acid used in the synthesis of polyorganosiloxane [A], a compound other than the carboxylic acid (mc-2) can be used as necessary. For example, formic acid, acetic acid, propionic acid, benzoic acid, methylbenzoic acid and the like can be mentioned.

  Regarding the ratio of the carboxylic acid (mc-1) used in the reaction between the epoxy-containing polyorganosiloxane and the carboxylic acid, the carboxylic acid (mc-1) is adjusted so that the number of moles of the photoalignable group per 1 g of the polyorganosiloxane falls within the above preferable numerical range. It is preferable to adjust the use ratio of mc-1) and other carboxylic acids. Moreover, about the usage-amount of carboxylic acid (mc-2), it is preferable to adjust so that the density | concentration of the (meth) acryloxy group of the polyorganosiloxane obtained may become the said preferable numerical range.

  The reaction between the epoxy-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. The proportion of the carboxylic acid to be reacted with the epoxy-containing polyorganosiloxane is preferably 0.001 to 1.0 mol with respect to 1 mol in total of the epoxy groups of the polyorganosiloxane, and 0.01 to 0 More preferably, the amount is 0.9 mol, and even more preferably 0.05 to 0.8 mol. Further, by setting the use ratio to 0.9 mol or less, a sufficient amount of oxetanyl group or oxiranyl group can be left in the polyorganosiloxane [A] as the polymer [A], which will be described later. This is preferable in that it can be reacted with the polymer [B].

As the catalyst used in the above reaction, for example, a compound known as a so-called curing accelerator that accelerates the reaction of an organic base or an epoxy compound can be used.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine and piperidine; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine and pyridine; tetramethylammonium hydroxy And quaternary organic amines such as Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphorus compounds such as diphenylphosphine; quaternary phosphonium salts such as benzyltriphenylphosphonium chloride. Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7; organometallic compounds such as zinc octylate and tin octylate; quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide In addition to boron compounds such as boron trifluoride; metal halogen compounds such as zinc chloride and stannic chloride; and well-known latent curing accelerators can be used.
The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane to be reacted with the carboxylic acid. Can be used.

  Examples of the organic solvent that can be used in the reaction between the epoxy-containing polyorganosiloxane and the carboxylic acid include hydrocarbons, ethers, esters, ketones, amides, alcohols, and the like. Of these, ethers, esters, and ketones are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, and methylisobutyl. Examples thereof include ketones and butyl acetate. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.

  The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Moreover, after completion | finish of reaction, it is preferable to wash | clean the organic-solvent layer fractionated from the reaction liquid with water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as necessary, and then the solvent is removed to obtain the desired photo-alignable polyorganosiloxane [A]. In addition, according to the said method (a-I), since the photo-alignment group was introduce | transduced using reaction of an epoxy group and carboxylic acid, the polymer [A] which has a hydroxyl group with a photo-alignment group The polyorganosiloxane [A] can be obtained.

  For the polyorganosiloxane [A], the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography improves the liquid crystal alignment of the liquid crystal alignment film to be formed, and the liquid crystal alignment over time. From the standpoint of ensuring mechanical stability, it is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000.

[(Meth) acrylic polymer having photo-alignment group]
In the present invention, the (meth) acrylic polymer (hereinafter also referred to as “(meth) acrylic polymer [A]”) having a photoalignable group as the polymer [A] is, for example, an oxetanyl group and The (meth) acrylic monomer (ma-1) having at least one of oxiranyl groups, or the (meth) acrylic monomer (ma-1) and other (meth) acrylic monomers (ma -2) is polymerized in the presence of a polymerization initiator, the resulting polymer (hereinafter also referred to as “epoxy-containing (meth) acrylic polymer”), and a photo-alignment group are obtained. It can obtain by the method of making it react with the carboxylic acid (mc-1) which has.

  Examples of the (meth) acrylic monomer (ma-1) include unsaturated carboxylic acid esters having an oxetanyl group or an oxiranyl group. Specific examples thereof include, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate. Α-ethyl acrylate 3,4-epoxybutyl, (meth) acrylate 3,4-epoxycyclohexylmethyl, (meth) acrylate 6,7-epoxyheptyl, α-ethyl acrylate 6,7-epoxyheptyl, Examples include 4-hydroxybutyl glycidyl ether of acrylic acid, (meth) acrylic acid (3-ethyloxetane-3-yl) methyl, and the like. Among these, from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate and 4-hydroxybutyl glycidyl ether acrylate At least one selected is preferable. In addition, as a (meth) acrylic-type monomer (ma-1), said thing can be used individually by 1 type or in combination of 2 or more types.

The (meth) acrylic monomer (ma-2) is an unsaturated compound having no oxetanyl group and oxiranyl group, such as an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated polyvalent carboxylic acid anhydride. Etc. Specific examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid, (meth) acrylic acid ω-carboxypolycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α- n-butyl acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid and the like;
Examples of unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, allyl (meth) acrylate, and (meth) acrylic. Acid-n-butyl, (meth) acrylic acid-isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-ethylhexyl, (meta ) Lauryl acrylate, (meth) acrylic acid trimethoxysilylpropyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid-N, N-diethylaminoethyl, (Meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid octoxy (Meth) acrylic acid esters such as reethylene glycol and tetrahydrofurfuryl (meth) acrylate: α-alkoxyacrylic acid esters such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate: methyl crotonate, ethyl crotonate, etc. Crotonic acid esters, etc .;
Examples of unsaturated polycarboxylic anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride and the like;
Other examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. In addition, as a (meth) acrylic-type monomer (ma-2), the said thing can be used individually by 1 type or in combination of 2 or more types.

In the synthesis of the (meth) acrylic polymer [A], the total amount (number of moles) of epoxy groups per 1 g of the epoxy-containing (meth) acrylic polymer is preferably 5.0 × 10 ⁻⁵ or more. 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻² mol / g, more preferably 5.0 × 10 ^{−4 to} 5.0 × 10 ⁻³ mol / g. . Therefore, the use ratio of the (meth) acrylic monomer (ma-1) is adjusted so that the total number of moles of epoxy groups per gram of the (meth) acrylic polymer falls within the above numerical range. Is preferred.
In addition, as a monomer used for synthesis, for example, 1,3-butadiene or the like can be used in addition to the (meth) acrylic monomers (ma-1) and (ma-2) within the scope of the effects of the present invention. Vinyl monomers such as isoprene, styrene monomers such as styrene and hydroxystyrene, unsaturated carboxylic acid amide compounds such as N-isopropylacrylamide and N, N-dimethylmethacrylamide, and unsaturated ketones such as methyl vinyl ketone It may contain other monomers such as compounds.

The polymerization reaction using the (meth) acrylic monomer is preferably performed by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include initiators usually used in radical polymerization. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4 -Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis ( Examples thereof include organic peroxides such as t-butylperoxy) cyclohexane; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents. Of these, azo compounds are preferable, and 2,2′-azobis (isobutyronitrile) is more preferable. As a polymerization initiator, these can be used individually by 1 type or in combination of 2 or more types.
The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of all monomers used in the reaction.

  The polymerization reaction of the (meth) acrylic monomer is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like. Among these, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred examples thereof include diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate. In addition, as an organic solvent, these can be used individually by 1 type or in combination of 2 or more types.

  In the polymerization reaction of the (meth) acrylic monomer, the reaction temperature is preferably 30 to 120 ° C, more preferably 60 to 110 ° C. The reaction time is preferably 1 to 36 hours, and more preferably 2 to 24 hours. The amount of organic solvent used (a) is such that the total amount (b) of monomers used in the reaction is 0.1 to 50% by weight with respect to the total amount of reaction solution (a + b). It is preferable to do.

  In this way, a solution containing an epoxy-containing (meth) acrylic polymer can be obtained. This reaction solution may be directly subjected to the reaction with carboxylic acid (mc-1), or may be subjected to the reaction with carboxylic acid (mc-1) after concentration or dilution of the reaction solution as necessary. . Moreover, after isolating the epoxy-containing (meth) acrylic polymer contained in the reaction solution, it may be subjected to a reaction with carboxylic acid (mc-1). From the viewpoint of reducing the number of steps, it is preferable that the epoxy-containing (meth) acrylic polymer is subjected to the reaction with the carboxylic acid (mc-1) while being contained in the reaction solution.

Next, the epoxy-containing (meth) acrylic polymer thus obtained is reacted with a carboxylic acid (mc-1) having a photoalignment group. As the carboxylic acid (mc-1), the description of the compound exemplified as the carboxylic acid having a photoalignment group used for the reaction between the epoxy-containing polyorganosiloxane and the carboxylic acid can be applied. In addition, as the carboxylic acid used in the reaction, the carboxylic acid (mc-1) may be used alone, or other carboxylic acids other than the carboxylic acid (mc-1) may be used in combination. Good. As other carboxylic acid used here, the other carboxylic acid illustrated by reaction of epoxy-containing polyorganosiloxane and carboxylic acid can be mentioned.
The use ratio of the carboxylic acid to be reacted with the epoxy-containing (meth) acrylic polymer may be 0.001 to 0.95 mol with respect to a total of 1 mol of epoxy groups of the (meth) acrylic polymer. preferable. By setting the amount to 0.001 mol or more, the photo-alignment group can be suitably introduced. By setting the amount to 0.95 mol or less, an amount of oxetanyl group sufficient for reaction with the polymer [B] or The oxiranyl group can be left in the polymer [A]. More preferably, it is 0.01-0.9 mol, and it is still more preferable to set it as 0.05-0.8 mol.

  The reaction between the epoxy-containing (meth) acrylic polymer and the carboxylic acid can be preferably performed in the presence of a catalyst and an organic solvent. Here, as a catalyst used for reaction, the compound illustrated as a catalyst which can be used for reaction of the said epoxy-group-containing polyorganosiloxane and carboxylic acid can be mentioned, for example. Among these, a quaternary ammonium salt is preferable. The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight or less, and still more preferably 0.1 to 100 parts by weight of the (meth) acrylic polymer to be reacted with the carboxylic acid. ~ 20 parts by weight.

As the organic solvent used for the reaction, examples of the organic solvent that can be used in the polymerization of the (meth) acrylic monomer can be applied, and among them, an ester is preferable. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.
In the reaction between the epoxy-containing (meth) acrylic polymer and the carboxylic acid, the reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  Thus, as the (meth) acrylic polymer [A] as the polymer [A] in the present invention, the main chain contains a structural unit derived from at least one of an unsaturated carboxylic acid and an unsaturated carboxylic acid ester, and light. A solution containing a polymer having an orientation group can be obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after isolating the (meth) acrylic polymer [A] contained in the reaction solution, Or you may use for preparation of a liquid crystal aligning agent, after refine | purifying the isolated photo-alignment (meth) acrylic-type polymer [A]. Isolation and purification of the (meth) acrylic polymer [A] can be performed according to a known method.

  In addition, the synthesis | combining method of (meth) acrylic-type polymer [A] in this invention is not limited to said method. For example, a (meth) acrylic monomer having a photo-alignment group or a mixture of the (meth) acrylic monomer and another (meth) acrylic monomer is polymerized in the presence of a polymerization initiator. It can be obtained also by the method of making it.

  For the (meth) acrylic polymer [A], the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography improves the liquid crystal alignment of the liquid crystal alignment film to be formed and the liquid crystal alignment. From the viewpoint of ensuring the stability of the property over time, it is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

[Polymer [B]]
The polymer [B] in the present invention has the repeating unit (b) and the repeating unit (c), whereby at least one of an oxetanyl group and an oxiranyl group and the adhesion-imparting structure are side-chained. It has to have. By including such a polymer [B] in the liquid crystal aligning agent, good adhesion to the substrate can be imparted to the liquid crystal alignment film to be formed. In addition, the introduction of oxetanyl group and oxiranyl group can improve the liquid crystal alignment.

As the main skeleton of the polymer [B], for example, the skeleton exemplified as the main skeleton in the polymer [A], polyvinyl alcohol, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, cellulose or a derivative thereof, Examples thereof include a skeleton formed from polyalkyleneimine, polyallylamine, hydroxyalkylcyclodextrin and the like.
The main skeleton of the polymer [B] may be the same as or different from the polymer [A]. The polymer [B] is preferably a polyorganosiloxane and a (meth) acrylic polymer, and is a (meth) acrylic polymer in terms of good adhesion to the substrate and high transparency. It is particularly preferred.
The content ratio of the adhesion-providing structure in the polymer [B] is preferably 0.05 to 5 mmol as the total amount of moles of the adhesion-providing structure per 1 g of the polymer [B]. More preferably, it is 0.1 to 4 mmol.
In addition, the content ratio of the oxetanyl group and the oxiranyl group in the polymer [B] is 0.1 to 6 mmol as the total amount of moles of the oxetanyl group and the oxiranyl group per 1 g of the polymer [B]. Preferably, it is more preferable to set it as 0.3-5 mmol.

  The polymer [B] preferably further has an alkoxysilyl group. By having the said group, the adhesiveness with respect to the board | substrate of a liquid crystal aligning film and the improvement effect of liquid crystal alignability can further be heightened. In particular, when the below-described silica particles are blended as an additive in the liquid crystal aligning agent of the present invention, the above improvement effect can be suitably obtained.

The alkoxysilyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, and the like. The number of alkoxy groups bonded to the silicon atom is preferably two or three, and more preferably three, from the viewpoint of further improving the effect of improving adhesion and liquid crystal orientation.
The alkoxysilyl group may be directly bonded to the main skeleton of the polymer or may be bonded via a divalent linking group. Examples of the divalent linking group include a divalent chain hydrocarbon group, a carbon-carbon bond between the chain hydrocarbon groups, -O-, -CO-, -COO-, -NH-, -CO. A divalent group containing —NH— or the like, a divalent group in which at least one hydrogen atom in the chain hydrocarbon group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and the like. Can be mentioned.

The alkoxysilyl group may be contained in at least one of the repeating units (b) and (c), or in a repeating unit different from the repeating units (b) and (c). It may be contained.
The content of the alkoxysilyl group in the polymer [B] is preferably 0.05 to 3 mmol, and preferably 0.1 to 2 mmol, as the number of moles of alkoxysilyl group per 1 g of the polymer [B]. More preferably.

  It is preferable that the polymer [B] does not substantially have the photo-alignment group. Here, “substantially free” means that the number of moles of the photoalignable group per gram of the polymer [B] is preferably 0.01 mmol or less, and More preferably, it is 005 mmol or less.

The method of synthesizing the polymer [B] is not particularly limited, and can be performed by appropriately combining organic chemistry methods. For example, a (meth) acrylic polymer (hereinafter also referred to as “(meth) acrylic polymer [B]”) having at least one of an oxetanyl group and an oxiranyl group and the above-described adhesion-providing structure in a side chain. ,
(B-I) A mixture of the (meth) acrylic monomer (ma-3) having the adhesion-providing structure and the (meth) acrylic monomer (ma-1), or the (meth) acrylic A method of polymerizing a mixture of the monomer (ma-3), the (meth) acrylic monomer (ma-1) and another (meth) acrylic monomer in the presence of a polymerization initiator;
(B-II) A method of reacting the epoxy-containing (meth) acrylic polymer with the carboxylic acid (mc-3) having the adhesion-providing structure.

In the case of the above method (b-I), as the (meth) acrylic monomer (ma-3) used for the synthesis, as a (meth) acrylate having a 5-membered or higher heterocyclic ring, for example, tetrahydrofurfuryl ( Such as meth) acrylate;
Examples of (meth) acrylate having an aromatic ring include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
Examples of the (meth) acrylate having an alkyl chain include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate;
Examples of the (meth) acrylic monomer (ma-1) include those exemplified as compounds that can be used in the synthesis of the epoxy-containing (meth) acrylic polymer.

  In addition, as a monomer used for the synthesis of the polymer [B], like the polymer [A], a vinyl monomer, a styrene monomer, an unsaturated carboxylic acid amide compound, an unsaturated ketone compound, etc. You may use the said other monomer. Moreover, the said adhesion provision structure can be introduce | transduced into the side chain of polymer [B] by using the compound which has the said adhesion provision structure as said other monomer. Examples of such monomers include N-vinyl-2-pyrrolidone, allyl benzyl ether, 2-methyl-3-phenyl-1-propene, o-allylcyclohexanone, and 2-methyl-6-allylcyclohexanone. Examples thereof include vinyl monomers and styrene monomers such as styrene, 4-methylstyrene, and α-methylstyrene.

  As said other (meth) acrylic-type monomer, the compound etc. which were illustrated as said (meth) acrylic-type monomer (ma-2) can be used. Moreover, the (meth) acrylic-type polymer [B] which has an alkoxysilyl group in a side chain is obtained by using the (meth) acrylate which has an alkoxysilyl group as said other (meth) acrylic-type monomer. Can do. Examples of the compound include 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, and 3- (meth) acryloxy. Examples thereof include propyltriethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane, and 6- (meth) acryloxyhexyltrimethoxysilane.

  For the details of the reaction conditions when the (meth) acrylic polymer [B] is synthesized by the method (b-I), the description of the epoxy-containing (meth) acrylic polymer can be applied. In addition, the usage ratio of each monomer is such that the concentration of the adhesion-imparting structure per gram of the polymer [B], the concentration of the total amount of oxetanyl group and oxiranyl group, and the concentration of the alkoxysilyl group are within the above preferable numerical ranges. It is preferable to adjust so that it becomes.

  In the case of the method (b-II), the carboxylic acid (mc-3) used in the reaction is a carboxylic acid having a 5- or more-membered heterocyclic ring, a carboxylic acid having a cyclic ketone, or a carboxylic acid having an aromatic ring. It is at least one selected from the group consisting of an acid and a carboxylic acid having an alkyl chain. Specific examples thereof include carboxylic acids having a 5-membered or higher heterocyclic ring such as tetrahydrofuran-2-carboxylic acid, nicotinic acid, furoic acid, etc .; carboxylic acids having a cyclic ketone such as 2-oxocyclopentane. Carboxylic acid, 2-oxocyclohexanecarboxylic acid, etc .; Examples of carboxylic acids having an aromatic ring include benzoic acid, toluic acid, naphthoic acid, etc .; Examples of carboxylic acids having an alkyl chain include propionic acid, butyric acid, etc. be able to.

In the reaction between the epoxy-containing (meth) acrylic polymer and the carboxylic acid, the proportion of the carboxylic acid to be reacted with the epoxy-containing (meth) acrylic polymer is the sum of the epoxy groups of the (meth) acrylic polymer. The amount is less than 1.0 mol, preferably 0.01 to 0.9 mol, and more preferably 0.05 to 0.8 mol with respect to 1 mol.
The reaction between the epoxy-containing (meth) acrylic polymer and the carboxylic acid can be preferably performed in the presence of a catalyst and an organic solvent. Regarding the catalyst and organic solvent used in the reaction, reaction temperature, time, and the like, the description in the above polymer [A] can be applied.

  For the (meth) acrylic polymer [B] obtained above, the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography is preferably 250 to 500,000, and 500 to 100, Is more preferably 1,000, and even more preferably 1,000 to 50,000.

  When the liquid crystal aligning agent of this invention contains the said polymer [A] and the said polymer [B] as a polymer component, the content rate of a polymer (B) is 100 weight part of polymers (A). The amount is preferably 1 to 300 parts by weight. More preferably, it is 1-200 weight part, More preferably, it is 3-100 weight part. The total amount of the polymer [A] and the polymer [B] is preferably 40 parts by weight or more with respect to 100 parts by weight of the total amount of polymer components contained in the liquid crystal aligning agent. The amount is more preferably 50 parts by weight or more, and still more preferably 60 parts by weight or more. The upper limit of the total amount is not particularly limited, and can be arbitrarily set within a range of 100 parts by weight or less.

[Polymer [C]]
The polymer [C] in the present invention has the repeating unit (a), the repeating unit (b), and the repeating unit (c). That is, the polymer [C] has the photo-alignment group, and has the adhesion imparting structure and at least one of an oxetanyl group and an oxiranyl group in the polymer side chain.

Examples of the main skeleton of the polymer [C] include skeletons exemplified as the main skeleton in the polymer [A]. Especially, it is preferable that it is at least 1 type chosen from the group which consists of a (meth) acrylic-type polymer and polyorganosiloxane.
Regarding the content ratio of the photo-alignable group in the polymer [C], the description of the polymer [A] can be applied. Moreover, description of the said polymer [B] is applicable about the content rate of the said adhesive provision structure in polymer [C], and the content rate of an oxetanyl group and an oxiranyl group.

The method for synthesizing the polymer [C] is not particularly limited, and can be performed by appropriately combining organic chemistry methods. For example, as an example of a method for synthesizing a polyorganosiloxane as a polymer [C] (hereinafter also referred to as “polyorganosiloxane [C]”), the epoxy-containing polyorganosiloxane and a carboxyl having a photo-alignment group are used. And a method of reacting an acid (mc-1) and a carboxylic acid (mc-2) having the above adhesion-imparting structure.
In the reaction of the epoxy-containing polyorganosiloxane with the carboxylic acid, the use ratio of the carboxylic acid to be reacted with the epoxy-containing polyorganosiloxane has the epoxy-containing polyorganosiloxane so that a sufficient amount of oxetanyl groups and oxiranyl groups remain. The amount is less than 1.0 mol, preferably 0.01 to 0.9 mol, more preferably 0.05 to 0.8 mol, based on 1 mol of the total epoxy group.
The reaction between the epoxy-containing polyorganosiloxane and the carboxylic acid can be preferably performed in the presence of a catalyst and an organic solvent. Regarding the catalyst and organic solvent used in the reaction, reaction temperature, time, and the like, the description in the above polymer [A] can be applied.

  About the said polyorganosiloxane [C], it is preferable that the weight average molecular weights (Mw) of polystyrene conversion measured by the gel permeation chromatography are 1,000-20,000, and are 3,000-15,000. It is more preferable.

The (meth) acrylic polymer (hereinafter also referred to as “(meth) acrylic polymer [C]”) as the polymer [C] is, for example, the epoxy-containing (meth) acrylic polymer described above. And a carboxylic acid containing a photoalignable group (mc-1) and a carboxylic acid containing a carboxylic acid (mc-2) having the above adhesion-imparting structure.
In the reaction between the epoxy-containing (meth) acrylic polymer and the carboxylic acid, the use ratio of the carboxylic acid to be reacted with the epoxy-containing (meth) acrylic polymer is sufficient to leave a sufficient amount of oxetanyl group and oxiranyl group. The amount of epoxy groups in the (meth) acrylic polymer is less than 1.0 mol, preferably 0.01 to 0.9 mol, and preferably 0.05 to 0.8 mol. It is more preferable.
The reaction between the epoxy-containing (meth) acrylic polymer and the carboxylic acid can be preferably performed in the presence of a catalyst and an organic solvent. Regarding the catalyst and organic solvent used in the reaction, reaction temperature, time, and the like, the description in the above polymer [A] can be applied.

  For the (meth) acrylic polymer [C], the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography is preferably 250 to 500,000, and preferably 500 to 100,000. Is more preferable, and it is still more preferable that it is 1,000-50,000.

<Other ingredients>
The liquid crystal aligning agent of this invention may contain the other component as needed. Examples of such other components include a silane compound [D] having a specific functional group, the above-described other polymer, metal chelate compound, curing accelerator, surfactant, silica particles, and (meth) acrylate compound [E]. And so on.

[Silane compound [D]]
The liquid crystal aligning agent of the present invention has, as an additive, a silane compound having at least one functional group selected from the group consisting of (meth) acryloxy group, oxetanyl group, oxiranyl group, vinyl group, isocyanate group, amino group and thiol group [D] may be included. By including such a silane compound [D] in the liquid crystal aligning agent, the liquid crystal alignment property of the liquid crystal alignment film to be formed and the adhesion to the substrate can be further improved.

（式（ｄ−１）中、Ｘ^１は、（メタ）アクリロキシ基、グリシドキシ基、エポキシシクロヘキシル基、ビニル基、イソシアネート基、アミノ基又はチオール基である。Ｒ^７は、炭素数１〜５のアルキル基であり、Ｒ^８は、炭素数１〜５のアルキル基又は＊−ＣＯ−Ｒ^Ｉ（但し、Ｒ^Ｉは、炭素数１〜５のアルキル基であり、「＊」は酸素原子との結合手を示す。）である。Ｒ^９は、Ｘ^１が（メタ）アクリロキシ基、イソシアネート基、アミノ基、チオール基、グリシドキシ基又はエポキシシクロヘキシル基である場合、炭素数１〜１０の２価の炭化水素基であり、Ｘ^１がビニル基である場合、単結合又は炭素数１〜１０の２価の炭化水素基である。ｎは０〜２の整数である。但し、ｎが０又は１の場合、複数のＲ^８は互いに同じでも異なっていてもよく、ｎが２の場合、複数のＲ^７は互いに同じでも異なっていてもよい。） Preferable specific examples of the silane compound [D] include, for example, a compound represented by the following formula (d-1), an organic polymer having the specific functional group, and a reactive silyl group such as an alkoxysilyl group. The silane compound etc. which become can be mentioned.

(In Formula (d-1), X ¹ is a (meth) acryloxy group, a glycidoxy group, an epoxycyclohexyl group, a vinyl group, an isocyanate group, an amino group, or a thiol group. R ⁷ has 1 to 5 carbon atoms. R ⁸ is an alkyl group having 1 to 5 carbon atoms or * —CO—R ^I (where R ^I is an alkyl group having 1 to 5 carbon atoms, and “*” is an oxygen atom) R ⁹ is a divalent group having 1 to 10 carbon atoms when X ¹ is a (meth) acryloxy group, an isocyanate group, an amino group, a thiol group, a glycidoxy group or an epoxycyclohexyl group. When it is a hydrocarbon group and X ¹ is a vinyl group, it is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 2, provided that n is 0 or 1 A plurality of R ⁸ may be the same or different from each other. And when n is 2, the plurality of R ⁷ may be the same as or different from each other.)

In the above formula (d-1), examples of the alkyl group having 1 to 5 carbon atoms of R ⁷ , R ⁸ and R ^I include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. These may be linear or branched. The alkyl group for R ⁷ , R ⁸ and R ^I preferably has 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms.
R ⁹ is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, and octane. Examples thereof include a linear or branched alkanediyl group such as a diyl group and a nonanediyl group; a divalent alicyclic hydrocarbon group such as a cyclohexylene group; and a divalent aromatic hydrocarbon group such as a phenylene group. R ⁹ preferably has 2 to 6 carbon atoms.
X ¹ is a (meth) acryloxy group, a vinyl group, an isocyanate group, an amino group, a thiol group, or an epoxy-containing group (glycidoxy group, epoxycyclohexyl group). However, regarding the vinyl group, the unsaturated double bond of the (meth) acryloxy group is not applicable. The “amino group” here includes a primary amino group, a secondary amino group, and a tertiary amino group. X ¹ is preferably a (meth) acryloxy group, a vinyl group, an epoxy-containing group, a primary amino group or an isocyanate group from the viewpoint of adhesion of the coating film to the substrate, and a (meth) acryloxy group, an epoxy-containing group. Or it is more preferable that it is an isocyanate group.
n is an integer of 0 to 2, and 0 or 1 is preferable.

Preferable specific examples of the compound represented by the formula (d-1) include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxy as a silane compound having a (meth) acryloxy group. Propylmethyldimethoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyl Trimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane and the like;
Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, and p-styrenetrimethoxy. Silane, p-styrene triethoxysilane, etc .;
Examples of the silane compound having an isocyanate group include 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane;
Examples of the silane compound having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl). ) -3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-methyl- 3- (trimethoxysilyl) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltri Ethoxysilane etc .;
Examples of the compound having a thiol group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Examples of the compound having an epoxy-containing group include the compounds exemplified as the silane compound (ms-1);
Examples of the silane compound formed by bonding a reactive silyl group and an organic polymer include a compound having one or more (meth) acryloxy groups. Silane coupling agents such as “12-1048”, “X-12-1049”, “X-12-1050” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

  Among these, the silane compound [D] includes a silane compound having a (meth) acryloxy group, a silane compound having a vinyl group, a silane compound having an epoxy-containing group, a compound having an amino group, and a silane compound having an isocyanate group. It is preferably at least one selected from the group consisting of silane compounds having a (meth) acryloxy group, silane compounds having an epoxy-containing group, and at least one selected from the group consisting of silane compounds having an isocyanate group. preferable.

  The blending ratio of the silane compound [D] is the weight contained in the liquid crystal aligning agent in that the effect of improving the adhesion of the formed liquid crystal aligning film to the substrate can be suitably obtained without impairing the liquid crystal aligning property. It is preferable to set it as 1-300 weight part with respect to 100 weight part of coalescence. In order to obtain the effect of improving the adhesion more suitably, it is more preferably 2 parts by weight or more, and still more preferably 5 parts by weight or more with respect to 100 parts by weight of the polymer. The upper limit is more preferably 250 parts by weight or less, and still more preferably 200 parts by weight or less, from the viewpoint of maintaining the liquid crystal orientation.

[Other polymers]
The above other polymers can be used for improving the solution properties and the like. Examples of the main skeleton of such other polymer include polyorganosiloxane, (meth) acrylic polymer, polyamic acid, polyamic acid ester, polyimide, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, and poly (styrene-phenyl). Maleimide) derivatives, poly (meth) acrylates and the like.
When the other polymer is added to the liquid crystal aligning agent, the blending ratio is preferably 50 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it to -40 weight part, and it is still more preferable to set it as 0.1-30 weight part.

[Metal chelate compounds]
The metal chelate compound is a component having a catalytic action for a crosslinking reaction between epoxy structures when the polymer component of the liquid crystal aligning agent has an epoxy structure (a structure having an oxetanyl group or an oxiranyl group), and is formed by low-temperature treatment. It is contained in the liquid crystal aligning agent for the purpose of ensuring the mechanical strength of the film.
As the metal chelate compound, an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium, and zirconium is preferable. Specifically, as an aluminum chelate compound, for example, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris ( Ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum, etc .; titanium chelate compounds such as diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (Acetylacetonate) titanium, etc .; as a chelate compound of zirconium, for example, tri-n-butoxyethylacetate Cetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonate) zirconium, tetrakis (ethylacetoacetate) ) Zirconium and the like can be mentioned respectively. As a metal chelate compound, 1 type selected from these can be used individually or in combination of 2 or more types.

Among these, it is preferable to use an aluminum chelate compound as the metal chelate compound, which is selected from the group consisting of diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum. It is more preferable to use 1 or more types, and it is particularly preferable to use tris (acetylacetonate) aluminum.
The proportion of the metal chelate compound used is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and 1 to 30 parts by weight with respect to 100 parts by weight of the total components including the epoxy structure. More preferably.

[Curing accelerator]
The curing accelerator is a component having a function of accelerating a crosslinking reaction between epoxy structures when the polymer component in the liquid crystal aligning agent has an epoxy structure. It is contained in the liquid crystal aligning agent in order to ensure the strength and stability over time of the liquid crystal alignment.
As a hardening accelerator, the compound which has a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group etc. can be used, for example. Of these, compounds having a phenol group, silanol group or carboxyl group are preferred, and compounds having a phenol group or silanol group are more preferred.
Specific examples of the compound having a phenol group or silanol group include a curing accelerator having a phenol group such as cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, bis (4-hydroxyphenyl) sulfone, bis (hydroxy Naphthyl) sulfone, (3-hydroxyphenyl) (4-hydroxyphenyl) sulfone, phenyl (4-hydroxyphenyl) sulfone, (methoxyphenyl) (4-hydroxyphenyl) sulfone, 4-benzylphenol, 2,2-bis ( 4-hydroxyphenyl) propane and the like;
Examples of the curing accelerator having a silanol group include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, and triphenylsilanol. , Tri (p-tolyl) silanol, tri (m-trifluoromethylphenyl) silanol, tri (o-trifluoromethylphenyl) silanol, tri (m-fluorophenyl) silanol, tri (o-fluorophenyl) silanol, diphenyl Examples thereof include silane diol and di (o-tolyl) silane diol. In addition, as a hardening accelerator, 1 type selected from these can be used individually or in combination of 2 or more types.

  As the curing accelerator, it is particularly preferable to use a compound having a silanol group. The use ratio of the curing accelerator is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and 1 to 30 parts by weight with respect to a total of 100 parts by weight of the components including the epoxy structure. More preferably.

[Surfactant]
The surfactant can be contained in the liquid crystal aligning agent for the purpose of improving the applicability of the liquid crystal aligning agent to the substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicon surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. be able to. In addition, as surfactant, 1 type selected from these can be used individually or in combination of 2 or more types.
The proportion of the surfactant used is preferably 10 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of the total amount of the liquid crystal aligning agent.

[Silica particles]
The silica particles can be contained in the liquid crystal aligning agent for the purpose of improving the adhesion between the substrate and the coating film. The preferable particle diameter of the silica particles is 1 to 200 nm, more preferably 2 to 100 nm, and particularly preferably 5 to 50 nm. Further, the shape is selected from spherical, hollow, porous, rod-like, plate-like, fibrous or indeterminate powders, preferably spherical silica particles.

The specific surface area of the silica particles is preferably 0.1 to 3000 m ² / g, more preferably 10 to 1500 m ² / g. The use form of these silica particles may be a powder in a dry state or a state dispersed in water or an organic solvent. In the latter case, a dispersion of fine-particle silica particles known in the art as colloidal silica can be used directly. In particular, the use of colloidal silica is preferred for the purpose of pursuing transparency.

  When the dispersion solvent of colloidal silica is water, the hydrogen ion concentration is in the range of 2 to 10 as a pH value, and preferably 3 to 7 acidic colloidal silica is used. In addition, when the colloidal silica dispersion solvent is an organic solvent, solvents such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide, etc. are used alone as the organic solvent. Can be used. Alternatively, a mixture of the organic solvent and at least one of an organic solvent compatible with these and water may be used. Preferred dispersing solvents are methanol, isopropyl alcohol, methyl ethyl ketone, xylene and the like.

  Examples of commercially available silica particles include colloidal silica such as methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST- 20, ST-40, ST-C, STN, ST-O, ST-50, ST-OL (manufactured by Nissan Chemical Industries, Ltd.) and the like. Moreover, as powder silica, AEROSIL130, AEROSIL300, AEROSIL380, AEROSILTT600, AEROSILOX50 (above, Nippon Aerosil Co., Ltd. product), Sildex H31, H32, H51, H52, H121, H122 (above, Asahi Glass Co., Ltd. make) , E220A, E220 (manufactured by Nippon Silica Industry Co., Ltd.), SYLYSIA470 (manufactured by Fuji Silysia Co., Ltd.), SG flake (manufactured by Nippon Sheet Glass Co., Ltd.), and the like.

The use ratio of the silica particles is preferably 1 to 50 parts by weight, and more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the total amount of the polymer components contained in the liquid crystal aligning agent. Further, the silane compound [D] combined with the silica particles is not particularly limited as long as it falls under the above, but has an epoxy group in that the effect of improving the adhesion by adding the silica particles can be sufficiently obtained. A combination of a silane compound and silica particles is preferable. More preferably, in the compound represented by the above formula (d-1), a combination of a compound having a glycidoxy group or an epoxycyclohexyl group as X ¹ and silica particles.

[(Meth) acrylate compound [E]]
The (meth) acrylate compound [E] is a compound having a (meth) acryloyl group in one molecule, and is contained in the liquid crystal aligning agent for the purpose of improving the adhesion of the film to the substrate. The (meth) acrylate compound [E] may be a monofunctional compound, a polyfunctional compound, or a mixture thereof.

  Examples of the monofunctional compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, Nonyl (meth) acrylate, Decyl (meth) acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate, Lauryl (meth) acrylate Relate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meta ) Acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadiene (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, (meth) acryloylmorpholine, 2- (meth) acryloyloxyethylphthalic acid, 2- ( (Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropyl Hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadeca Examples include fluorodecyl (meth) acrylate, mono [2- (meth) acryloyloxyethyl] phosphate, mono [2- (meth) acryloyloxyethyl] diphenyl phosphate, mono [2- (meth) acryloyloxypropyl] phosphate, and the like. .

  Examples of the polyfunctional compound include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopenty Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meta) ) Acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) L) Isocyanurate tri (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) Acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A diepoxy di (meth) acrylate, bisphenol F diepoxy di (meth) acrylate, bis [2- (meth) acryloyloxyethyl] phosphate, bis [2- (meth) acryloyl Oxypropyl] phosphate, tris [2- (meth) acryloyloxyethyl] phosphate, and the like.

Among the above, the (meth) acrylate compound [E] is preferably a monofunctional compound, more preferably a (meth) acrylate compound or a (meth) acrylic acid alkyl ester having a 5-membered or higher heterocyclic ring, tetrahydrofurfuryl ( More preferred are (meth) acrylates or methyl methacrylate.
The proportion of the (meth) acrylate compound [E] used is preferably 50 parts by weight or less, and preferably 1 to 40 parts by weight with respect to 100 parts by weight of the total amount of the polymer components contained in the liquid crystal aligning agent. More preferably, it is more preferably 2 to 30 parts by weight or less. In addition, (meth) acrylate compound [E] can be used individually by 1 type or in combination of 2 or more types.

  The liquid crystal aligning agent of the present invention may contain other additives such as a particle dispersant, an aggregation inhibitor, a stabilizer, and a viscosity modifier as necessary. These additives can be appropriately used in an amount generally used for a liquid crystal aligning agent.

  The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which a polymer component and other optional components are preferably dispersed or dissolved in an appropriate solvent. As the solvent that can be used in preparing the liquid crystal aligning agent, for example, an organic solvent such as alcohol, ether, ketone, amide, ester, and hydrocarbon can be suitably used. Specific examples thereof include alcohols such as methanol, ethanol, propanol, butanol, pentanol, 3-methoxybutanol, hexanol, heptanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3, 3, 5 -Monoalcohols such as trimethylcyclohexanol, benzyl alcohol, diacetone alcohol: polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol: ethylene glycol monomethyl ether, Ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Chirueteru, diethylene glycol propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, partial esters of polyhydric alcohols such as dipropylene glycol monopropyl ether;

Ethers such as diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of ketones 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-hexyl ketone, Di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone and the like;
Examples of amides include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methyl Propionamide, N-methylpyrrolidone and the like;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol acetate Monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid propylene glycol monomethyl ether, acetic acid propylene glycol monoethyl ether, acetic acid propylene glycol monopropyl ether, acetic acid dipropylene glycol monomethyl ether, diacetic acid glycol, acetic acid methoxytriglycol, Ethyl propionate, n-butyl propionate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Le, diethyl malonate, dimethyl and phthalic acid;
As hydrocarbons, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane Aliphatic hydrocarbons such as: benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, and aromatic hydrocarbons such as n-amyl naphthalene; In addition, as a solvent, 1 type selected from these can be used individually or in combination of 2 or more types.

  Among these solvents, it is preferable to use one or more selected from partial esters, ethers, ketones and esters of polyhydric alcohols. The partial ester of the polyhydric alcohol is propylene glycol monomethyl ether; the ether is diethylene glycol ethyl methyl ether; the ketone is at least one selected from methyl ethyl ketone, cyclopentanone and cyclohexanone; the ester is acetic acid One or more selected from ethyl, n-butyl acetate, i-butyl acetate, t-butyl acetate, ethyl acetoacetate and propylene glycol monomethyl ether acetate are more preferred. In addition, what is necessary is just to set the solvent in the liquid crystal aligning agent of this invention suitably considering the damage with respect to the board | substrate to be used, the adhesiveness to the board | substrate of the liquid crystal aligning film formed, etc.

  The proportion of the solvent used is determined based on the solid content concentration of the liquid crystal aligning agent (the total weight of all components other than the solvent in the liquid crystal aligning agent) from the viewpoint of making the coating property of the liquid crystal aligning agent and the film thickness of the coating film formed moderate. Is preferably a ratio of 0.2 to 10% by weight, and more preferably a ratio of 3 to 10% by weight. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 20-80 degreeC.

<Liquid crystal alignment film and retardation film>
By using the liquid crystal aligning agent of the present invention described above, a liquid crystal aligning film can be produced. The liquid crystal alignment film formed using the liquid crystal aligning agent of this invention is suitable for manufacture of retardation film. Below, the method to manufacture retardation film using the liquid crystal aligning agent of this invention is demonstrated. The retardation film of the present invention can be produced through the following steps (1) to (3).

[Step (1) Formation of coating film using liquid crystal aligning agent]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and a coating film is formed. As the substrate used here, a transparent substrate made of a synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, poly (meth) acrylate, polycarbonate, etc. is preferably exemplified. can do. Of these, TAC is generally used as a protective layer for a polarizing film in a liquid crystal display device. In addition, poly (meth) acrylate can be preferably used as a substrate in terms of low hygroscopicity of the solvent, good optical characteristics, and low cost.

In many cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to attach the retardation film by precisely controlling the angle with respect to the polarization axis of the polarizing film in a specific direction so that the desired optical characteristics can be exhibited. Therefore, the angle of the retardation film is controlled on the polarizing film by forming a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction on a substrate such as a TAC film or poly (meth) acrylate. However, the step of bonding can be omitted. Thereby, it can contribute to the improvement of productivity of a liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction, the liquid crystal alignment agent of the present invention can be used by a photo alignment method.
In addition, for the substrate used for coating the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the coating film, on the surface of the substrate surface on which the coating film is formed, for example, corona discharge treatment, Conventionally known pretreatments such as plasma treatment, flame treatment, and primer treatment may be performed.

  The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber. Doctor coater method, offset gravure coater method, single roll kiss coater method, reverse kiss coater method using small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method A positive rotation roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, an MB reverse coater method, and the like can be employed.

  After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. In addition, the liquid crystal aligning agent of this invention shows favorable adhesiveness and liquid crystal aligning property, even if the heating temperature at the time of coating-film formation shall be 100 degreeC. Therefore, the liquid crystal aligning agent of this invention does not need to consider the heat resistance of the board | substrate which applies this, and has the advantage that the freedom degree of board | substrate selection becomes high. The film thickness of the coating film formed on the substrate is preferably 1 to 1,000 nm, more preferably 5 nm to 500 nm.

[Step (2) Light irradiation step]
Next, the coating film formed on the substrate as described above is irradiated with light, thereby imparting liquid crystal alignment ability to the liquid crystal alignment film. Examples of light to be irradiated here include ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. Irradiation light may be polarized or non-polarized. As the polarized light, it is preferable to use light including linearly polarized light.
When the light to be used is polarized light, the light irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized light, it is necessary to carry out from a direction oblique 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). Polarized light can be obtained by means of using these light sources in combination with, for example, a filter or a diffraction grating.
The dose of light is preferably set to 0.1 mJ / cm ² or more 1,000 mJ / cm less than ^2, more preferably, to 1 to 500 mJ / cm ^2, further be 2~200mJ / cm ² preferable. In addition, when the liquid crystal aligning agent of this invention is used, even if light irradiation amount is 500 mJ / cm < ² > or less, Furthermore, 200 mJ / cm < ² > or less can provide favorable liquid crystal aligning ability by a photo-alignment method, and liquid crystal Contributes to reducing the manufacturing cost of the alignment film.

[Step (3) Formation of Liquid Crystal Layer]
Next, a polymerizable liquid crystal is applied and cured on the coating film after the light irradiation as described above. Thereby, the coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As such a polymerizable liquid crystal, a conventionally known liquid crystal can be used. Specifically, for example, Non-Patent Document 1 ("UV curable liquid crystal and its application", Liquid Crystal, Vol. 3, No. 1 (1999). Year), pp 34-42). Further, cholesteric liquid crystal; discotic liquid crystal; twisted nematic alignment type liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may further be a composition containing a known polymerization initiator, an appropriate solvent, and the like.
In order to apply the polymerizable liquid crystal as described above on the formed liquid crystal alignment film, for example, an appropriate application method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an ink jet method can be employed. .

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to at least one treatment selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable to perform these treatments in a superimposed manner because good alignment can be obtained.
The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes.
As irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm ^2, and more preferably a 100~5,000mJ / cm ^2.
The thickness of the liquid crystal layer to be formed is appropriately set depending on desired optical characteristics. For example, when manufacturing a half-wave plate for visible light having a wavelength of 540 nm, a thickness is selected such that the retardation of the formed retardation film is 240 to 300 nm. The thickness is selected such that the phase difference is 120 to 150 nm. The thickness of the liquid crystal layer from which the desired retardation is obtained varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness for manufacturing a quarter-wave plate is in the range of 0.6 to 1.5 μm.

<Liquid crystal display element>
The retardation film obtained as described above can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film manufactured using the liquid crystal aligning agent of the present invention is applied is not limited in its driving method. For example, the TN method, STN method, IPS method, FFS method, VA method (VA-) It is possible to use various known methods such as MVA method and VA-PVA method.
A liquid crystal display element generally has a structure in which a pair of substrates on which an electrode pair and a liquid crystal alignment film are formed are provided, and polarizing films are attached to both surfaces of a liquid crystal cell in which liquid crystal is sandwiched between the substrates. The retardation film is used by attaching the substrate-side surface of the retardation film to the outer surface of the polarizing film disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable that the retardation film substrate is made of TAC or an acrylic base, and the retardation film substrate also functions as a protective film for the polarizing film.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples and comparative examples, the weight average molecular weight Mw, number average molecular weight Mn, and epoxy equivalent of the polymer were measured by the following methods.
[Weight average molecular weight Mw, number average molecular weight Mn of polymer]
Mw and Mn are polystyrene conversion values measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

<Synthesis of Carboxylic Acid (mc-1)>
[Synthesis Example 1]
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 are added. Added and mixed. Next, 7 g of acrylic acid was added to the mixed solution with a syringe and stirred. The mixed solution was further stirred while heating at 120 ° C. for 3 hours. After confirming the completion of the reaction by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. By recrystallizing these precipitates with a 1: 1 (weight ratio) solution of ethyl acetate and hexane, 10.2 g of cinnamic acid derivative (mc-1-1) represented by the following formula (1) was obtained. .

<Synthesis of polymer>
[Synthesis Example 2-1: Synthesis of epoxy-containing polyorganosiloxane]
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 with. 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 mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy-containing polyorganosiloxane. Obtained as a viscous clear liquid.
This epoxy-containing polyorganosiloxane was subjected to ¹ H-NMR analysis, and 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. Was confirmed not to happen. The epoxy-containing polyorganosiloxane had a weight average molecular weight Mw of 2,200 and an epoxy equivalent of 186 g / mol.

[Synthesis Example 2-2: Synthesis of polyorganosiloxane [A-1]]
In a 100 mL three-necked flask, 10.1 g of the epoxy-containing polyorganosiloxane obtained in Synthesis Example 2-1, acrylic group-containing carboxylic acid (Toa Gosei Co., Ltd., trade name “Aronix M-5300”, acrylic acid ω-carboxypolycaprolactone (Polymerization degree n≈2)) 0.5 g, butyl acetate 20 g, cinnamic acid derivative (mc-1-1) 1.5 g obtained in Synthesis Example 1 and tetrabutylammonium bromide 0.3 g were charged at 90 ° C. Stir for 12 hours. After completion of the reaction, the reaction solution was diluted with an equal amount (by weight) of butyl acetate and washed three times with water. The operation of concentrating this solution and diluting with butyl acetate was repeated twice to finally obtain a solution containing polyorganosiloxane [A-1] having a photo-alignment group as polymer [A]. The weight average molecular weight Mw of this polyorganosiloxane [A-1] was 9,000.

[Synthesis Example 2-3: Synthesis of polyorganosiloxane [C-1]]
In a 100 mL three-necked flask, 10.5 g of the epoxy-containing polyorganosiloxane obtained in Synthesis Example 2-1, acrylic group-containing carboxylic acid (Toa Gosei Co., Ltd., trade name “Aronix M-5300”, acrylic acid ω-carboxypolycaprolactone (Polymerization degree n≈2)) 0.4 g, butyl acetate 20 g, cinnamic acid derivative (mc-1-1) 0.5 g obtained in Synthesis Example 1, 2-tetrahydropyrophilic mucoic acid (Wako Pure Chemical Industries, Ltd. )) 0.5 g and tetrabutylammonium bromide 0.3 g were charged and stirred at 90 ° C. for 12 hours. After completion of the reaction, the reaction solution was diluted with an equal amount (by weight) of butyl acetate and washed three times with water. The operation of concentrating the solution and diluting with butyl acetate was repeated twice, and finally, the polyorganosiloxane [C-1] having a photoalignable group, an oxiranyl group and a heterocyclic ring in the side chain as the polymer [C]. A solution containing was obtained. The weight average molecular weight Mw of this polyorganosiloxane [C-1] was 10,000.

[Synthesis Example 2-4: Synthesis of methacrylic polymer [A-2]]
A flask equipped with a condenser and a stirrer was charged with 1 part by weight of 2,2′-azobis (isobutyronitrile) as a polymerization initiator and 180 parts by weight of diethylene glycol methyl ethyl ether as a solvent. To this, 70 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate and 30 parts by weight of 3-methyl-3-oxetanylmethyl methacrylate were added, and the inside of the flask was purged with nitrogen. By raising the solution temperature to 80 ° C. and maintaining this temperature for 5 hours, a polymer solution containing 32.8% by weight of polymethacrylate having an epoxy group was obtained. The number average molecular weight Mn of the obtained epoxy-containing polymethacrylate was 16,000.

  Subsequently, in another reaction vessel, 305 parts by weight of the solution containing the epoxy-containing polymethacrylate obtained above (100 parts by weight in terms of polymethacrylate), cinnamic acid derivative obtained in Synthesis Example 1 (mc-1-1) ) 60 parts by weight, 10 parts by weight of tetrabutylammonium bromide as a catalyst, and 150 parts by weight of propylene glycol monomethyl ether acetate as a diluent solvent were reacted under stirring in a nitrogen atmosphere at 90 ° C. for 12 hours. After completion of the reaction, 100 parts by weight of propylene glycol monomethyl ether acetate was added to the reaction mixture for dilution, and this was washed with water three times. The organic layer after washing with water is poured into a large excess of methanol to precipitate a polymer, and the recovered precipitate is dried at 40 ° C. for 12 hours, whereby a methacrylic polymer having a photoalignable group as the polymer [A]. A polymer [A-2] was obtained.

[Synthesis Example 2-5: Synthesis of methacrylic polymer [B-1]]
A flask equipped with a condenser and a stirrer was charged with 1 part by weight of 2,2′-azobis (isobutyronitrile) as a polymerization initiator and 220 parts by weight of methylproxitol acetate as a solvent. To this, 46 parts by weight of tetrahydrofurfuryl methacrylate, 39 parts by weight of glycidyl methacrylate, and 15 parts by weight of 3-methacryloxypropyltrimethoxysilane were added as monomers, and the inside of the flask was purged with nitrogen. By raising the solution temperature to 80 ° C. and maintaining this temperature for 4 hours, as a polymer [B], 31 a methacrylic polymer [B-1] having a heterocyclic ring, an oxiranyl group and an alkoxysilyl group in the side chain was obtained. A polymer solution containing 5% by weight was obtained. The number average molecular weight Mn of the obtained methacrylic polymer [B-1] was 16,000.

[Synthesis Example 2-6: Synthesis of Methacrylic Polymer [B-2]]
The same operation as in Synthesis Example 2-5 was performed except that the monomers used for the synthesis were changed to 36 parts by weight of N-vinyl-2-pyrrolidone, 46 parts by weight of glycidyl methacrylate, and 18 parts by weight of 3-methacryloxypropyltrimethoxysilane. And a polymer solution containing 31.5% by weight of a methacrylic polymer [B-2] having a heterocyclic ring, an oxiranyl group and an alkoxysilyl group in the side chain as a polymer [B] was obtained. The number average molecular weight Mn of the obtained methacrylic polymer [B-2] was 17,000.

[Synthesis Example 2-7: Synthesis of Methacrylic Polymer [B-3]]
The same procedure as in Synthesis Example 2-5 was conducted, except that the monomers used for synthesis were changed to 47 parts by weight of benzyl methacrylate, 38 parts by weight of glycidyl methacrylate, and 15 parts by weight of 3-methacryloxypropyltrimethoxysilane, and the polymer [ A polymer solution containing 31.5% by weight of a methacrylic polymer [B-3] having a benzene ring, an oxiranyl group and an alkoxysilyl group in the side chain as B] was obtained. The number average molecular weight Mn of the obtained methacrylic polymer [B-3] was 17,000.

[Synthesis Example 2-8: Synthesis of Methacrylic Polymer [B-4]]
The same procedure as in Synthesis Example 2-5 was performed, except that the monomers used in the synthesis were changed to 65 parts by weight of tetrahydrofurfuryl methacrylate and 35 parts by weight of glycidyl methacrylate, and the heterocyclic ring and oxiranyl group were side by side as the polymer [B]. A polymer solution containing 31.5% by weight of the methacrylic polymer [B-4] in the chain was obtained. The number average molecular weight Mn of the obtained methacrylic polymer [B-4] was 16,000.

[Synthesis Example 2-9: Synthesis of methacrylic polymer [B-5]]
The same procedure as in Synthesis Example 2-5 was conducted, except that the monomers used for the synthesis were changed to 50 parts by weight of tetrahydrofurfuryl methacrylate and 50 parts by weight of (3-ethyloxetane-3-yl) methyl methacrylate. A polymer solution containing 31.5% by weight of a methacrylic polymer [B-5] having a heterocyclic ring and an oxetanyl group in the side chain as [B] was obtained. The number average molecular weight Mn of the obtained methacrylic polymer [B-5] was 17,000.

[Synthesis Example 2-10: Synthesis of methacrylic polymer [pa-1]]
A methacrylic polymer [pa-1] was prepared in the same manner as in Synthesis Example 2-5 except that the monomers used for the synthesis were changed to 50 parts by weight of glycidyl methacrylate and 50 parts by weight of 3-methacryloxypropyltrimethoxysilane. A polymer solution containing 31.4% by weight was obtained. The number average molecular weight Mn of the obtained methacrylic polymer [pa-1] was 17,000.

[Synthesis Example 2-11: Synthesis of methacrylic polymer [pa-2]]
A polymer solution containing 31.4% by weight of a methacrylic polymer [pa-2] is prepared in the same manner as in Synthesis Example 2-5 except that the monomer used in the synthesis is changed to 100 parts by weight of tetrahydrofurfuryl methacrylate. Got. The number average molecular weight Mn of the obtained methacrylic polymer [pa-2] was 17,000.

<Preparation and evaluation of liquid crystal aligning agent>
[Example 1]
(Preparation of liquid crystal aligning agent)
100 parts by weight of the polyorganosiloxane [A-1] obtained in Synthesis Example 2-2 as the polymer [A] and the methacrylic polymer obtained in Synthesis Example 2-5 as the polymer [B] [B- 1] 30 parts by weight, 10 parts by weight of colloidal silica (manufactured by Nissan Chemical Industries, product name “MEK-ST”, particle size 10-20 nm, TSC 31.6%) as silica particles, 3-glycid as compound [D] 5 parts by weight of xylpropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-403”), 40 parts by weight of tri (p-tolyl) silanol as a curing accelerator, tris (acetylacetonate) aluminum (as a metal chelate compound) 10 parts by weight of Kawaken Fine Chemical Co., Ltd., product name “Aluminum Chelate A (W)”) and butyl acetate as a solvent were added and stirred, and then filtered through a filter with a pore size of 1 μm. The Rukoto, to prepare a solid concentration of 7.5% by weight of the liquid crystal aligning agent. In the liquid crystal aligning agent obtained, polyorganosiloxane [A-1] and methacrylic polymer [B-1] were sufficiently dissolved in the solvent.

(Manufacture of retardation film)
The liquid crystal aligning agent prepared above was applied to the entire surface of one side of an acrylic film (200 mm × 100 mm, thickness 100 μm) with a bar coater, and baked for 1 minute in an oven adjusted to a temperature of 90 ° C. Formed. The surface of this coating film is irradiated with linearly polarized ultraviolet light 10 mJ / cm ² including a bright line having a wavelength of 313 nm generated using an Hg-Xe lamp and a Grand Taylor prism from a direction perpendicular to the coating film surface. An alignment film was formed.
Next, the polymerizable liquid crystal (product name “RMS03-013C”, manufactured by Merck & Co., Ltd.) immediately after being filtered through a 0.2 μm pore size filter was applied with a bar coater to form a polymerizable liquid crystal coating film. After baking for 1 minute in an oven adjusted to a temperature of 50 ° C., 1,000 mJ / cm ² of non-polarized ultraviolet light containing an emission line with a wavelength of 365 nm generated from an Hg-Xe lamp was observed in a direction perpendicular to the coating surface. A retardation film was produced by irradiating and curing the polymerizable liquid crystal to form a liquid crystal layer.

(Evaluation of retardation film)
(1) Liquid crystal orientation About the retardation film manufactured above, liquid crystal orientation was evaluated by visual observation under crossed Nicols and observation with a polarizing microscope (2.5 times magnification). In the evaluation, when the abnormal domain was not observed in both the visual observation and the observation with the polarizing microscope, the liquid crystal orientation was “excellent (◎)”, and the abnormal domain was observed in the observation with the polarizing microscope. Liquid crystal orientation “good (◯)” when no abnormal domain was observed, liquid crystal orientation “possible (Δ)” when a little abnormal domain was observed both visually and by a polarizing microscope. The case where anomalous domains were clearly observed both by visual observation and by observation with a polarizing microscope was performed as liquid crystal alignment “impossible (×)”. As a result, this retardation film had a liquid crystal orientation “excellent”.

(2) Adhesiveness Using the retardation film produced by the same operation as described above except that the baking temperature for forming the liquid crystal alignment film was changed to 100 ° C., the adhesion of the liquid crystal alignment film to the substrate was evaluated. . Specifically, using an equally spaced spacer with a guide, a cutter knife was used to cut from the surface on the liquid crystal layer side of the retardation film to form 10 × 10 lattice patterns within a range of 1 cm × 1 cm. . The depth of each cut was made to reach the middle of the substrate thickness from the surface of the liquid crystal layer. Next, after attaching a cellophane tape so as to cover the entire surface of the lattice pattern, the cellophane tape was peeled off. The notches in the lattice pattern after peeling were observed visually under crossed Nicols to evaluate the adhesion. In the evaluation, when no peeling was confirmed at the portion along the cut line and at the crossing portion of the lattice pattern, the adhesion was “excellent (◎)”, and the number of lattices where peeling was observed in the above portion was less than 14 Adhesion is “good (◯)”, and when the number of lattices where peeling is observed in the above part is 15 or more and less than 50, adhesion is “good (Δ)”, peeling is in the above part The case where the number of lattices in which the film was observed was 50 or more was determined as adhesion “impossible (×)”. As a result, the retardation film of this example had “excellent” adhesion. This evaluation method is a stricter evaluation than JIS K 5400, which counts the number of lattices that have been completely peeled off.

[Example 2]
The polymer [B] used was changed to 30 parts by weight of the methacrylic polymer [B-2] obtained in Synthesis Example 2-6, the amount of silica particles was changed to 40 parts by weight, and the compound [D] was changed to 3 parts. -A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that it was changed to 50 parts by weight of acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-5103"). In addition, in the obtained liquid crystal aligning agent, polyorganosiloxane [A-1] and the methacrylic polymer [B-2] were fully melt | dissolved in the solvent. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “excellent” and the adhesion was “excellent”.

[Example 3]
The polymer [B] used was changed to 10 parts by weight of the methacrylic polymer [B-3] obtained in Synthesis Example 2-7, and the blending amount of 3-glycidoxypropyltriethoxysilane was changed to 10 parts by weight. Except for the points described above, a liquid crystal aligning agent was prepared in the same manner as in Example 1. In addition, in the obtained liquid crystal aligning agent, polyorganosiloxane [A-1] and the methacrylic polymer [B-3] were fully melt | dissolved in the solvent. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “excellent” and the adhesion was “good”.

[Example 4]
The polymer [B] used was changed to 50 parts by weight of the methacrylic polymer [B-4] obtained in Synthesis Example 2-8, and the blending amount of 3-glycidoxypropyltriethoxysilane was changed to 10 parts by weight. Except for the points described above, a liquid crystal aligning agent was prepared in the same manner as in Example 1. In the obtained liquid crystal aligning agent, polyorganosiloxane [A-1] and methacrylic polymer [B-4] were fully dissolved in the solvent. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “good” and the adhesion was “good”.

[Example 5]
Except for the point that the polymer [B] used was changed to 30 parts by weight of the methacrylic polymer [B-5] obtained in Synthesis Example 2-9, and the silica particles and the compound [D] were not blended. A liquid crystal aligning agent was prepared in the same manner as in Example 1. In the obtained liquid crystal aligning agent, polyorganosiloxane [A-1] and methacrylic polymer [B-5] were fully dissolved in the solvent. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “good” and the adhesion was “excellent”.

[Example 6]
Example 1 except that the polymer [A] used was changed to 100 parts by weight of the methacrylic polymer [A-2] obtained in Synthesis Example 2-4 and the compound [D] was not blended. Similarly, a liquid crystal aligning agent was prepared. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “good” and the adhesion was “excellent”.

[Example 7]
Except for the point that the polymer [B] used was changed to 40 parts by weight of the methacrylic polymer [B-1] obtained in Synthesis Example 2-5, and the silica particles and the compound [D] were not blended, A liquid crystal aligning agent was prepared in the same manner as in Example 1. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “good” and the adhesion was “good”.

[Example 8]
Silica particles in which the polymer [A] and the polymer [B] are not used as the polymer component, and the polyorganosiloxane [C-1] obtained in Synthesis Example 2-3 is used as the polymer [C]. And the liquid crystal aligning agent was prepared like Example 1 except the point which did not mix | blend compound [D]. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “good” and the adhesion was “excellent”.

[Comparative Example 1]
Other than the point that the polymer [B] was not used, 30 parts by weight of the methacrylic polymer (pa-1) obtained in Synthesis Example 2-10 was used, and the silica particles and the compound [D] were not blended. Prepared a liquid crystal aligning agent in the same manner as in Example 1. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “good” and the adhesion was “good”.
[Comparative Example 2]
Other than the point that the polymer [B] was not used and 30 parts by weight of the methacrylic polymer (pa-2) obtained in Synthesis Example 2-11 was used, and the silica particles and the compound [D] were not blended. Prepared a liquid crystal aligning agent in the same manner as in Example 1. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “impossible” and the adhesion was “possible”.

[Comparative Example 3]
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the polymer [B] and silica particles were not blended, and the blending amount of 3-glycidoxypropyltriethoxysilane was changed to 30 parts by weight. did. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “impossible” and the adhesion was “possible”.
[Comparative Example 4]
A liquid crystal aligning agent was prepared in the same manner as in Example 6 except that the polymer [B] was not blended. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, with this retardation film, the liquid crystal orientation was “impossible” and the adhesion was “impossible”.
The composition and evaluation results of the liquid crystal aligning agents prepared in the above examples and comparative examples are shown in Table 1 below.

Abbreviations of component names in Table 1 have the following meanings, respectively.
(Silica particles)
m1: Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., product name “MEK-ST”, particle size 10-20 nm, TSC 31.6%)
(Silane compound [D])
S1: 3-Glycidoxypropyltriethoxysilane S2: 3-Acryloxypropyltrimethoxysilane The numerical values in Table 1 are the components for 100 parts by weight of the polymer [A-1] or the polymer [A-2]. Is used (parts by weight) (excluding Example 8). “-” Indicates that the component corresponding to the column was not used.

  In Examples 1 to 8, the liquid crystal alignment property of the coating film formed using the liquid crystal aligning agent and the adhesion of the liquid crystal alignment film to the substrate were “excellent” or “good”. On the other hand, in Comparative Examples 1-4, the liquid crystal orientation and the film adhesion were “possible” or “impossible”.

[Example 9]
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that 5 parts by weight of tetrahydrofurfuryl methacrylate was blended in place of 3-glycidoxypropyltriethoxysilane. In the liquid crystal aligning agent obtained, polyorganosiloxane [A-1] and methacrylic polymer [B-1] were sufficiently dissolved in the solvent. Further, a retardation film was produced in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used as the liquid crystal aligning agent, and performance evaluation was performed. As a result, in this retardation film, the liquid crystal orientation was “excellent” and the adhesion was “excellent”. The composition and evaluation results of the liquid crystal aligning agent prepared here are shown in Table 2 below.

Abbreviations of component names in Table 2 have the following meanings. Note that m1 is the same as in Table 1 above.
E1: Tetrahydrofurfuryl methacrylate The numerical value in Table 2 shows the usage-amount (weight part) of each component with respect to 100 weight part of polymer [A-1]. “-” Indicates that the component corresponding to the column was not used.

Claims (10)

Including one or more polymers as the polymer component,
In the polymer component, a repeating unit (a) having a photoalignable group and a repeating unit having at least one selected from the group consisting of a 5-membered or higher heterocyclic ring, a cyclic ketone, an aromatic ring and an alkyl chain in the side chain The liquid crystal aligning agent containing a unit (b) and the repeating unit (c) which has at least 1 type chosen from the group which consists of an oxetanyl group and an oxiranyl group.   The polymer component [A] having the repeating unit (a) and the polymer [B] having the repeating unit (b) and the repeating unit (c) are contained as the polymer component. Liquid crystal aligning agent as described in.   The liquid crystal aligning agent according to claim 2, wherein the polymer [B] has an alkoxysilyl group.   The polymer component containing the polymer [C] having the repeating unit (a), the repeating unit (b), and the repeating unit (c) as the polymer component. Liquid crystal aligning agent.   The polymer having at least one selected from the group consisting of the repeating unit (a), the repeating unit (b) and the repeating unit (c) is selected from the group consisting of a polyorganosiloxane and a (meth) acrylic polymer. The liquid crystal aligning agent as described in any one of Claims 1-4 which is at least 1 type.   It further contains a silane compound [D] having at least one functional group selected from the group consisting of (meth) acryloxy group, oxetanyl group, oxiranyl group, vinyl group, isocyanate group, amino group and thiol group. The liquid crystal aligning agent as described in any one of 5.   The liquid crystal aligning agent as described in any one of Claims 1-6 which further contains the (meth) acrylate compound [E].   The liquid crystal aligning agent as described in any one of Claims 1-7 which is an object for manufacture of retardation film. Applying the liquid crystal aligning agent according to any one of claims 1 to 8 on a substrate to form a coating film;
Irradiating the coating film with light;
A method of producing a retardation film, comprising: applying a polymerizable liquid crystal on the coating film after the light irradiation and curing the liquid crystal.   The retardation film which comprises the liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-8.