JP5678824B2 - Liquid crystal aligning agent, liquid crystal aligning film, retardation film production method, retardation film and liquid crystal display element - Google Patents

Description

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

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

  As a production method for efficiently producing a retardation film, a roll-to-roll method is known in which a retardation film is continuously produced on a long base film (Japanese Patent Laid-Open No. 2000-86786). reference). In the roll-to-roll method described in Japanese Patent Application Laid-Open No. 2000-86786, a liquid crystal alignment film is formed on a substrate film, a liquid crystal compound is applied on the formed liquid crystal alignment film, and then aligned. A retardation film is produced by curing a liquid crystalline compound by irradiation. The liquid crystal alignment film is an important material that affects the productivity and quality of the retardation film. However, since the roll-to-roll method includes a winding process of the retardation film at the time of manufacture, the liquid crystal alignment film includes Adhesion with the material film and relatively high film hardness are required. Moreover, in order to avoid the influence of a deformation | transformation etc. of a base film, it is desirable to carry out as low as possible the heat processing temperature required at the time of liquid crystal aligning film formation. Furthermore, in consideration of manufacturing cost and productivity, it is desirable that the heat treatment be performed in a shorter time.

  Therefore, as a liquid crystal aligning agent for retardation film, for example, an epoxy-based material is selected, and an amine compound is added as a curing agent, so that a cross-linking reaction can proceed even at a low temperature. However, the addition of a general amine compound causes a reaction with the epoxy group over time, resulting in a disadvantage that storage stability is lowered.

  In view of such a situation, a liquid crystal aligning agent excellent in storage stability, manufactured using the liquid crystal aligning agent, and adhesion to a base film, film hardness and liquid crystal alignment even at low temperature and short heat treatment The development of a liquid crystal alignment film that is excellent in the properties is desired.

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

  The present invention has been made on the basis of the circumstances as described above, and the object thereof is a liquid crystal aligning agent excellent in storage stability, manufactured using the liquid crystal aligning agent, and is based on heat treatment at a low temperature for a short time. It is to provide a liquid crystal alignment film having excellent adhesion to a material film, film hardness and liquid crystal alignment, a retardation film provided with the liquid crystal alignment film, a method for producing the retardation film, and a liquid crystal display element.

The invention made to solve the above problems is
[A] A liquid crystal aligning agent containing an epoxy group and a hydrogen donor in the same or different molecules (hereinafter also referred to as “[A] component”), and [B] a metal chelate compound.

  When the liquid crystal aligning agent contains an [A] component having an epoxy group and a hydrogen donor in the same or different molecules, the liquid crystal aligning film formed from the liquid crystal aligning agent has adhesiveness, film hardness, and Excellent liquid crystal alignment. In addition, the [B] metal chelate compound contained in the liquid crystal alignment agent acts as a catalyst, promotes a crosslinking reaction, and can produce a liquid crystal alignment film that exhibits the above effects even at low temperature and short time heat treatment. it can.

The component [A] is
(A1) a polymer having an epoxy group (hereinafter also referred to as “(a1) polymer”), and (a2) a curing accelerator having a hydrogen donor (hereinafter also referred to as “(a2) curing accelerator”). It is preferable to include. The effect of the present invention is further improved by including (a1) a polymer having an epoxy group and (a2) a curing accelerator having a hydrogen donor as one embodiment of the component (A).

  The hydrogen donor is preferably a silanol group. By making the hydrogen donor a silanol group, the catalytic activity for the epoxy group can be made more appropriate.

  In the component [A], the polymer (a1) preferably further has a silanol group. As an embodiment of the component (A), the effect of the present invention is further improved by the fact that (a1) the polymer has an epoxy group and a lanol group.

  The epoxy group is preferably an alicyclic epoxy group. By making the said epoxy group into an alicyclic epoxy group, a crosslinking reaction can be accelerated | stimulated more and hardening of the said liquid crystal aligning agent can be accelerated | stimulated.

  [A] It is preferable that a component further has a photo-alignment group. When the component [A] further has a photo-alignment group, the liquid crystal aligning agent has a high-sensitivity photo-alignment property, and can impart liquid crystal alignment ability without using, for example, a rubbing treatment.

  The photo-alignment group is preferably a group having a cinnamic acid structure. By using a group having a cinnamic acid structure having cinnamic acid or a derivative thereof as a basic skeleton as the photo-aligning group, introduction of the photo-aligning group is facilitated, and the liquid crystal aligning agent has higher photo-alignment performance.

  The group having a cinnamic acid structure is preferably at least one selected from the group consisting of a group derived from a compound represented by the following formula (1) and a group derived from a compound represented by the formula (2).

（式（１）中、
Ｒ^１は、フェニレン基、ビフェニレン基、ターフェニレン基又はシクロヘキシレン基である。上記フェニレン基、ビフェニレン基、ターフェニレン基及びシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０のアルキル基、フッ素原子を有していてもよい炭素数１〜１０のアルコキシ基、フッ素原子又はシアノ基で置換されていてもよい。
Ｒ^２は、単結合、炭素数１〜３のアルカンジイル基、酸素原子、硫黄原子、−ＣＨ＝ＣＨ−、−ＮＨ−、−ＣＯＯ−又は−ＯＣＯ−である。
ａは、０〜３の整数である。但し、ａが２以上の場合、複数のＲ^１及びＲ^２はそれぞれ同一であっても異なっていてもよい。
Ｒ^３は、フッ素原子又はシアノ基である。
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は同一であっても異なっていてもよい。
式（２）中、
Ｒ^４は、フェニレン基又はシクロヘキシレン基である。このフェニレン基又はシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０の鎖状若しくは環状のアルキル基、炭素数１〜１０の鎖状若しくは環状のアルコキシ基、フッ素原子又はシアノ基で置換されていてもよい。
Ｒ^５は、単結合、炭素数１〜３のアルカンジイル基、酸素原子、硫黄原子又は−ＮＨ−である。
ｃは、１〜３の整数である。但し、ｃが２以上の場合、複数のＲ^４及びＲ^５はそれぞれ同一であっても異なっていてもよい。
Ｒ^６は、フッ素原子又はシアノ基である。
ｄは、０〜４の整数である。但し、ｄが２以上の場合、複数のＲ^６は同一であっても異なっていてもよい。
Ｒ^７は、酸素原子、−ＣＯＯ−又は−ＯＣＯ−である。
Ｒ^８は、２価の芳香族基、２価の脂環式基、２価の複素環式基又は２価の縮合環式基である。
ｅは、０〜３の整数である。但し、ｅが２以上の場合、複数のＲ^７及びＲ^８はそれぞれ同一であっても異なっていてもよい。
Ｒ^９は、単結合、−ＯＣＯ−（ＣＨ_２）_ｆ−＊又は−Ｏ（ＣＨ_２）_ｇ−＊である。但し、＊がカルボキシル基と結合する。
ｆ及びｇは、それぞれ１〜１０の整数である。）

(In the formula (1),
R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group, biphenylene group, terphenylene group and cyclohexylene group are alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms which may have a fluorine atom. , May be substituted with a fluorine atom or a cyano group.
R ² is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, —CH═CH—, —NH—, —COO— or —OCO—.
a is an integer of 0-3. However, when a is 2 or more, the plurality of R ¹ and R ² may be the same or different.
R ³ is a fluorine atom or a cyano group.
b is an integer of 0-4. However, when b is 2 or more, the plurality of R ³ may be the same or different.
In formula (2),
R ⁴ is a phenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group or cyclohexylene group are a chain or cyclic alkyl group having 1 to 10 carbon atoms, a chain or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom, or a cyano group. May be substituted.
R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or —NH—.
c is an integer of 1 to 3. However, when c is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different.
R ⁶ is a fluorine atom or a cyano group.
d is an integer of 0-4. However, when d is 2 or more, the plurality of R ⁶ may be the same or different.
R ⁷ is an oxygen atom, —COO— or —OCO—.
R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group.
e is an integer of 0-3. However, when e is 2 or more, the plurality of R ⁷ and R ⁸ may be the same or different.
R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. However, * couple | bonds with a carboxyl group.
f and g are each an integer of 1 to 10. )

  By using a group derived from the specific cinnamic acid derivative as the group having the cinnamic acid structure, the photo-alignment performance can be particularly improved.

The liquid crystal aligning agent is
[C] At least one curing inhibitor selected from the group consisting of β-diketones, β-keto acid esters and basic compounds (hereinafter also referred to as “[C] curing inhibitor”)
It is preferable to further contain. The liquid crystal aligning agent is excellent in storage stability because the liquid crystal aligning agent further contains a [C] curing inhibitor.

  In the present invention, a liquid crystal alignment film formed of the liquid crystal alignment agent, a liquid crystal alignment film including regions having different directions of liquid crystal alignment ability, a retardation film including these liquid crystal alignment films, and a liquid crystal display element for 3D video The retardation film used is also suitably included. The liquid crystal alignment film manufactured from the liquid crystal alignment agent is excellent in adhesion, film hardness and liquid crystal alignment even in low-temperature heat treatment, and in particular, a manufacturing method excellent in productivity such as a roll-to-roll method. It is suitable for production of the used retardation film.

The method for producing the retardation film of the present invention comprises:
(1) A step of applying the liquid crystal aligning agent on a substrate to form a coating film,
(2) A step of irradiating the coating film with radiation to form a liquid crystal alignment film for retardation film, and (3) a step of applying a polymerizable liquid crystal to the liquid crystal alignment film for retardation film and curing the liquid crystal.

  According to the production method, a liquid crystal alignment film excellent in adhesion, film hardness and liquid crystal alignment can be obtained. Moreover, it becomes possible to manufacture a retardation film at low cost and high productivity by using the alignment film.

A method for producing a retardation film comprising a liquid crystal alignment film including regions having different directions of the liquid crystal alignment ability,
The above step (2)
(2-1) A step of irradiating a part or all of the coating film with the first radiation, and (2-2) a second part of the coating film having a different incident direction or polarization direction from the first radiation. The step of irradiating the radiation.

In addition, as another method for producing a retardation film including a liquid crystal alignment film including regions having different directions of the liquid crystal alignment ability,
The above step (2-2)
(2-2 ′) A manufacturing method which is a step of irradiating at least a portion of the coating film where the first radiation is not irradiated with the second radiation.

  The retardation film manufactured from the manufacturing method of a retardation film provided with the liquid crystal aligning film containing the area | region from which the direction of these liquid crystal aligning ability differs can be used suitably for 3D image | video use etc.

  A liquid crystal display element provided with the liquid crystal aligning film manufactured from the said liquid crystal aligning agent is contained in this invention. The liquid crystal display element is excellent in liquid crystal alignment.

  According to the present invention, a liquid crystal aligning agent having excellent storage stability, manufactured using the liquid crystal aligning agent, and having low adhesion at low temperatures and short heat treatment, film hardness and liquid crystal alignment An excellent liquid crystal alignment film, a retardation film including the liquid crystal alignment film, a method for producing the retardation film, and a liquid crystal display element can be provided. Therefore, the liquid crystal aligning agent can be suitably used in a process excellent in productivity such as a roll-to-roll method. In addition, a liquid crystal display element having excellent liquid crystal orientation can be provided, and the liquid crystal display element is used in a driving mode such as TN, STN, IPS, FFS, and VA (including VA-MVA mode, VA-PVA mode, and the like). Can also be suitably applied.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains a [A] component and a [B] metal chelate compound. Moreover, it is preferable that the said liquid crystal aligning agent contains a [C] hardening inhibitor, and also may contain other arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.

<[A] component>
The [A] component is not particularly limited as long as it has an epoxy group and a hydrogen donor in the same or different molecules.

As an aspect of such [A] component,
[A] embodiment in which component (a1) contains a polymer having a hydrogen donor;
An embodiment in which the component (A) includes (a1) a polymer and (a2) a curing accelerator; and an embodiment in which the component (A) includes a (a1) polymer having a hydrogen donor and (a2) a curing accelerator. Can be mentioned.

  Examples of the hydrogen donor of the “(a1) polymer having a hydrogen donor” include a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, and a carboxylic acid group. Among these, a phenol group, a silanol group, and a carboxylic acid group are preferable, a phenol group and a silanol group are more preferable, and a silanol group is particularly preferable.

  Hereinafter, the (a1) polymer, the (a1) polymer having a hydrogen donor, and (a2) the curing accelerator will be described in detail.

[(A1) Polymer]
(A1) The polymer is not particularly limited as long as it has an epoxy group. As said epoxy group, an alicyclic epoxy group is preferable. By making the said epoxy group into an alicyclic epoxy group, a crosslinking reaction can be accelerated | stimulated more and hardening of the said liquid crystal aligning agent can be accelerated | stimulated. Moreover, it is preferable that it is a structure which can introduce | transduce the photo-alignment group mentioned later, As a structure which can introduce | transduce a photo-alignment group, in addition to an epoxy group, for example, a hydroxyl group, an amino group, a carboxyl group, a mercapto group, ester group And a structure having an amide group or the like. The synthesis of such a polymer (a1) is not particularly limited and can be performed by combining conventionally known methods.

[(A1) Polymer having a hydrogen donor]
(A1) The polymer preferably has a hydrogen donor together with an epoxy group, and more preferably has a silanol group as the hydrogen donor.

  Examples of the (a1) polymer having a silanol group include a polysiloxane containing a structural unit represented by the following formula (3) (hereinafter also referred to as “epoxy group-containing polysiloxane”), a hydrolyzate thereof, and a hydrolysis product thereof. Particularly preferred is at least one selected from the group consisting of condensates.

In the above formula (3), X ¹ is a monovalent organic group having an epoxy group. Y ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, when the epoxy group-containing polysiloxane further has a silanol group, the epoxy group-containing polysiloxane includes at least a structural unit in which Y ¹ is a hydroxyl group.

  The hydrolysis condensate of the epoxy group-containing polysiloxane is not only a hydrolysis condensate of the polysiloxanes but also a process in which polysiloxane is generated by hydrolysis condensation of the structural unit represented by the above formula (3). Is a concept including a hydrolysis-condensation product when the polysiloxane obtained by branching or crosslinking of the main chain has a structural unit represented by the above formula (3).

X ¹ in the above formula (3) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include a group containing a glycidyl group, a glycidyloxy group, and an epoxycyclohexyl group. X ¹ is preferably a group represented by the following formula (X ¹ -1) or (X ¹ -2).

In the above formula (X ¹ -1), A represents an oxygen atom or a single bond. h is an integer of 1 to 3. i is an integer of 0-6. However, when i is 0, A is a single bond. In the formula ^(X 1 -2), j is an integer from 1 to 6. In formulas (X ¹ -1) and (X ¹ -2), * is bonded to a silicon atom in formula (3).

Of the epoxy groups represented by the above formula (X ¹ -1) or (X ¹ -2), the groups represented by the following formula (X ¹ -1-1) or (X ¹ -2-1) are more preferred. preferable.

In the formula (X ¹ -1-1) or the formula (X ¹ -2-1), * is bonded to the silicon atom in the formula (3).

Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y ¹ include a methoxy group and an ethoxy group; and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group Group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like; Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group.

  Such an epoxy group-containing polysiloxane preferably hydrolyzes a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent and water. Alternatively, it can be synthesized by hydrolysis and condensation.

  Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane etc. are mentioned.

  Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, Trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, Fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, Rutriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (trifluoro Methyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxy Shi 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2 -(Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluorosilane Fluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro (Ro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri -N-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryl Loxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxy Silane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercapto Methyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysila Vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, Allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec- Butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxy Orchid, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-o (Til) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) ( 3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i- Propoxysilane, (methyl) (3-mercaptopropyl) di-n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) Dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di- -Propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane , Divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi- n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, Chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (Chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl ) Silane compounds having one silicon atom such as diphenylsilane.

Examples of commercially available products include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5586, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X- 22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41 -1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N , KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
Glass resin (made by Showa Denko);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning);
FZ3711, FZ3722 (above, made by Nihon Unicar);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, manufactured by Chisso);
Methyl silicate MS51, methyl silicate MS56 (above, manufactured by Mitsubishi Chemical);
Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcoat);
Examples include partial condensates such as GR100, GR650, GR908, GR950 (manufactured by Showa Denko).

  Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acrylic are used from the viewpoint of the orientation and chemical stability of the obtained liquid crystal alignment film. Loxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane are preferred.

  In the case of using an epoxy group-containing polysiloxane, the epoxy equivalent as an epoxy equivalent in order to suppress unintended side reactions due to excessive introduction of the epoxy group while introducing a sufficient amount of side chains having photo-alignment properties. Is preferably 100 g / mol to 10,000 g / mol, more preferably 150 g / mol to 1,000 g / mol. Therefore, when synthesizing the epoxy group-containing polysiloxane, it is preferable to prepare such that the epoxy equivalent of the obtained polysiloxane is in the above range.

  When using another silane compound, it is preferable to use 0 mass%-50 mass% with respect to the sum total of an epoxy-group-containing polysiloxane and another silane compound, and it is more preferable to use 5 mass%-30 mass%.

  Examples of the organic solvent that can be used for the synthesis of the epoxy group-containing polysiloxane include hydrocarbon compounds, ketone compounds, ester compounds, ether compounds, alcohol compounds, and the like.

  Examples of the hydrocarbon compound include toluene and xylene; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; Examples of the ester include ethyl acetate, n-butyl acetate, I-Amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; Examples of the alcohol include 1-hexanol. 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n Propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether. Of these, water-insoluble ones are preferred. These organic solvents can be used alone or in admixture of two or more.

  As the usage-amount of an organic solvent, 10 mass parts-10,000 mass parts are preferable with respect to 100 mass parts of all the silane compounds, and 50 mass parts-1,000 mass parts are more preferable. Moreover, as the usage-amount of water at the time of manufacturing an epoxy-group-containing polysiloxane, 0.5 times mole-100 times mole are preferable with respect to all the silane compounds, and 1 time mole-30 times mole are more preferable.

  Hydrolysis or hydrolysis / condensation reaction when producing an epoxy group-containing polysiloxane is carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, and dissolving this solution with an organic base and water. It is preferable to carry out by mixing with, for example, heating in an oil bath or the like.

  During the hydrolysis / condensation reaction, the heating temperature of the oil bath is preferably 130 ° C. or lower, more preferably 40 ° C. to 100 ° C., preferably 0.5 hours to 12 hours, more preferably 1 hour to 8 hours. Is desirable. During heating, the mixture may be stirred or placed under reflux.

  After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this cleaning, it is preferable to perform cleaning with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by mass in view of facilitating the cleaning operation. 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 sieves as necessary, and then the target is removed by removing the solvent. An epoxy group-containing polysiloxane can be obtained.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of a polymer having an epoxy group and a silanol group is preferably 500 to 100,000, more preferably 1,000 to 10,000. 1,000 to 5,000 are preferable, and particularly preferable.
In addition, Mw in this specification is a polystyrene conversion value measured by GPC having the following specifications.
Column: Tosoh, TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 6.8 MPa

  The molar ratio of the silanol group to the epoxy group contained in the solid content of the polymer having an epoxy group and a silanol group is preferably 0.01 or more, more preferably 0.03 or more, and particularly preferably 0.05 or more.

[(A2) Curing accelerator]
(A2) The curing accelerator is not particularly limited as long as it is a curing accelerator having a hydrogen donor and exhibits catalytic activity for the epoxy group in the component [A]. Examples of the (a2) curing accelerator include compounds having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxylic acid group, and carboxylic acid anhydrides. Of these, a compound having a phenol group, a silanol group or a carboxylic acid group or a carboxylic acid anhydride is preferred, a compound having a phenol group or a silanol group is more preferred, and a compound having a silanol group (hereinafter referred to as “(a2) containing a silanol group” Particularly preferred are also "curing accelerators".

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

  (A2) Examples of the silanol group-containing curing accelerator include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, Silanol compounds, such as a compound represented by following formula (6), are mentioned.

In the above formula ^{(6), R 22} represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, a halogen atom, an NO ₂ or CN. R ²² may be bonded to a phenyl group as —COOR ²⁴ or SO ₂ OR ²⁴ . R ²⁴ is an alkyl group having 1 to 4 carbon atoms. R ²³ is an alkyl group having 1 to 4 carbon atoms or an alicyclic group. l and n are each independently an integer of 1 to 3. m is an integer of 0-2. However, l + n + m satisfies the condition of 4. v is an integer of 0-5. However, when R ²² is plural, plural R ²² may be different even in the same.

The alkyl group having 1 to 4 carbon atoms represented by ^R 22 ^{to R 24,} for example a methyl group, an ethyl group, a propyl group.

(A2) As the silanol group-containing curing accelerator is preferably a compound represented by the above formula (6), n and is a 2 or 3 R ²² is a hydrogen atom, carbon atoms, which is substituted with a fluorine atom More preferred are compounds having 1 to 4 alkyl groups, fluorine atoms or CN (for example, compounds represented by the following formulas (6-1) to (6-8)), n is 3 and R ²² is a hydrogen atom. Or the compound (For example, the compound represented by following formula (6-1)-(6-4)) which is a C1-C4 alkyl group which may be substituted by the fluorine atom is especially preferable, and following formula (6) The compounds represented by -1) and (6-2) are most preferable.

  Examples of the (a2) silanol group-containing curing accelerator include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethylisobutoxysilane, trimethyl-1-methylpropoxysilane, Trimethylbutoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenylmethylethoxysilane, methylphenyldi Ethoxysilane, methyldimethoxysilane, trimethoxysilane, triethoxysilane, dimethylethoxysilane, diethoxysilane Tetramethoxysilane, vinyltrimethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, ethyltrimethoxysilane, methyldiethoxysilane, butyltrimethoxysilane, trimethylphenoxysilane, trimethyl-3-hydroxyphenoxysilane, methyl-2- Hydroxyphenoxytrisilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, trimethylcyclohexyloxysilane, allyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, hexyltrimethoxysilane, Dimethylphenylethoxysilane, tripropylmethoxysilane, methyltripropoxysilane, octyloxytrimethoxy Silane, phenyltriethoxysilane, benzyltriethoxysilane, diphenyldimethoxysilane, diphenylvinylethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, tetraphenoxysilane, 1,2-bis (trimethylsiloxy) benzene, 1,3- Examples thereof include hydrolysis condensates such as bis (trimethylsiloxy) benzene, 1,4-bis (trimethylsiloxy) benzene, 1,3-dimethoxytetramethyldisiloxane, and 1,3-diethoxytetramethyldisiloxane.

  In addition, about the compound which has the said phenol group, and (a2) silanol group containing hardening accelerator, a phenol group or a silanol group can be protected by the protective group represented, for example by a following formula. By protecting, the storage stability at room temperature can be improved while maintaining the catalytic activity.

  When the component [A] contains (a2) a curing accelerator, the molar ratio of the hydrogen donor to the epoxy group in the component [A] is preferably 0.01 or more, more preferably 0.03 or more, and 0 .05 or more is particularly preferable. (A2) As a use ratio of the curing accelerator, it is preferable to prepare such that the molar ratio of the hydrogen donor to the epoxy group falls within the above specific range. Specifically, (a1) with respect to 100 parts by mass of the polymer 0.5 parts by mass to 70 parts by mass, preferably 1 part by mass to 50 parts by mass, more preferably 2 parts by mass to 40 parts by mass.

[Photo-alignment group]
[A] It is preferable that a component further has a photo-alignment group. When the component [A] further has a photo-alignment group, the liquid crystal aligning agent has a high-sensitivity photo-alignment property, and can impart liquid crystal alignment ability without using, for example, a rubbing treatment.

  As the photo-alignment group, groups derived from various compounds exhibiting photo-alignment can be adopted. For example, azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, cinnamic acid containing a cinnamic acid or a derivative thereof as a basic skeleton Group having structure, chalcone-containing group containing chalcone or derivative thereof as basic skeleton, benzophenone-containing group containing benzophenone or derivative as basic skeleton, coumarin-containing group having coumarin or derivative thereof as basic skeleton, polyimide or derivative thereof And a polyimide-containing structure containing as a basic skeleton. Of these photo-orientable groups, in view of high orientation ability and ease of introduction, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable.

  The structure of the group having a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton, but is represented by a group derived from the compound represented by the above formula (1) and the formula (2). Preferably, at least one selected from the group consisting of groups derived from the above compounds (hereinafter also referred to as “specific cinnamic acid derivatives”).

In formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group, biphenylene group, terphenylene group and cyclohexylene group are alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms which may have a fluorine atom. , May be substituted with a fluorine atom or a cyano group. R ² is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, —CH═CH—, —NH—, —COO— or —OCO—. a is an integer of 0-3. However, when a is 2 or more, the plurality of R ¹ and R ² may be the same or different. R ³ is a fluorine atom or a cyano group. b is an integer of 0-4. However, when b is 2 or more, the plurality of R ³ may be the same or different. In Formula (2), R ⁴ is a phenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group or cyclohexylene group are a chain or cyclic alkyl group having 1 to 10 carbon atoms, a chain or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom, or a cyano group. May be substituted. R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or —NH—. c is an integer of 1 to 3. However, when c is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group. d is an integer of 0-4. However, when d is 2 or more, the plurality of R ⁶ may be the same or different. R ⁷ is an oxygen atom, —COO— or —OCO—. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. e is an integer of 0-3. However, when e is 2 or more, the plurality of R ⁷ and R ⁸ may be the same or different. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. However, * couple | bonds with a carboxyl group. f and g are each an integer of 1 to 10.

Among these, R ¹ is preferably an unsubstituted phenylene group or a phenylene group substituted with a fluorine atom or an alkyl group having 1 to 3 carbon atoms. R ² is preferably a single bond, an oxygen atom, or —CH ₂ ═CH ₂ —. b is preferably from 0 to 1. When a is plural, b is preferably 0.

  Examples of the compound represented by the formula (1) include a compound represented by the following formula.

  Examples of the compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-2).

  In the above formula, Q is a linear or cyclic alkyl group having 1 to 10 carbon atoms, a linear or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom, or a cyano group. f is synonymous with e in Formula (2).

The procedure for synthesizing the specific cinnamic acid derivative is not particularly limited, and can be performed by combining conventionally known methods. As a typical synthesis procedure, for example, a method of obtaining a specific cinnamic acid derivative by reacting a compound having a benzene ring skeleton substituted with a halogen atom under a basic condition with acrylic acid in the presence of a transition metal catalyst;
Under basic conditions, cinnamic acid in which the hydrogen atom of the 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 to obtain a specific cinnamic acid derivative. Methods and the like.

<Synthesis Method of [A] Component Having Photo-Orienting Group>
The [A] component having a photo-alignable group can be synthesized, for example, by reacting the above-described polymer having an epoxy group and silanol group with a specific cinnamic acid derivative, preferably in the presence of a catalyst.

  Here, the use amount of the specific cinnamic acid derivative is preferably 0.001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and more preferably 0.05 mol to 2 mol with respect to 1 mol of the epoxy group of the polysiloxane. Mole is particularly preferred.

  As said catalyst, the well-known compound which accelerates | stimulates reaction with an organic base or an epoxy compound, and an acid anhydride can be used. As said organic base, the thing similar to what was mentioned above is mentioned, for example.

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

  Among these catalysts, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

  As a usage-amount of a catalyst, 100 mass parts or less are preferable with respect to 100 mass parts of polymers which have an epoxy group and a hydrogen donor, 0.01 mass part-100 mass parts are more preferable, 0.1 mass part-20 Part by mass is particularly preferred.

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

  [A] component which has a photo-alignment group is compoundable in presence of an organic solvent as needed. Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent has a solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution), preferably 0.1% by mass to 70% by mass, more preferably 5% by mass to 50% by mass. % Is used in an amount of less than%.

  This synthesis method is simple and is a very suitable method in that the introduction rate of the structure derived from the specific cinnamic acid derivative can be increased.

  Although it does not specifically limit as Mw of the [A] component which has a photo-alignment group obtained in this way, 1,000-20,000 are preferable and 2,000-15,000 are more preferable. By setting it as such a molecular weight range, the favorable orientation and stability of a liquid crystal aligning film are securable.

  Moreover, you may replace and use a part of said specific cinnamic acid derivative by the compound represented by following formula (4) in the range which does not impair the effect of this invention. In this case, the synthesis of the component [A] having a photo-alignment group is performed by reacting, for example, a polymer having an epoxy group and a hydrogen donor, and a mixture of a specific cinnamic acid derivative and a compound represented by the following formula (4). Is done.

R ¹⁰ in the above formula (4) is preferably an alkyl group or alkoxy group having 8 to 20 carbon atoms, or a fluoroalkyl group or fluoroalkoxy group having 4 to 21 carbon atoms. R ¹¹ is preferably a single bond, a 1,4-cyclohexylene group or a 1,4-phenylene group. R ¹² is preferably a carboxyl group.

  Examples of the compound represented by the above formula (4) include compounds represented by the following formulas (4-1) to (4-3).

  The compound represented by the above formula (4) can contribute to improving the stability of the liquid crystal aligning agent by deactivating the active site of the component [A]. In the present invention, when the compound represented by the above formula (4) is used together with the specific cinnamic acid derivative, the total use ratio of the specific cinnamic acid derivative and the compound represented by the above formula (4) 0.001 mol-1.5 mol is preferable with respect to 1 mol of epoxy groups to have, 0.01 mol-1 mol is more preferable, and 0.05 mol-0.9 mol is especially preferable. In this case, the amount of the compound represented by the above formula (4) is preferably 50 mol% or less, more preferably 25 mol% or less, based on the total amount with the specific cinnamic acid derivative. When the proportion of the compound represented by the above formula (4) exceeds 50 mol%, there is a risk of causing a problem that the orientation in the liquid crystal alignment film is lowered.

<[B] Metal chelate compound>
Since the liquid crystal aligning agent contains a [B] metal chelate compound, the [B] metal chelate compound acts as a catalyst, promotes a crosslinking reaction, and exhibits the above effects even at low temperature and short heat treatment. An alignment film can be manufactured. [B] Examples of the metal chelate compound include a zirconium compound, a titanium compound, and an aluminum compound.

  The structures of the zirconium compound, the titanium compound, and the aluminum compound are represented by the following formulas (5-1) to (5-4), for example.

In the above formulas (5-1) to (5-3), R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group, A cycloalkyl group or an alkoxy group. R ¹⁵ , R ¹⁸ and R ²¹ are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group or an alkoxy group. R ^A is a hydrogen atom or a methyl group. p and p ′ are each independently an integer of 0 to 3. p '' is an integer of 0-2. ^However, R 13 ^{to R 21} is, when a plurality of each of a plurality of ^R 13 ^{to R 21} may each be the same or different.
In the above formula (5-4), R ^B represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, a cycloalkyl group, or an alkoxy group. Ar is an aryl group. However, when there are a plurality of R ^B and Ar, the plurality of R ^B and A may be the same or different. R ^c is an alkyl group having 1 to 6 carbon atoms, an aryl group, a cycloalkyl group, or an alkoxy group. p '''is an integer of 0-2. However, if the R ^C is plural, R ^C may be different even in the same.

  As said C1-C6 alkyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group etc. are mentioned, for example. Examples of the alkoxy group having 1 to 16 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, and stearyloxy. Groups and the like. Examples of the aryl group include a phenyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aryl group include a benzyl group.

  Specific aluminum compounds include, for example, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate). ) Aluminum, tris (acetylacetonato) aluminum, monoacetylacetonato-bis (ethylacetoacetate) aluminum, compounds represented by the following formula, and the like.

  Specific zirconium compounds include, for example, tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate). Zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium and the like can be mentioned.

  Specific examples of the titanium compound include titanium compounds such as diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium, and diisopropoxybis (acetylacetone) titanium.

  Among these [B] metal chelate compounds, aluminum compounds are preferable, and diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonato) aluminum, and tris (ethylacetoacetate) aluminum are more preferable.

  These [B] metal chelate compounds can be used alone or in admixture of two or more. Moreover, as a [B] metal chelate compound, the partial hydrolyzate of these metal chelate compounds can also be used. The blending ratio of the [B] metal chelate compound in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the [A] component. preferable. [B] By setting the blending ratio of the metal chelate compound within the above specified range, the crosslinking reaction is promoted, and the liquid crystal alignment film can be produced even at a low temperature for a short time and the storage stability is improved. Can be held.

<[C] Curing inhibitor>
The liquid crystal aligning agent may further contain at least one curing inhibitor selected from the group consisting of [C] β-diketones, β-keto acid esters and basic compounds as suitable components. The liquid crystal aligning agent is excellent in storage stability because the liquid crystal aligning agent further contains a [C] curing inhibitor.

  Examples of β-diketones and β-keto acid esters include acetylacetone, benzoylacetone, dibenzoylacetone, methyl acetoacetate, ethyl acetoacetate, benzoylacetoacetate, ethyl benzoylacetate, and methylbenzoyl acetate.

  Examples of the basic compound include fillers such as calcium carbonate and alumina, and amine-modified products.

  Of these [C] curing inhibitors, β-diketones and β-keto acid esters are preferable, and acetylacetone, methyl acetoacetate, and ethyl acetoacetate are more preferable. In addition, these [C] hardening inhibitors can be used individually or in mixture of 2 or more types. When the liquid crystal aligning agent is blended with a [C] curing inhibitor, the blending ratio of the [C] curing inhibitor is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the [A] component. Part to 500 parts by weight is more preferable, and 2.5 parts to 100 parts by weight is particularly preferable. [C] The storage stability of the liquid crystal aligning agent can be satisfactorily maintained by setting the blending ratio of the curing inhibitor in the specific range.

<Other optional components>
The liquid crystal aligning agent is at least one polymer selected from the group consisting of a polyamic acid, a polyimide and a polymer having no epoxy group (hereinafter referred to as “[D] and others” within the range not impairing the effects of the present invention. And [E] a crosslinking agent, a curing agent, a curing accelerator, a surfactant, a photosensitizer and the like. Hereinafter, each other arbitrary component is explained in full detail.

[[D] Other polymers]
[D] Examples of the other polymer include at least one polymer selected from the group consisting of polyamic acid, polyimide, and a polymer having no epoxy group.

(Polyamic acid)
A polyamic acid is obtained by reacting a tetracarboxylic dianhydride and a diamine compound.

  Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4. , 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene -1,2-dicarboxylic acid Water, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane- 2: 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2010-97188.

  Of these tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides are preferred, and 2,3,5-tricarboxycyclopentylacetic dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride. An anhydride is more preferable, and 2,3,5-tricarboxycyclopentylacetic acid dianhydride is particularly preferable.

  The amount of 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride used is 10 mol% or more based on the total tetracarboxylic dianhydride. And more preferably 20 mol% or more, and it is particularly preferably composed of only 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

  Examples of the diamine compound include aliphatic diamine, alicyclic diamine, diaminoorganosiloxane, and aromatic diamine. These diamine compounds can be used alone or in combination of two or more.

  Examples of the aliphatic diamine include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like.

  Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like.

  Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in Japanese Patent Application No. 2009-97188.

  Examples of the aromatic diamine include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl. 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-pheny Diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4 -Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl)- Piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diamy Benzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2 , 5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy- 2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bi (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4 ′ -Trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-(( Aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) ) Phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, - diallyl aniline, 4-amino-benzylamine, diamines compounds represented by the 3-amino-benzylamine and the following formula can be mentioned.

In the above ^{formula, R 22} is a divalent alkyl group having 1 to 3 carbon atoms, * - O -, * - COO- or * -OCO- is. However, * couple | bonds with a diaminophenyl group. r is 0 or 1. s is an integer of 0-2. t is an integer of 1-20.

  The ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0 with respect to 1 equivalent of the amino group contained in the diamine compound. .2 equivalents to 2 equivalents are preferable, and 0.3 equivalents to 1.2 equivalents are more preferable.

  The synthesis reaction is preferably performed in an organic solvent. The reaction temperature is preferably −20 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C. The reaction time is preferably 0.5 hours to 24 hours, and more preferably 2 hours to 12 hours.

  The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol .

  As the usage-amount (a) of an organic solvent, it is 0.1 mass%-50 with respect to the total (a + b) of the total amount (b) of a tetracarboxylic dianhydride and a diamine compound, and the usage-amount (a) of an organic solvent. % By mass is preferable, and 5% by mass to 30% by mass is more preferable.

  The polyamic acid solution obtained after the reaction may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution. You may use for preparation of a liquid crystal aligning agent, after refine | purifying an acid. Examples of the method for isolating the polyamic acid include a method of pouring a reaction solution into a large amount of a poor solvent and drying a precipitate obtained under reduced pressure, and a method of distilling the reaction solution under reduced pressure using an evaporator. Examples of the method for purifying the polyamic acid include a method in which the isolated polyamic acid is dissolved again in an organic solvent and precipitated with a poor solvent, and a method in which the step of distilling off the organic solvent or the like with an evaporator is performed once or a plurality of times. .

(Polyimide)
The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid to imidize it. The polyimide may be a completely imidized product in which all of the amic acid structure of the precursor polyamic acid has been dehydrated and cyclized, and only a part of the amic acid structure may be dehydrated and cyclized to form an amic acid structure and an imide. It may be a partially imidized product in which a ring structure coexists.

  As a method for synthesizing polyimide, for example, (i) a method of heating polyamic acid (hereinafter sometimes referred to as “method (i)”), (ii) polyamic acid is dissolved in an organic solvent, and dehydration is performed in this solution. Examples thereof include a method based on a dehydration ring-closing reaction of a polyamic acid, such as a method in which an agent and a dehydration ring-closing catalyst are added and heated as necessary (hereinafter sometimes referred to as “method (ii)”).

  As reaction temperature in method (i), 50 to 200 degreeC is preferable and 60 to 170 degreeC is more preferable. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 0.5 hours to 48 hours, and more preferably 2 hours to 20 hours.

  The polyimide obtained in the method (i) may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after isolating the polyimide, or may be obtained after purifying the isolated polyimide. You may use for the preparation of a liquid crystal aligning agent, after refine | purifying the polyimide obtained.

  Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.

  Although the usage-amount of a dehydrating agent is suitably selected by the desired imidation rate, 0.01 mol-20 mol are preferable with respect to 1 mol of amic acid structures of a polyamic acid.

  Examples of the dehydration ring closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine and the like.

  The amount of the dehydration ring closure catalyst used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent contained. In addition, the imidation rate can be increased as the content of the dehydrating agent and the dehydrating ring-closing agent is increased.

  Examples of the organic solvent used in the method (ii) include organic solvents similar to those exemplified as those used for the synthesis of polyamic acid.

  The reaction temperature in method (ii) is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hour to 20 hours, and more preferably 1 hour to 8 hours. By setting the reaction conditions in the above range, the dehydration ring-closing reaction proceeds sufficiently, and the molecular weight of the resulting polyimide can be made appropriate.

  In the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, it may be used for the preparation of the liquid crystal aligning agent. You may use for preparation of an agent, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide. Examples of a method for removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution include a solvent replacement method. Examples of the polyimide isolation method and purification method include the same methods as those exemplified as the polyamic acid isolation method and purification method.

(Polymer without epoxy group)
As a polymer which does not have an epoxy group, if it is a polymer which does not have an epoxy group in a structure, it will not specifically limit. Such a polymer having no epoxy group can be carried out by combining conventionally known methods.

  When the liquid crystal aligning agent contains [D] other polymer, the content ratio of [D] other polymer is different depending on the type of [D] other polymer, but [A] component is 100 masses. The amount is preferably 10,000 parts by mass or less based on parts.

[[E] cross-linking agent]
The liquid crystal aligning agent can contain an [E] crosslinking agent for the purpose of strengthening the crosslinking reaction of the component [A]. By including the [E] crosslinking agent in the liquid crystal alignment agent, the heat treatment in the coating film forming step is sufficient at a low temperature and in a short time, and the liquid crystal alignment film can be produced at low cost and high productivity.

  [E] The crosslinking agent is not particularly limited and known ones can be used, but an epoxy group-containing polyfunctional monomer, an epoxy group-containing polyfunctional oligomer, or an epoxy group-containing polyfunctional polymer is preferable. [E] As a crosslinking agent, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, Epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 2- ( 3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone modified 3, 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3, 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis 3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexyl epoxycyclohexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; one kind of aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin Or polyglycidyl ethers of polyether polyols obtained by adding two or more alkylene oxides; Diglycidyl esters of basic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide; glycidyl esters of higher fatty acids; epoxidation Examples include soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil; epoxidized polybutadiene and the like.

  Among these [E] crosslinking agents, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F di Ricidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether are preferred, More preferred are compounds having two or more alicyclic epoxy groups in one molecule such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. .

  Examples of commercially available products include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide. 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403 (above, manufactured by Daicel Chemical Industries), KRM-2100, KRM-2110, KRM-2199, KRM- 2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (above, manufactured by Asahi Denka Kogyo), CER-4221, CER-422 -E, CER-4221-H (above, made by Darian Trico Chemical), Rapi-cure DVE-3, CHVE, PEPC (above, made by ISP) Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, Japan Epoxy Resin), XDO (Toagosei Co., Ltd.), VECOMER 2010, 2020, 4010, and 4020 (above, Allied Signal).

  [E] A crosslinking agent can be used individually or in mixture of 2 or more types. Furthermore, as said epoxy group containing polyfunctional polymer, the above-mentioned (a1) polymer etc. can be used, for example.

  When the liquid crystal aligning agent is blended with the [E] crosslinking agent, the blending ratio of the [E] crosslinking agent is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the [A] component, and 1 part by weight. -30 mass parts is preferable, and 2 mass parts-20 mass parts is more preferable.

[Curing agent and curing accelerator]
A hardening | curing agent can be contained in order to make the crosslinking reaction of [A] component stronger. Moreover, the said hardening accelerator can be contained in the said liquid crystal aligning agent in order to accelerate | stimulate the hardening reaction which a hardening | curing agent controls.

  As the curing agent, a curable compound having an epoxy group or a curing agent generally used for curing a curable composition containing a compound having an epoxy group can be used. Examples include acid anhydrides, polyvalent carboxylic acids, and polyvalent carboxylic acid esters.

  Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides. Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4- And tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride and the like. . Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, Diels of maleic anhydride and alicyclic compounds having conjugated double bonds such as α-terpinene and allocymene in addition to compounds represented by the formula and tetracarboxylic dianhydrides generally used for the synthesis of polyamic acids Examples include Alder reaction products and hydrogenated products thereof.

  In said formula, u is an integer of 1-20.

  Examples of the polyvalent carboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid. Acid, 1,2,4,5-cyclohexanetetracarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 4-methylphthalic acid, 4,4-dicarboxydiphenyl ether, 4,4-biphenyldicarboxylic acid, benzophenone-4,4 -Dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, trimellitic acid, pyromellitic acid, 1,3,5-tris (4-carboxyphenyl) benzene and the like.

  In addition, about the said polyvalent carboxylic acid, a carboxyl group can be protected by the protecting group represented, for example by a following formula. By protecting, the cross-linking reaction of the component [A] can be strengthened while improving the storage stability at room temperature.

In the above formula, R ²⁵ is a hydrocarbon group having 1 to 10 carbon atoms.

  As a usage-amount of a hardening | curing agent, 100 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 50 mass parts or less are more preferable.

  Examples of the curing accelerator include imidazole compounds; quaternary phosphorus compounds; quaternary amine compounds; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; zinc octylate , Organometallic compounds such as tin octylate and aluminum acetylacetone complex; boron compounds such as boron trifluoride and triphenylborate; metal halogen compounds such as zinc chloride and stannic chloride; addition of dicyandiamide, amine and epoxy resin High melting point dispersion type latent curing accelerators such as amine addition type accelerators, etc .; microcapsule type latent curing accelerators coated with polymer on the surface of quaternary phosphonium salts, etc .; amine salt type latent curing accelerators Agents: High temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

  As a usage-amount of a hardening accelerator, 20 mass parts or less are preferable with respect to 100 mass parts of [A] polymers.

[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

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

[Photosensitizer]
The photosensitizer that can be contained in the liquid crystal aligning agent includes a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = A compound having at least one group selected from the group consisting of CH ₂ and SO ₂ Cl and a photosensitizing structure. By reacting the epoxy group-containing polysiloxane with a mixture of a specific cinnamic acid derivative and a photosensitizer, the [A] component having a photoalignable group is synthesized, and a photosensitive structure derived from the specific cinnamic acid derivative ( Cinnamic acid structure) and a photosensitizing structure derived from a photosensitizer. This photosensitizing structure has a function of being excited by light irradiation and giving this excitation energy to the adjacent photosensitive structure in the polymer. This excited state may be a singlet or a triplet, but is preferably a triplet in view of long life and efficient energy transfer. The light absorbed by the photosensitizing structure is preferably ultraviolet rays or visible rays having a wavelength in the range of 150 nm to 600 nm. Light with a wavelength shorter than the above lower limit cannot be used in a photo-alignment method because it cannot be handled by a normal optical system. On the other hand, light having a wavelength longer than the above upper limit has a small energy and hardly induces an excited state of the photosensitizing structure.

  Examples of such photosensitizing structures include acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure, fluorene structure, naphthalene structure, anthracene structure, acridine structure, indole structure, etc. Or in combination of two or more. These photosensitizing structures are groups obtained by removing 1 to 4 hydrogen atoms from acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene, acridine or indole, respectively. A structure consisting of Here, each of the acetophenone structure, the carbazole structure, and the indole structure is preferably a structure composed of groups obtained by removing 1 to 4 hydrogen atoms of the benzene ring of acetophenone, carbazole, or indole. Among these photosensitizing structures, it is preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure. Particularly preferred is at least one selected from the group consisting of a structure and a nitroaryl structure.

  The photosensitizer is preferably a compound having a carboxyl group and a photosensitizing structure, and more preferable compounds include compounds represented by the following formulas (H-1) to (H-10).

  In the above formulas (H-1) to (H-10), q is an integer of 1 to 6.

  [A] component having a photo-alignment group is combined with the above-mentioned epoxy group-containing polysiloxane and the specific cinnamic acid derivative, and combined with a photosensitizer, preferably in the presence of a catalyst, preferably in an organic solvent. Can be synthesized.

  In this case, the amount of the specific cinnamic acid derivative used is preferably 0.001 mol to 10 mol, more preferably 0.01 mol to 5 mol, relative to 1 mol of silicon atom of the epoxy group-containing polysiloxane. 05 mol to 2 mol is particularly preferred. The amount of the photosensitizer used is preferably from 0.0001 mol to 0.5 mol, more preferably from 0.0005 mol to 0.2 mol, based on 1 mol of silicon atom in the epoxy group-containing polysiloxane. 0.001 mol to 0.1 mol is particularly preferable.

<Method for preparing liquid crystal aligning agent>
The liquid crystal aligning agent contains the [A] component and the [B] metal chelate compound as essential components, and may contain optional components as necessary. Preferably, each component is dissolved in an organic solvent. It is prepared as a composition.

  As an organic solvent, the thing which melt | dissolves a [A] component, a [B] metal chelate compound, and arbitrary components, and does not react with these is preferable. The organic solvent that can be preferably used in the liquid crystal aligning agent varies depending on the type of [D] other polymer that is optionally contained.

  Preferred organic solvents in the case where the liquid crystal aligning agent contains [A] component, [B] metal chelate compound and [D] other polymer include organic solvents exemplified as those used for the synthesis of polyamic acid. It is done. These organic solvents can be used alone or in combination of two or more.

  As a solvent used for the preparation of the liquid crystal aligning agent capable of being cured at low temperature, a solvent having a low boiling point is preferable, and a solvent that has little influence on the base material to which the aligning agent is applied is preferable. For example, cyclohexane, cyclopentanone, cyclohexanone, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, methylproxitol, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, acetic acid tert-butyl, isobutyl acetate, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, propylene glycol monomethyl ether, ethyl cellosolve, 2,3-pentanedione, 1,2-dimethoxyethane, 1,1 -Diethoxyethane, 1,2-diethoxyethane, etc. are mentioned. Further, for the purpose of improving the solubility and coating property, a low boiling point solvent and a high boiling point solvent can be used in combination with a distribution that does not prevent low temperature curing.

The solid content concentration of the liquid crystal aligning agent, that is, the ratio of the mass of all components other than the solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, Preferably they are 0.2 mass%-10 mass%. If the solid content concentration is less than 0.2% by mass, the film thickness of the liquid crystal alignment film formed from the liquid crystal aligning agent may be too small to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by mass, the film thickness of the coating film may be excessive and a good liquid crystal alignment film may not be obtained. There may be a shortage. The range of the preferable solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, the range of the solid content concentration in the case of the spinner method is preferably 1.5% by mass to 4.5% by mass. In the case of the printing method, it is preferable that the solid content concentration is in the range of 3% by mass to 9% by mass, and thereby the solution viscosity is in the range of 12 mPa · s to 50 mPa · s. In the case of the ink jet method, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, and thereby the solution viscosity is preferably in the range of 3 mPa · s to 15 mPa · s.

<Liquid crystal alignment film, retardation film and method for producing retardation film>
In the present invention, a liquid crystal alignment film formed of the liquid crystal alignment agent, a liquid crystal alignment film including regions having different directions of liquid crystal alignment ability, a retardation film including these liquid crystal alignment films, and a liquid crystal display element for 3D video The retardation film used is also suitably included. The liquid crystal alignment film manufactured from the liquid crystal alignment agent is excellent in adhesion, film hardness and liquid crystal alignment even in low-temperature heat treatment, and in particular, a manufacturing method excellent in productivity such as a roll-to-roll method. It is suitable for production of the used retardation film.

The method for producing the retardation film is as follows:
(1) A step of applying the liquid crystal aligning agent on a substrate to form a coating film (hereinafter also referred to as “step (1)”),
(2) A step of irradiating the coating film with radiation to form a liquid crystal alignment film for retardation film (hereinafter also referred to as “process (2)”), and (3) polymerization on the liquid crystal alignment film for retardation film. Step of applying and curing a functional liquid crystal (hereinafter also referred to as “step (3)”)
Have

  According to this production method, it is possible to produce a retardation film having excellent adhesion, film hardness and liquid crystal orientation with low cost and high productivity. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, the liquid crystal aligning agent is applied onto the substrate to form a coating film. Examples of the coating method include a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber doctor coater method, an offset gravure coater method, and a single roll kiss coater method. , Reverse kiss coater method with small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method, forward rotation roll coater method, blade coater method, knife coater method, Appropriate coating methods such as impregnation coater method, MB coater method, MB reverse coater method and the like can be mentioned. Next, a coating film is formed by heat-treating the coated surface. As temperature of heat processing, 40 to 120 degreeC is preferable and 90 to 110 degreeC is more preferable. The heat treatment time is preferably 0.1 minute to 15 minutes, and more preferably 1 minute to 10 minutes. The film thickness of the coating film is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

  Examples of the material of the base material include transparent substrates including plastic base materials such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, and polycarbonate. In particular, TAC is generally used as a protective layer for polarizing films that bear important functions in LCDs. In many cases, a retardation film is used in combination with a polarizing film. The retardation film needs to be precisely controlled and bonded to an angle at which desired optical characteristics can be exhibited with respect to the polarization axis of the polarizing film. Therefore, a liquid crystal alignment film capable of aligning liquid crystals in an arbitrary direction by a photo-alignment method is formed on a TAC film, and a polymerizable liquid crystal is applied and cured so as to exhibit desired optical characteristics. If a phase difference film can be produced, the pasting process of the conventional polarizing film and phase difference film can be omitted, which contributes to productivity improvement. Furthermore, it contributes to reducing the size and weight of the LCD material, and can be applied to flexible displays. However, the TAC film is characterized by poor solvent resistance, and the solvent that can be used for forming the alignment film is limited, and a highly soluble solvent such as NMP cannot be used. In addition, the TAC film has low heat resistance and cannot be processed at a high temperature for forming an alignment film.

  Furthermore, the liquid crystal aligning agent can be used as a liquid crystal aligning film after being applied on an LCD component member such as a color filter or an optical film including a polarizing plate and a retardation film, and passing through step (2) described later. In addition, the liquid crystal aligning agent can be applied on the retardation film manufactured using the liquid crystal aligning agent, and the liquid crystal aligning film can be used through the same process.

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

[Step (2)]
In this step, the coating film is irradiated with radiation to form a liquid crystal alignment film for retardation film. Examples of the radiation include ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. The radiation may be polarized or non-polarized. In the case of polarized light, it may be linearly polarized light or partially polarized light. Note that “non-polarized light” in this specification is included in “non-polarized light” if it is substantially non-polarized light even if it is partially polarized light.

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

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

The irradiation dose of ^radiation, preferably less than ^{1J / m 2 ~10,000J / m 2} , more preferably ^{10J / m 2 ~3,000J / m 2} , 20J / m 2 ~1,000J / m 2 is particularly preferable. When imparting liquid crystal alignment ability to a coating film formed from a conventionally known liquid crystal aligning agent by a photo-alignment method, a radiation irradiation amount of 10,000 J / m ² or more is required, and the liquid crystal aligning agent is used. Even when the radiation irradiation amount in the photo-alignment method is 3,000 J / m ² or less, and even 1,000 J / m ² or less, good liquid crystal aligning ability can be imparted, which contributes to the reduction of manufacturing cost.

[Step (3)]
In this step, a polymerizable liquid crystal is applied to the liquid crystal alignment film for retardation film and cured. Examples of the method for applying the polymerizable liquid crystal include appropriate application methods such as a roll coater method, a spinner method, a printing method, and an ink jet method.

  The polymerizable liquid crystal is not particularly limited as long as it is a compound that can be polymerized by heating and / or radiation irradiation. For example, it may be a nematic liquid crystal compound as described in UV curable liquid crystal and its application (see Liquid Crystal Vol. 3, No. 1, 1999, pages 34 to 42), or may be a mixture with a plurality of compounds. Moreover, a well-known photoinitiator or thermal polymerization initiator may be included. These polymerizable liquid crystal compounds and mixtures thereof can be used by dissolving in an appropriate solvent. Further, a liquid crystal having a twisted nematic orientation twisted in a direction perpendicular to the substrate by adding a chiral agent or the like, a cholesteric liquid crystal, or a discotic liquid crystal may be used.

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

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

Examples of radiation when irradiating with radiation include non-polarized ultraviolet rays. The irradiation dose of the radiation ^is preferably ^{1,000J / m 2 ~100,000J / m 2} , 10,000J / m 2 ~50,000J / m 2 is more preferable.

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

<Manufacturing method of retardation film provided with liquid crystal alignment film including regions having different directions of liquid crystal alignment ability>
Using the liquid crystal aligning agent, a retardation film including a liquid crystal alignment film including regions having different directions of liquid crystal alignment ability can also be produced. Such a retardation film can be suitably used for 3D video applications and the like.

As a method for producing a retardation film comprising a liquid crystal alignment film containing regions having different directions of the liquid crystal alignment ability,
The above step (2)
(2-1) A step of irradiating a part or all of the coating film with the first radiation, and (2-2) a second part of the coating film having a different incident direction or polarization direction from the first radiation. Or (2-1 ″) a step of irradiating a part of the coating film with the first radiation, and (2-2 ″) all of the coating film is different from the first radiation. Irradiating a second radiation having an incident direction or a polarization direction.
Preferably, it is a manufacturing method which has the process of said (2-1) and (2-2).

In addition, as another method for producing a retardation film including a liquid crystal alignment film including regions having different directions of the liquid crystal alignment ability,
The production method is preferably a step in which the step (2-2) is a step of irradiating at least a portion of the coating film (2-2 ′) that has not been irradiated with the second radiation.

  As the second incident direction or polarization direction in the steps (2-2) and (2-2 ′), liquid crystal alignment ability is imparted by radiation irradiation in the step (2-1) or (2-1 ″). However, it is preferably 70 ° to 110 °, more preferably 85 ° to 95 °, and most preferably 90 °. Examples of means for irradiating in different incident directions include a method of irradiating radiation through a mask. The mask is preferably patterned in a strip shape so that transmissive portions and light shielding portions are alternately arranged.

<Liquid crystal display element>
The present invention includes a liquid crystal display device including a liquid crystal alignment film formed from the liquid crystal alignment agent. The liquid crystal display element of the present invention is excellent in liquid crystal orientation.

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

<Method for manufacturing liquid crystal display element>
The liquid crystal display element can be manufactured, for example, as follows. A liquid crystal alignment film is formed on the substrate by applying the liquid crystal alignment agent on the substrate and then heating the coated surface. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic polyolefin, or the like can be used. A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

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

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

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

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

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

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

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

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

<Synthesis of [A] Component>
[(A1) Synthesis of polymer]
[Synthesis Example 1]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone (MIBK) and triethylamine 10 0.0 g was charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2% by mass ammonium nitrate aqueous solution until the water after washing becomes neutral, and then has an epoxy group and a silanol group by distilling off the solvent and water under reduced pressure. The polymer (a1-1) was obtained as a viscous transparent liquid.

As a result of ¹ H-NMR analysis of this (a1-1), a peak based on an epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and a side reaction of the epoxy group during the reaction. Was confirmed not to happen. Mw of the obtained (a1-1) was 2,200, and the epoxy equivalent was 186 g / mol. The amount of silanol groups contained in (a1-1) was calculated by performing ²⁹ Si-NMR analysis. From the integrated intensity ratio of the peak derived from the component having no silanol group of about 68 ppm (T3 component) and the peak derived from the component having a silanol group of about 58 ppm (T2 component), the ratio of the T3 component to the T2 component is 100: 8. 2 As a result of calculation assuming that the T3 component has one epoxy and the T2 component has one epoxy and one silanol, the molar ratio of the silanol group to the epoxy group was 0.076.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile), 3 parts by mass of α-methylstyrene dimer and 220 parts by mass of diethylene glycol methyl ethyl ether (EDM). It is. Subsequently, 40 parts by mass of epoxycyclohexylmethyl methacrylate, 20 parts by mass of methacrylic acid, 20 parts by mass of tetrahydrofurfuryl methacrylate and 20 parts by mass of 2-hydroxyethyl methacrylate were charged and the mixture was gently agitated. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a1-2). The resulting polymer solution had a solid content concentration of 32.0% by mass. The Mw of (a1-2) was 8,200.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), 3 parts by weight of α-methylstyrene dimer and 220 parts by weight of EDM. Subsequently, 100 parts by weight of epoxycyclohexylmethyl methacrylate was charged, and the atmosphere was purged with nitrogen, followed by gentle heating and stirring. The solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a1-3). It was. The obtained polymer solution was dropped into hexane and reprecipitated. The polymer was recovered by filtration and then dried to obtain a white powdery polymethacrylate copolymer having an epoxy group. Mw of (a1-3) was 8,000.

<Synthesis of specific cinnamic acid derivatives>
[Synthesis Example 4]
All synthetic reactions of specific cinnamic acid derivatives were carried out in an inert atmosphere.
In a 500 mL three-necked flask equipped with a condenser tube, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide were mixed. Next, 7 g of acrylic acid was added to the solution with a syringe and stirred. This mixed solution was further heated and stirred at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. 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 (mass ratio) solution of ethyl acetate and hexane, 8.4 g of a specific cinnamic acid derivative (K-1) represented by the following formula (K-1) was obtained. .

[Synthesis Example 5]
In a 300 mL three-necked flask equipped with a condenser, 6.5 g of 4-fluorophenylboronic acid, 10 g of 4-bromocinnamic acid, 2.7 g of tetrakistriphenylphosphine palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran, and 39 mL of pure water were mixed. Subsequently, the reaction solution was heated and stirred at 80 ° C. for 8 hours, and the completion of the reaction was confirmed by TLC. The reaction solution was cooled to room temperature, poured into 200 mL of 1N hydrochloric acid aqueous solution, and the precipitated solid was separated by filtration. The obtained solid was dissolved in ethyl acetate and subjected to liquid separation washing in the order of 100 mL of 1N hydrochloric acid aqueous solution, 100 mL of pure water, and 100 mL of saturated saline. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was vacuum-dried to obtain 9 g of a specific cinnamic acid derivative (K-2) represented by the following formula (K-2).

[Synthesis Example 6]
A specific cinnamic acid derivative (K-3) was synthesized according to the following scheme. In a 1,000 mL three-necked flask equipped with a condenser tube, 11.2 g of 4-fluorophenol, 25.5 g of ethyl (2E) -3- (4-bromophenyl) -2-propenoic acid, tripotassium phosphate in a nitrogen atmosphere 42.5 g, palladium acetate 0.45 g, 2- (di-tert-butylphosphino) biphenyl 0.90 g, and toluene 300 mL were mixed, and the mixture was heated and stirred at 100 ° C. for 24 hours. The reaction solution was cooled to room temperature and the precipitate was removed by filtration, and then mixed with 300 mL of ethyl acetate. Separated and washed four times with 200 mL of 1M aqueous sodium hydroxide and 200 mL of distilled water. After concentrating the organic layer, the obtained solid was recrystallized from ethanol to obtain 27.5 g of the following intermediate (1). A 300 mL three-necked flask equipped with a condenser tube was mixed with 27.5 g of intermediate (1), 12.1 g of lithium hydroxide monohydrate, 100 mL of methanol, and 50 mL of distilled water, and heated and stirred at reflux for 2 hours. The reaction solution was cooled to room temperature, mixed with 300 mL of diluted hydrochloric acid, acidified, and extracted with 300 mL of ethyl acetate. The organic layer was station washed 4 times with 100 mL of distilled water and then concentrated. The obtained solid was recrystallized with ethanol to obtain 20.33 g of a specific cinnamic acid derivative (K-3).

[Synthesis Example 7]
In a 500 mL three-necked flask equipped with a condenser tube, 19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide were mixed. Next, 7 g of acrylic acid was added to the mixed solution with a syringe and stirred. This mixed solution was further heated and stirred at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. 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 (mass ratio) solution of ethyl acetate and hexane, 10.2 g of a specific cinnamic acid derivative (K-4) represented by the following formula (K-4) was obtained. .

[Synthesis Example 8]
A specific cinnamic acid derivative (K-5) was synthesized according to the following scheme. A 1-L eggplant-shaped flask was charged with 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone, stirred at room temperature for 1 hour, and then 99.7 g of 1-bromopentane. And stirred at 100 ° C. for 5 hours. After completion of the reaction, water was added to precipitate the reaction product, which was collected by filtration. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate and refluxed for 3 hours to perform a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 102 g of white crystals of the compound (K-5). 10.41 g of this compound (K-5) was placed in a reaction vessel, and 100 mL of thionyl chloride and 77 μL of N, N-dimethylformamide were added thereto, followed by stirring at 80 ° C. for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution. Next, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran and 100 mL of water were charged into a 500 mL three-necked flask different from the above. The aqueous solution was ice-cooled, the tetrahydrofuran solution was slowly added dropwise, and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction mixture was neutralized by adding hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, concentrated, and recrystallized from ethanol to give a white cinnamic acid derivative (K-5). 9.0 g of crystals were obtained.

<Synthesis of [A] Component Having Photo-Orienting Group>
[Synthesis Example 9]
In a 100 mL three-necked flask, (a1) 4.6 g of (a1-1) as a polymer, 31 g of MIBK, 3 g of (K-1) as a specific cinnamic acid derivative and a quaternary amine salt (manufactured by San Apro, UCAT 18X) 10 g was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, methanol was added to precipitate the reaction product, which was collected by filtration. The precipitate was dissolved in ethyl acetate, this solution was washed with water three times, and then the solvent was distilled off to obtain 6.3 g of [A] component (A-1) having a photo-alignable group as a white powder. It was. Mw of (A-1) was 3,900.

[Synthesis Example 10]
Except that 3 g of (K-2) as a specific cinnamic acid derivative was used, the same operation as in Synthesis Example 9 was carried out to prepare 7.0 g of [A] component (A-2) having a photo-alignable group as a white powder. Obtained. Mw of (A-2) was 4,200.

[Synthesis Example 11]
In a 200 mL three-necked flask, (a1) 4.3 g of (a1-1) as a polymer, 62.0 g of dimethylacetamide, 3 g of (K-3) as a specific cinnamic acid derivative, and a quaternary amine salt (manufactured by San Apro, UCAT) 18X) 0.10 g was charged and stirred at 110 ° C. for 9 hours. After completion of the reaction, reprecipitation is performed with methanol, and the precipitate is dissolved in ethyl acetate to obtain a solution. The solution is washed three times with water, and then the solvent is distilled off to thereby have a photo-alignment group [A]. 7.0g of components (A-3) were obtained as white powder. Mw of (A-3) was 4,300.

[Synthesis Example 12]
A white powder of [A] component (A-4) having a photo-alignable group was obtained in the same manner as in Synthesis Example 9 except that 3.1 g of (K-4) as a specific cinnamic acid derivative was used. .5 g was obtained. The Mw of (A-4) was 3,900.

[Synthesis Example 13]
In a 200 mL three-necked flask, (a1) 5.0 g of (a1-1) as a polymer, 46.4 g of MIBK, 4.76 g of (K-5) as a specific cinnamic acid derivative, and a quaternary amine salt (UCAT 18X, Sunapro) 0.10 g) was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, methanol was added to precipitate the reaction product, which was collected by filtration. The precipitate was dissolved in ethyl acetate, this solution was washed with water three times, and then the solvent was distilled off to obtain 2.8 g of [A] component (A-5) having a photoalignable group as a white powder. It was. The Mw of (A-5) was 10,100.

[Synthesis Example 14]
In a 100 mL three-necked flask, (a1) 4.9 g of (a1-3) as a polymer, 31.6 g of methyl isobutyl ketone, 3 g of (K-1) as a specific cinnamic acid derivative, and a quaternary amine salt (manufactured by San Apro, UCAT 18X) 0.10 g was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation is performed with methanol, and the precipitate is dissolved in ethyl acetate to obtain a solution. The solution is washed three times with water, and then the solvent is distilled off to thereby have a photo-alignment group [A]. 7.9g of components (A-6) were obtained as white powder. The Mw of (A-6) was 14,000.

<Preparation of liquid crystal aligning agent>
[Example 1]
(A-1) 30 parts by mass of aluminum compound (Aluminum Chelate A (W)) (B-1) as a [B] metal chelate compound is added to 1,000 parts by mass of MIBK and methyl ethyl ketone ( MEK) was mixed to obtain a solution having a solvent composition of MIBK: MEK = 70: 30 (mass ratio) and a solid content concentration of 3.0 mass%. A liquid crystal aligning agent (S-1) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 2]
(B-1) 30 parts by mass as (B) metal chelate compound and (a2) 1,000 parts by mass of (A-1) represented by the above formula (6-1) as a silanol group-containing curing accelerator. 400 parts by mass of triphenylsilanol (a2-1) was added, and MIBK and MEK were further mixed to obtain a solution having a solvent composition of MIBK: MEK = 70: 30 (mass ratio) and a solid content concentration of 3.0% by mass. . A liquid crystal aligning agent (S-2) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 3]
(B-1) 30 parts by mass as (B) metal chelate compound, (a2) 300 parts by mass (a2-1) as silanol group-containing curing accelerator, and [C ] 500 parts by mass of ethyl acetoacetate (C-1) as a curing inhibitor was added, MIBK and MEK were further mixed, the solvent composition was MIBK: MEK = 80: 20 (mass ratio), and the solid content concentration was 3.0. A mass% solution was obtained. A liquid crystal aligning agent (S-3) was prepared by filtering this solution through a filter having a pore size of 1 μm.

[Example 4]
The solution containing (a1-2) is converted to (a1-2) and takes an amount corresponding to 600 parts by mass, and (A-1) 400 parts by mass, [B] (B) B-1) 20 parts by mass and (a2) 100 parts by mass of (a2-1) as a silanol group-containing curing accelerator, MIBK and EDM are further mixed, and the solvent composition is MIBK: EDM = 70: 30 (mass) Ratio) and a solid content concentration of 3.0% by mass. A liquid crystal aligning agent (S-4) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 5]
(B-1) 30 parts by mass as (B) metal chelate compound in (A-1) 1,000 parts by mass, (a2) 200 parts by mass as silanol group-containing curing accelerator, and [E ] 50 parts by mass of a polyfunctional epoxy compound (Dacel Chemical Industries, Celoxide 2021P) as a crosslinking agent is added, and MIBK and MEK are further mixed. The solvent composition is MIBK: MEK = 90: 10 (mass ratio), solid content concentration Was 3.0% by mass. A liquid crystal aligning agent (S-5) was prepared by filtering this solution through a filter having a pore size of 1 μm.

[Example 6]
(A-1) 500 parts by mass and (a1) (a1-1) 500 parts by mass as a polymer, (B-1) 40 parts by mass as a metal chelate compound, (a2) Silanol group-containing curing acceleration (A2-1) 200 parts by mass as an agent, and MIBK and MEK are further mixed, and the solvent composition is MIBK: MEK = 70: 30 (mass ratio) and the solid content concentration is 3.0% by mass. did. The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent (S-6).

[Example 7]
(A-6) 200 parts by mass of 1,000 parts by mass of (B-1) 30 parts by mass as a metal chelate compound and (a2) triphenylsilanol (a2-1) as a silanol group-containing curing accelerator In addition, MIBK and MEK were further mixed to obtain a solution having a solvent composition of MIBK: MEK = 70: 30 (mass ratio) and a solid content concentration of 3.0 mass%. A liquid crystal aligning agent (S-7) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 8]
(A-2) 200 parts by mass of 1,000 parts by mass of (B-1) 30 parts by mass as a metal chelate compound and (a2) triphenylsilanol (a2-1) as a silanol group-containing curing accelerator In addition, 1,2-diethoxyethane was further mixed to obtain a solution having a solid concentration of 3.0% by mass. A liquid crystal aligning agent (S-8) was prepared by filtering this solution through a filter having a pore size of 1 μm.

[Example 9]
(A-3) 200 parts by mass of 1,000 parts by mass of (B-1) 30 parts by mass as a metal chelate compound and (a2) triphenylsilanol (a2-1) as a silanol group-containing curing accelerator Further, butyl acetate was further mixed to obtain a solution having a solid concentration of 3.0% by mass. A liquid crystal aligning agent (S-9) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 10]
(A-4) 30 parts by mass of (B-1) as a metal chelate compound [B] and 200 parts by mass of triphenylsilanol (a2-1) as a silanol group-containing curing accelerator in 1,000 parts by mass In addition, MIBK was further mixed to obtain a solution having a solid concentration of 3.0% by mass. A liquid crystal aligning agent (S-10) was prepared by filtering this solution through a filter having a pore size of 1 μm.

[Example 11]
An amount corresponding to 1,000 parts by mass in terms of (a1-1) is taken, and 30 parts by mass of (B-1) as a [B] metal chelate compound is added thereto, and MIBK and MEK are further mixed. The solvent composition was MIBK: MEK = 70: 30 (mass ratio), and the solid content concentration was 3.0% by mass. A liquid crystal aligning agent (S-11) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 12]
(A-5) 30 parts by mass of (B-1) as a metal chelate compound [B-1] and 1,000 parts by mass of MIBK and MEK are mixed, and the solvent composition is MIBK: MEK = 70: 30 (mass ratio). A solution having a solid content concentration of 3.0% by mass was obtained. A liquid crystal aligning agent (S-12) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 30]
(A2) A liquid crystal aligning agent (S-13) was prepared in the same manner as in Example 2 except that the silanol group-containing curing accelerator was changed to the compound represented by the above formula (6-2).

[Example 31]
(A2) A liquid crystal aligning agent (S-14) was prepared in the same manner as in Example 2 except that the silanol group-containing curing accelerator was changed to the compound represented by the above formula (6-3).

[Example 32]
(A2) A liquid crystal aligning agent (S-15) was prepared in the same manner as in Example 2 except that the silanol group-containing curing accelerator was changed to the compound represented by the above formula (6-4).

[Example 33]
(A2) A liquid crystal aligning agent (S-16) was prepared in the same manner as in Example 2 except that the silanol group-containing curing accelerator was changed to the compound represented by the above formula (6-5).

[Example 34]
(A2) A liquid crystal aligning agent (S-17) was prepared in the same manner as in Example 2 except that the silanol group-containing curing accelerator was changed to the compound represented by the above formula (6-6).

[Comparative Example 1]
(A-1) 200 parts by mass of (a2) (a2) as a curing accelerator is added to 1,000 parts by mass, and MIBK and MEK are further mixed. The solvent composition is MIBK: MEK = 70: 30 (mass) Ratio) and a solid content concentration of 3.0% by mass. A liquid crystal aligning agent (CS-1) was prepared by filtering this solution through a filter having a pore size of 1 μm.

[Comparative Example 2]
(A-1) 30 parts by mass of a sulfonium salt (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-100) is added to 1,000 parts by mass, MIBK and MEK are further mixed, and the solvent composition is MIBK: MEK = 70: 30 ( Mass ratio) and a solid content concentration of 3.0% by mass. A liquid crystal aligning agent (CS-2) was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

<Evaluation>
The following evaluation was performed about the prepared liquid crystal aligning agent. The results are shown in Table 1.

[Storage stability]
Each liquid crystal aligning agent of Examples 1-10, 30-34, and Comparative Examples 1-2 is each stored on the conditions of 40 degreeC from the preparation day to the 0th day, the 3rd day, the 5th day, and the 14th day. A retardation film was produced in the same manner as in Example 13 described later, and the presence or absence of abnormal domains was observed with a polarizing microscope. The case where no abnormal domain was observed was judged as good (“A”), and the case where an abnormal domain was observed was judged as bad (“B”). Stability was evaluated. However, in the production of the retardation film for use in the storage stability evaluation, the liquid crystal aligning agents of Example 1, Comparative Example 1 and Comparative Example 2 were used as the baking conditions in the step (1) described in Example 13 below. In the case of producing a retardation film, the hot plate at 120 ° C. was used for 10 minutes. In addition, "-" in Table 1 shows that evaluation is not performed.

<Manufacture of retardation film>
[Example 13]
Step (1): The liquid crystal aligning agent (S-1) prepared in Example 1 was applied to one surface of the TAC film using a spinner, and baked on a hot plate at 100 ° C. for 5 minutes to have a film thickness of 0.04 μm. A coating film was formed.
Step (2); Next, the coating film surface is irradiated with polarized ultraviolet rays 300 J / m ² containing a 313 nm emission line perpendicularly from the substrate normal line using a Hg-Xe lamp and a Grand Taylor prism, and a liquid crystal for retardation film An alignment film was formed.
Step (3); Next, a polymerizable liquid crystal (Merck, RMS03-013C) is filtered through a filter having a pore diameter of 0.2 μm on the liquid crystal alignment film for retardation film, and then applied using a spinner, and heated at 60 ° C. The plate was baked for 1 minute, then irradiated with 15,000 J / m ² of non-polarized ultraviolet light containing a 365 nm emission line using an Hg-Xe lamp, and cured to produce a retardation film. .

[Examples 14-22, 35-39 and Comparative Examples 3-4]
A retardation film was produced in the same manner as in Example 13 except that each liquid crystal aligning agent shown in Table 2 was used as the liquid crystal aligning agent.

<Evaluation>
The following evaluation was performed about the manufactured retardation film. The results are shown in Table 2. In addition, “-” in Table 2 indicates that evaluation is not performed.

[Liquid crystal orientation (i)]
About the retardation film manufactured in Examples 13-22, 35-39, and Comparative Examples 3-4, the presence or absence of the abnormal domain was observed with the polarization microscope. When the abnormal domain was not observed, the liquid crystal alignment was good (“A”), and when the abnormal domain was observed, the liquid crystal alignment was judged poor (“B”).

[Liquid crystal orientation (ii)]
For the retardation film (Example 13, Comparative Examples 3 and 4) having an evaluation of the liquid crystal orientation (i) of “B”, the baking condition in the step (1) described in Example 13 is 120. A retardation film was produced by operating in the same manner as in Example 13 except that the temperature was changed to 10 minutes on a hot plate at 0 ° C., and the operation was evaluated in the same manner as in the evaluation of liquid crystal orientation (i).

[Adhesion (i)]
The liquid crystal alignment film for retardation film formed when producing the retardation films of Examples 13 to 22, 35 to 39 and Comparative Examples 3 to 4 was used with an equally spaced spacer having a guide, and 1 mm intervals with a cutter knife. Cuts were made to form a 10 × 10 lattice pattern. Subsequently, the cellophane tape was placed on the lattice pattern and brought into close contact, and then the cellophane tape was peeled off. The cut part of the coating film after peeling off the cellophane tape was observed. Excellent when the number of grids where peeling occurs at the point where the coating film cuts along or intersects the cut line is not confirmed relative to the total number of grid patterns ("A") The case of less than 15% was judged to have good adhesion ("B"), and the case of 15% or more was judged to have poor adhesion ("C").

[Adhesion (ii)]
Moreover, it was the same as that of the said Example 13 except having changed the baking conditions at the time of manufacturing the liquid crystal aligning film for phase difference films of the process (1) described in the said Example 13 with a 120 degreeC hotplate for 10 minutes. A liquid crystal alignment film for a retardation film was produced by operating and evaluated in the same manner as the evaluation of adhesion (i).

[Film hardness (i)]
A liquid crystal alignment film for retardation film was formed in the same manner as in Example 13 except that a glass substrate was used instead of the TAC film in the step (1) described in Example 13. About this liquid crystal aligning film for retardation films, film | membrane hardness was measured with the pencil scratch test machine for coating films. When the pencil hardness measurement result is 3H or more, the film hardness is judged to be excellent ("A"), when it is H or more, the film hardness is judged to be good ("B"), and when it is less than H, the film hardness is poor. ("C").

[Film hardness (ii)]
Moreover, it was the same as that of the said Example 13 except having changed the baking conditions at the time of manufacturing the liquid crystal aligning film for phase difference films of the process (1) described in the said Example 13 with a 120 degreeC hotplate for 10 minutes. A liquid crystal alignment film for retardation film was produced by operating and evaluated in the same manner as the evaluation of film hardness (i).

  As is clear from the results in Tables 1 and 2, it was found that the liquid crystal aligning agent was excellent in storage stability. Moreover, it turned out that the liquid crystal aligning film manufactured from the said liquid crystal aligning agent has the outstanding liquid crystal aligning property, adhesiveness, and film | membrane hardness. Furthermore, when the liquid crystal aligning agent was used, it turned out that the liquid crystal aligning film which is excellent in adhesiveness, film | membrane hardness, and liquid crystal aligning property can be manufactured even if it is low-temperature and short-time heat processing.

<Manufacture of liquid crystal display element (IPS mode)>
[Example 23]
A liquid crystal aligning agent (S-1) is applied to a glass substrate on which a chromium metal electrode is patterned in a comb shape and one surface of an opposing glass substrate on which no electrode is provided, using a spinner, and a 140 ° C. hot The plate was baked for 10 minutes to form a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 300 J / m ² containing a 313 nm emission line perpendicularly from the substrate normal line using a Hg—Xe lamp and a Grand Taylor prism to form a liquid crystal alignment film. The same operation was repeated to produce a pair (two) of substrates on which electrodes were formed and substrates without electrodes. An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface having one liquid crystal alignment film among the above substrates by screen printing, and the liquid crystal alignment film surfaces of a pair of substrates are made to face each other. The adhesive was pressure-bonded so that the projection direction of the optical axis of the ultraviolet ray of each substrate onto the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, a polymerizable liquid crystal (MLC, MLC-7028) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature. Next, a polarizing plate is bonded to both outer surfaces of the substrate, and the liquid crystal display element is bonded by bonding so that the polarization directions are orthogonal to each other and the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface is the same or orthogonal. Manufactured.

[Example 24]
A liquid crystal aligning agent (S-11) is applied to a glass substrate on which a chromium metal electrode is patterned in a comb shape and one surface of an opposing glass substrate on which no electrode is provided using a spinner, and a hot plate at 140 ° C. Was baked for 10 minutes to form a coating film having a thickness of 0.1 μm. Next, the coating film is rubbed with a rubbing machine having a roll wrapped with rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm to impart liquid crystal alignment ability. did. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes. The same operation was repeated to prepare a pair (two) of substrates having a liquid crystal alignment film. An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface having one liquid crystal alignment film among the above substrates by screen printing, and the liquid crystal alignment film surfaces of a pair of substrates are made to face each other. The liquid crystal alignment film surfaces were overlapped and pressed so as to face each other, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, liquid crystal (Merck, MLC-7028) was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature. Next, a liquid crystal display element was manufactured by bonding polarizing plates on both outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other and matched or orthogonal to the alignment direction of the liquid crystal.

[Example 25]
A liquid crystal display device was produced in the same manner as in Example 24 except that the liquid crystal aligning agent (S-1) was used.

<Manufacture of liquid crystal display element (VA mode)>
[Example 26]
A liquid crystal aligning agent (S-12) is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner and baked on a hot plate at 140 ° C. for 10 minutes to form a film having a thickness of 0.1 μm. A film was formed. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 1,000 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the substrate normal using a Hg—Xe lamp and a Grand Taylor prism, and a liquid crystal alignment film did. The same operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film. An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface having one liquid crystal alignment film among the above substrates by screen printing, and the liquid crystal alignment film surfaces of a pair of substrates are made to face each other. The adhesive was pressure-bonded so that the projection direction of the optical axis of the ultraviolet ray of each substrate onto the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling a gap between the substrates from the liquid crystal injection port with negative liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature. Next, a polarizing plate is bonded to both outer surfaces of the substrate, and the polarization directions thereof are orthogonal to each other, and the liquid crystal alignment film is bonded so that an angle of 45 ° is formed with the projection direction of the ultraviolet optical axis of the liquid crystal alignment film onto the substrate surface. A device was manufactured.

[Example 27]
A liquid crystal aligning agent (S-12) is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner and baked on a hot plate at 140 ° C. for 10 minutes to form a film having a thickness of 0.1 μm. A film was formed. An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling a gap between the substrates from the liquid crystal injection port with negative liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature. Next, a liquid crystal display element was manufactured by laminating polarizing plates on both outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other.

<Evaluation>
The following evaluation was performed about the manufactured liquid crystal display element. The results are shown in Table 3.

[Liquid crystal orientation]
The presence or absence of an abnormal domain in the change in brightness when a voltage of 5 V is turned on / off (applied / released) to the liquid crystal display element is observed with an optical microscope, and the case where no abnormal domain is observed is good (“A”). Was observed as bad (“B”).

  As is clear from the results in Table 3, the liquid crystal display element was found to have excellent liquid crystal alignment properties in both the IPS mode and the VA mode. Further, it was found that the alignment method was excellent in liquid crystal alignment, whether it was photo alignment or rubbing treatment.

<Manufacture of a retardation film including a liquid crystal alignment film including regions having different directions of liquid crystal alignment ability>
[Example 28]
After forming the coating film on the substrate by operating in the same manner as in the step (1) described in Example 13, the transmission part and the light-shielding part in the polarization direction rotated by 90 ° from the polarized ultraviolet ray irradiated with the first radiation. A second polarized ultraviolet ray (polarized ultraviolet ray 300 J / m ² including a 313 nm emission line obtained using a Hg-Xe lamp and a Grand Taylor prism) was irradiated through a mask patterned in a strip shape so as to be alternately arranged. Next, after the polymerizable liquid crystal (Merck, RMS03-013C) is filtered through a filter having a pore size of 0.2 μm on the surface on which the liquid crystal alignment film for retardation film is formed, it is applied using a spinner, After baking for 1 minute on a hot plate, the direction of the liquid crystal alignment ability is different by irradiating the surface of the polymerizable liquid crystal with 15,000 J / m ² of non-polarized light containing a 365 nm emission line using a Hg-Xe lamp. A retardation film including a liquid crystal alignment film including a region was produced.

[Example 29]
In the same manner as in step (1) described in Example 13 above, after forming a coating film on the substrate, the first polarized ultraviolet rays (Hg-Xe lamp and Grand Taylor prism are used while half of the substrate is shielded from light. Irradiates polarized ultraviolet rays (300 J / m ² ) containing a 313 nm emission line. Next, the second exposed portion of the ultraviolet light (Hg-Xe) is irradiated so that the exposed portion exposed first in the polarization direction rotated by 90 ° from the first polarized ultraviolet light is shielded and the unexposed portion is irradiated with the polarized ultraviolet light. Polarized ultraviolet rays (300 J / m ² ) including an emission line of 313 nm were performed using a lamp and a Grand Taylor prism. Next, after the polymerizable liquid crystal (Merck, RMS03-013C) is filtered through a filter having a pore size of 0.2 μm on the surface on which the liquid crystal alignment film is formed, it is applied using a spinner, and 1 on a hot plate at 60 ° C. After baking for a minute, using a Hg-Xe lamp, a non-polarized ultraviolet ray of 15,000 J / m ² containing a 365 nm emission line is irradiated on the surface of the polymerizable liquid crystal to be applied to a liquid crystal containing regions having different directions of liquid crystal alignment ability. A retardation film provided with an alignment film was produced.

<Evaluation>
The following evaluation was performed about the retardation film provided with the liquid crystal aligning film containing the area | region where the direction of the manufactured liquid crystal aligning ability differs.

  When a retardation film is placed between polarizing plates placed under crossed Nicols conditions and observed using transmitted light from the opposite direction to the observation side, it is placed so that it is parallel or perpendicular to the polarization direction of the irradiated polarized ultraviolet light The entire surface was dark regardless of patterning. On the other hand, when the retardation film was rotated by 45 ° in the plane, the retardation film became bright all over regardless of patterning, indicating that it had birefringence.

  When the retardation film was observed in the same manner as described above, it was found that the entire surface was dark regardless of the polarization direction of the irradiated polarized ultraviolet rays when the retardation film was arranged in parallel or perpendicular to the polarization direction of the irradiated polarized ultraviolet rays. On the other hand, when the retardation film was rotated by 45 ° in its plane, the retardation film became brighter and birefringent regardless of the polarization direction of the irradiated polarized ultraviolet rays.

  In addition, the polarized ultraviolet light polarized on each of the retardation film obtained in Example 13 and the retardation film including regions having different directions of liquid crystal alignment ability obtained in Example 28 or Example 29 described above. When they are arranged so that the directions are parallel or perpendicular, and observed under the crossed Nicols condition, it has been confirmed that the brightened pattern and the darkened pattern are separated by a clear edge.

  According to the present invention, a liquid crystal aligning agent having excellent storage stability, manufactured using the liquid crystal aligning agent, and having low adhesion at low temperatures and short heat treatment, film hardness and liquid crystal alignment An excellent liquid crystal alignment film, a retardation film including the liquid crystal alignment film, a method for producing the retardation film, and a liquid crystal display element can be provided. Therefore, the liquid crystal aligning agent can be suitably used in a process excellent in productivity such as a roll-to-roll method. In addition, a liquid crystal display element having excellent liquid crystal orientation can be provided, and the liquid crystal display element is used in a driving mode such as TN, STN, IPS, FFS, and VA (including VA-MVA mode, VA-PVA mode, and the like). Can also be suitably applied.

Claims (17)

[A] A component having an epoxy group and a hydrogen donor in the same or different molecules, and [B] a liquid crystal aligning agent containing a metal chelate compound. [A] component is
The liquid crystal aligning agent of Claim 1 containing (a1) the polymer which has an epoxy group, and (a2) the hardening accelerator which has a hydrogen donor.   The liquid crystal aligning agent according to claim 1, wherein the hydrogen donor is a silanol group.   (A1) The liquid crystal aligning agent of Claim 2 or Claim 3 in which a polymer further has a silanol group.   The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the epoxy group is an alicyclic epoxy group.   The liquid crystal aligning agent of any one of Claims 1-5 in which a [A] component further has a photo-alignment group.   The liquid crystal aligning agent according to claim 6, wherein the photoalignable group is a group having a cinnamic acid structure. The group having a cinnamic acid structure is at least one selected from the group consisting of a group derived from a compound represented by the following formula (1) and a group derived from a compound represented by the formula (2) Item 8. A liquid crystal aligning agent according to Item 7.

(In the formula (1),
R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group, biphenylene group, terphenylene group and cyclohexylene group are alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms which may have a fluorine atom. , May be substituted with a fluorine atom or a cyano group.
R ² is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, —CH═CH—, —NH—, —COO— or —OCO—.
a is an integer of 0-3. However, when a is 2 or more, the plurality of R ¹ and R ² may be the same or different.
R ³ is a fluorine atom or a cyano group.
b is an integer of 0-4. However, when b is 2 or more, the plurality of R ³ may be the same or different.
In formula (2),
R ⁴ is a phenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group or cyclohexylene group are a chain or cyclic alkyl group having 1 to 10 carbon atoms, a chain or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom, or a cyano group. May be substituted.
R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or —NH—.
c is an integer of 1 to 3. However, when c is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different.
R ⁶ is a fluorine atom or a cyano group.
d is an integer of 0-4. However, when d is 2 or more, the plurality of R ⁶ may be the same or different.
R ⁷ is an oxygen atom, —COO— or —OCO—.
R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group.
e is an integer of 0-3. However, when e is 2 or more, the plurality of R ⁷ and R ⁸ may be the same or different.
R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. However, * couple | bonds with a carboxyl group.
f and g are each an integer of 1 to 10. ) 9. The method according to claim 1, further comprising at least one curing inhibitor selected from the group consisting of [C] β-diketones, β-keto acid esters, and basic compounds. Liquid crystal aligning agent.   The liquid crystal aligning film formed with the liquid crystal aligning agent of any one of Claims 1-9.   The liquid crystal aligning film of Claim 10 containing the area | region from which the direction of liquid crystal aligning ability differs.   A retardation film comprising the liquid crystal alignment film according to claim 10.   The retardation film according to claim 12, which is used for a liquid crystal display element for 3D video. (1) The process of apply | coating the liquid crystal aligning agent of any one of Claims 1-9 on a board | substrate, and forming a coating film,
(2) A step of irradiating the coating film with radiation to form a liquid crystal alignment film for retardation film, and (3) a step of applying a polymerizable liquid crystal to the liquid crystal alignment film for retardation film and curing it. A method for producing a phase difference film. The above step (2)
(2-1) A step of irradiating a part or all of the coating film with the first radiation, and (2-2) a second part of the coating film having a different incident direction or polarization direction from the first radiation. The method for producing a retardation film according to claim 14, comprising a step of irradiating the radiation. The above step (2-2)
(2-2 ') The method for producing a retardation film according to claim 15, which is a step of irradiating at least the first radiation of the coating film with the second radiation.   A liquid crystal display element provided with the liquid crystal aligning film of Claim 10 or Claim 11.