JP2012058280A - Cholesteric liquid crystal display, method for manufacturing the same, and liquid crystal aligning agent - Google Patents

Abstract

A cholesteric liquid crystal display having high liquid crystal alignment uniformity by including a liquid crystal alignment film having excellent liquid crystal alignment ability, a method for manufacturing the cholesteric liquid crystal display, and a method for forming such a liquid crystal alignment film An object of the present invention is to provide a liquid crystal aligning agent.
The present invention provides a pair of opposing substrates, a cholesteric liquid crystal disposed in each of a plurality of regions between the substrates divided in the vertical direction, and a space between each of the substrates and the cholesteric liquid crystal. A cholesteric liquid crystal display including a liquid crystal alignment film to be laminated, wherein the liquid crystal alignment film on at least one side is formed of a radiation-sensitive liquid crystal alignment agent.
[Selection] Figure 1

Description

  The present invention relates to a cholesteric liquid crystal display, a manufacturing method thereof, and a liquid crystal aligning agent.

  A cholesteric liquid crystal display using cholesteric liquid crystal (chiral nematic liquid crystal) with a predetermined chiral agent added to the base liquid crystal selectively reflects light of a color corresponding to the chiral pitch. And a clear color display can be performed. In addition, cholesteric liquid crystal displays have a property (memory) that keeps the writing state even when the electric field is turned off once the voltage is applied. Therefore, active elements that increase manufacturing costs are used. Even without this, it is possible to display with good quality. Further, according to the cholesteric liquid crystal display, by using this memory property, it is possible to cut off the electric field for driving the liquid crystal when there is no change in the display signal, so that the power consumption can be suppressed. For this reason, application of cholesteric liquid crystal displays to flexible displays such as electronic paper is being studied.

  In this cholesteric liquid crystal display, those corresponding to color display generally have a three-layer structure in which liquid crystal layers corresponding to the three primary colors of blue, green and red are laminated. However, a cholesteric liquid crystal display having such three liquid crystal layers is difficult to manufacture because of its complicated structure, and there is a limit to reducing the thickness because it has a thickness of three layers. Therefore, cholesteric liquid crystal displays having a structure in which the liquid crystals corresponding to the three primary colors are divided and arranged on one plane have been proposed (see Japanese Patent Laid-Open Nos. 2000-267142 and 2007-72419). .

  However, in such a cholesteric liquid crystal display, since a partition for dividing each liquid crystal is provided, a liquid crystal alignment film for imparting alignment to the liquid crystal may not be formed on one plane. That is, in this case, the liquid crystal alignment film is formed in a concavo-convex shape so as to cover the partition walls, or is formed by being divided by the partition walls. In the liquid crystal alignment film formed in such a shape, it is difficult to perform a rubbing process that is usually performed in order to exhibit liquid crystal alignment properties in a desired direction and uniformly. Therefore, the liquid crystal alignment ability of these liquid crystal alignment films may be low in uniformity, and the alignment uniformity of the liquid crystal in contact with the liquid crystal alignment film is not sufficient. For this reason, there is room for improvement in display performance such as resolution of the cholesteric liquid crystal display.

JP 2000-267142 A JP 2007-72419 A

  The present invention has been made based on the above circumstances, and a cholesteric liquid crystal display having high liquid crystal alignment uniformity by including a liquid crystal alignment film having excellent liquid crystal alignment ability, and a method of manufacturing the cholesteric liquid crystal display An object of the present invention is to provide a liquid crystal aligning agent for forming such a liquid crystal aligning film.

The invention made to solve the above problems is
A pair of opposing substrates,
A cholesteric liquid crystal display comprising: a cholesteric liquid crystal disposed in a plurality of regions between each substrate and a substrate divided in a vertical direction; and a liquid crystal alignment film laminated between each of the substrates and the cholesteric liquid crystal. ,
The liquid crystal alignment film on at least one side is formed of a radiation-sensitive liquid crystal aligning agent.

  In the cholesteric liquid crystal display, at least one liquid crystal alignment film is formed of a radiation-sensitive liquid crystal aligning agent. For this reason, even if the liquid crystal alignment film is not formed on a single plane, it is possible to provide a uniform liquid crystal alignment ability in a desired direction by radiation irradiation. Therefore, according to the cholesteric liquid crystal display, the alignment uniformity of the liquid crystal is excellent, and excellent display performance such as high resolution can be exhibited.

  The plurality of regions may be divided by partition walls formed in a lattice shape. According to the cholesteric liquid crystal display, since the plurality of regions are divided by the partition walls, the cholesteric liquid crystal disposed in each region can be prevented from moving and display performance can be further improved.

  The radiation-sensitive liquid crystal aligning agent may contain [A] a polyorganosiloxane having a photo-alignment group (hereinafter also referred to as “[A] photo-alignment polyorganosiloxane”). [A] In the liquid crystal alignment film obtained by irradiating the coating film formed from the liquid crystal aligning agent containing the photo-alignable polyorganosiloxane, the alignment property of the molecules forming the alignment film is increased. be able to. As a result, the alignment uniformity of the liquid crystal in the cholesteric liquid crystal display is improved.

  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 a photo-aligning group, introduction is easy, and a liquid crystal alignment film formed from such a liquid crystal aligning agent has higher light. Has orientation performance. As a result, the alignment uniformity of the liquid crystal in the cholesteric liquid crystal display can be further increased.

（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。このフェニレン基、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−又は−ＣＯＯ−である。ａは０〜３の整数である。但し、ａが２以上の場合、それぞれのＲ^１及びＲ^２は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。
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、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。Ｒ^７は酸素原子、−ＣＯＯ−＊又は−ＯＣＯ−＊である。但し、＊を付した結合手がＲ^８と結合する。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。Ｒ^９は単結合、−ＯＣＯ−（ＣＨ_２）_ｆ−＊又は−Ｏ（ＣＨ_２）_ｇ−＊である。但し、＊を付した結合手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。ｅは０〜３の整数である。但し、ｅが２以上の場合、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。） The group having a cinnamic acid structure may be 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). .

(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 or cyclohexylene group are It may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom, a fluorine atom or a cyano group, and R ² is a single bond, having 1 to 1 carbon atoms. 3 is an alkanediyl group, an oxygen atom, a sulfur atom, —CH═CH—, —NH— or —COO—, a is an integer of 0 to 3, provided that when a is 2 or more, each R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, and b is an integer of 0 to 4.
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, 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. R ⁷ is an oxygen atom, —COO— * or —OCO— *. However, bond binds to R ⁸ marked with *. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. However, a bond marked with * is bonded to a carboxyl group. f and g are each an integer of 1 to 10. e is an integer of 0-3. However, when e is 2 or more, R ⁷ and R ⁸ may be the same or different. )

  By using the group derived from the specific cinnamic acid derivative as the group having the cinnamic acid structure, the optical alignment performance of the obtained liquid crystal alignment film can be further improved. As a result, the alignment uniformity of the liquid crystal in the cholesteric liquid crystal display can be improved. Further improvement can be achieved.

  [A] The polyorganosiloxane is an epoxy group-containing polyorganosiloxane and at least one selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2). A reaction product is preferred. In the [A] polyorganosiloxane contained in the radiation-sensitive liquid crystal aligning agent, by utilizing the reactivity between the polyorganosiloxane having an epoxy group and the specific cinnamic acid derivative, the polyorganosiloxane as the main chain is irradiated with light. A side chain group derived from a specific cinnamic acid derivative having an orientation group can be easily introduced.

  The liquid crystal aligning agent is at least one polymer selected from the group consisting of [B] polyamic acid, polyimide, ethylenically unsaturated compound polymer, and polyorganosiloxane having no photo-alignable group (hereinafter referred to as “ [B] Other polymer ”is also preferably contained. In the liquid crystal alignment film formed from the above liquid crystal aligning agent, it is clear that polyorganosiloxane is unevenly distributed in the vicinity of the surface layer. For this reason, even if the content of polyorganosiloxane in the liquid crystal aligning agent is reduced by adding [B] another polymer, the polyorganosiloxane is unevenly distributed on the surface of the liquid crystal alignment layer, and the photo-alignment of the liquid crystal alignment film The performance can be enhanced, and as a result, the alignment uniformity of the liquid crystal can be maintained high. Accordingly, it is possible to reduce the content of polyorganosiloxane having a high production cost in the liquid crystal aligning agent, and as a result, the production cost of the cholesteric liquid crystal display can be reduced.

  The liquid crystal aligning agent is at least selected from the group consisting of an acetal ester structure of [C] carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid, and a t-butyl ester structure of carboxylic acid. It is preferable to further contain a compound having two or more of one type of structure (hereinafter also referred to as “[C] ester structure-containing compound”). When the liquid crystal aligning agent contains the [C] ester structure-containing compound, an acid is generated when a coating film made of the liquid crystal aligning agent is baked, and the generated acid promotes cross-linking of [A] polyorganosiloxane. As a result, it is possible to improve the heat resistance of the obtained liquid crystal alignment film and thus the cholesteric liquid crystal display.

The method for producing a cholesteric liquid crystal display of the present invention includes:
A pair of opposing substrates, a cholesteric liquid crystal disposed in a plurality of regions between the substrates divided in the vertical direction, and a liquid crystal alignment film stacked between the substrates and the cholesteric liquid crystal, respectively. A method of manufacturing a cholesteric liquid crystal display,
(1) A step of applying a radiation-sensitive liquid crystal aligning agent on a plurality of divided regions of at least one of the substrates to form a coating film,
(2) A step of forming a liquid crystal alignment film by irradiating the coating film with radiation, and (3) a step of filling a cholesteric liquid crystal in each divided region where the liquid crystal alignment film is formed.

  According to the production method of the present invention, a cholesteric liquid crystal display excellent in liquid crystal alignment uniformity can be efficiently produced, and improvement in productivity and reduction in production cost can be promoted.

  The radiation-sensitive liquid crystal aligning agent in the production method may be applied by an ink jet method. By applying by the inkjet method, the alignment agent can be efficiently applied on the plurality of divided regions.

The liquid crystal aligning agent of the present invention is
A pair of opposing substrates, a cholesteric liquid crystal disposed in a plurality of regions between the substrates divided in the vertical direction, and a liquid crystal alignment film stacked between the substrates and the cholesteric liquid crystal, respectively. A liquid crystal aligning agent for the liquid crystal alignment film in a cholesteric liquid crystal display, characterized by having radiation sensitivity.

  According to the liquid crystal aligning agent of the present invention, the liquid crystal alignment film provided in the cholesteric liquid crystal display can be imparted with a liquid crystal alignment ability in a uniform and desired direction, and as a result, the liquid crystal alignment uniformity can be enhanced.

  According to the cholesteric liquid crystal display of the present invention, by providing a liquid crystal alignment film having excellent liquid crystal alignment ability, the alignment uniformity of the liquid crystal is high, and as a result, display performance such as resolution can be improved. Therefore, the cholesteric liquid crystal display can be suitably used for various liquid crystal display devices including a flexible display such as electronic paper.

1 is a schematic cross-sectional view of a cholesteric liquid crystal display according to an embodiment of the present invention. It is a schematic diagram which shows one process in the manufacturing method of the cholesteric liquid crystal display of FIG.

A cholesteric liquid crystal display of the present invention, a liquid crystal aligning agent used therefor, and a method for producing a cholesteric liquid crystal display will be described with reference to the drawings as appropriate.
<Cholesteric liquid crystal display>
A cholesteric liquid crystal display 1 of FIG. 1 includes a pair of opposing substrates 2 (2a and 2b), cholesteric liquid crystals 3 disposed in a plurality of regions between the substrates 2a and 2b and the substrate 2 divided in the vertical direction. In addition, liquid crystal alignment films 4a and 4b are provided between the substrates 2a and 2b and the cholesteric liquid crystal 3, respectively. The plurality of regions (each cholesteric liquid crystal 3) are divided by the partition walls 5. In addition, the cholesteric liquid crystal display 1 includes transparent electrodes 6a and 6b that are stacked on opposite surfaces of the substrates 2a and 2b, respectively.

  In FIG. 1, light is incident from the upper side, reflected, and emitted from the upper side. That is, the upper side in FIG.

  The pair of substrates 2a and 2b are transparent. Examples of the substrates 2a and 2b include glass substrates such as float glass and soda glass, triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, and cyclic. Examples include olefin ring-opening polymers and hydrogenated products thereof, cyclic olefin addition polymers, and transparent substrates including plastic substrates such as aromatic polyethers. By using the substrates 2a and 2b as plastic base materials, the cholesteric liquid crystal display 1 can be used for flexible displays including electronic paper.

  The transparent electrode 6a is laminated on the opposite surface side surface of the substrate 2a, and the transparent electrode 6b is laminated on the opposite surface side surface of the substrate 2b. The transparent electrodes 6a and 6b are striped thin films, and the transparent electrodes 6a and 6b are provided so as to be orthogonal to 90 degrees when viewed from the upper side in FIG. Each portion where each intersects becomes a substantially central portion of each pixel, and each pixel corresponds to the plurality of divided areas.

Examples of the transparent conductive electrode (thin film) include a NESA film (US PPG, registered trademark) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), and the like. Is mentioned.

  The partition wall 5 is erected directly or partially through the transparent electrode 6b on the surface on the opposite surface side of the substrate 2b. Further, the partition walls 5 are formed in a lattice shape so as to divide a plurality of regions corresponding to each pixel when viewed from the upper side in FIG. According to the cholesteric liquid crystal display 1, the plurality of regions are divided by the partition walls 5 in the vertical direction of the two substrates, in other words, in the opposing direction of the two substrates, so that the cholesteric liquid crystal disposed in each region. 3 can be prevented from moving, and the display performance can be further improved. The material of the partition wall 5 is not particularly limited, and for example, a known photoresist material, an acrylic or polyimide protective film material, or the like can be used.

  The liquid crystal alignment film 4a is partially laminated on the entire opposing surface side of the substrate 2a via the transparent electrode 6a. In addition, the liquid crystal alignment film 4b is partially laminated on the portion where the partition wall 5 is not erected on the opposite surface side of the substrate 2b via the transparent electrode 6b.

  The liquid crystal alignment films 4a and 4b are formed of a radiation-sensitive liquid crystal aligning agent described in detail later. Therefore, even when the rubbing treatment is difficult (when the liquid crystal alignment film 4b is divided and laminated by the partition walls 5 and is not formed on one plane), uniform liquid crystal in a desired direction by radiation irradiation is obtained. Orientation ability can be provided.

  The cholesteric liquid crystal 3 is disposed in a plurality of regions divided by the partition walls 5, and the upper surface is in contact with the liquid crystal alignment film 4a and the lower surface is in contact with the liquid crystal alignment film 4b. Each cholesteric liquid crystal 3 disposed in each region is excellent in alignment uniformity by being sandwiched between liquid crystal alignment films 4a and 4b formed from a radiation-sensitive liquid crystal aligning agent.

  In the cholesteric liquid crystal 3, three types of cholesteric liquid crystals having a chiral pitch adjusted so as to selectively reflect red, green, or blue light are repeatedly arranged in order in a plurality of divided areas. According to the cholesteric liquid crystal display 1, by arranging the three types of cholesteric liquid crystals corresponding to the three primary colors in a mosaic manner as described above, it is possible to perform color display in substantially one liquid crystal layer. In the case of a monochrome liquid crystal display, one type of cholesteric liquid crystal may be used, or two or more types of cholesteric liquid crystal may be used.

  A known cholesteric liquid crystal 3 can be used. For example, the cholesteric liquid crystal 3 can be obtained by adding a chiral agent to the base liquid crystal at a ratio of several tens of mass%. The wavelength of light that is selectively reflected can be adjusted according to the type and amount of the chiral agent. As this base liquid crystal, nematic liquid crystal such as cyano group, fluorine group and ester group can be used. The chiral agent is appropriately selected in consideration of solubility, twisting force, pitch temperature dependency, and the like. In addition, derivatives of cholesterol ester and the like can also be used as they are as cholesteric liquid crystals. It is also possible to use a cholesteric liquid crystal containing a polymer. In this case, a photopolymerizable polymer precursor such as acrylate or methacrylate or a thermosetting polymer precursor such as epoxy is used as the cholesteric liquid crystal. It can mix | blend beforehand and can add and use a reaction initiator as needed.

  In the cholesteric liquid crystal display 1, the transmission or reflection of incident light can be controlled by controlling the alignment state of the cholesteric liquid crystal 3 by application between the transparent electrodes 6a and 6b. Therefore, the cholesteric liquid crystal display 1 can perform color display without using a polarizing plate and a color filter by arranging three types of cholesteric liquid crystals in a mosaic pattern. At this time, the liquid crystal alignment film provided in the cholesteric liquid crystal display 1 has a uniform liquid crystal alignment ability in a desired direction by irradiation even though it is not formed on one plane as described above. . Therefore, according to the cholesteric liquid crystal display 1, excellent alignment performance of liquid crystal and excellent display performance such as high resolution can be exhibited.

  The cholesteric liquid crystal display can be used for various liquid crystal display devices such as a television receiver, a monitor device of a personal computer, a mobile phone, and a game machine, and can be suitably used particularly for a flexible display including electronic paper. .

<Radiation sensitive liquid crystal aligning agent>
The liquid crystal alignment films 4a and 4b are formed from a radiation-sensitive liquid crystal aligning agent (hereinafter also simply referred to as “liquid crystal aligning agent”) as described above. By forming from a radiation-sensitive liquid crystal aligning agent, it is not formed on one plane, and even if it is considered difficult to improve the orientation by rubbing treatment, it enhances the orientation of the alignment film forming molecules. As a result, the alignment uniformity of the obtained liquid crystal alignment film can be improved.

  As said liquid crystal aligning agent, the liquid crystal aligning agent containing the polyorganosiloxane which has [A] photo-alignment group is preferable. When the liquid crystal aligning agent contains [A] photo-alignable polyorganosiloxane, the amount of light irradiation necessary for alignment can be reduced due to the high-sensitivity photo-alignment. Moreover, since the said liquid crystal aligning agent does not require the heating process during irradiation and after irradiation, a liquid crystal aligning film can be manufactured efficiently. Furthermore, the liquid crystal aligning film obtained from the said liquid crystal aligning agent is excellent in liquid crystal aligning performance and thermal stability. The liquid crystal aligning agent preferably contains [B] another polymer and a [C] ester structure-containing compound, and may further contain other optional components as long as the effects of the present invention are not impaired. . Hereinafter, [A] photo-alignable polyorganosiloxane, [B] other polymer, [C] ester structure-containing compound, and optional components will be described in detail.

<[A] Photoalignable polyorganosiloxane>
[A] The photo-alignment polyorganosiloxane has photo-alignment in a portion derived from at least one selected from the group consisting of polyorganosiloxane as a main chain, a hydrolyzate thereof and a condensate of the hydrolyzate. A group has been introduced. By the photo-alignment group, the sensitivity of photo-alignment is improved, a low light irradiation amount can be realized, and the liquid crystal alignment property of the liquid crystal alignment film is excellent. Further, since polyorganosiloxane is employed as the main chain, the liquid crystal alignment film formed from the liquid crystal aligning agent has excellent chemical stability and thermal stability.

  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 a group derived from the specific cinnamic acid derivative is preferable. R ¹ is a phenylene group, a biphenylene group, a terphenylene group, or a cyclohexylene group. Some or all of the hydrogen atoms of this phenylene group, biphenylene group, terphenylene group or cyclohexylene group are alkyl groups having 1 to 10 carbon atoms and alkoxy groups having 1 to 10 carbon atoms which may have fluorine atoms. , 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— or —COO—. a is an integer of 0-3. However, when a is 2 or more, each 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.

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

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. It is particularly preferable that b is 0 when a is 1 to 3.

In the 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, 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. R ⁷ is an oxygen atom, —COO— * or —OCO— *. However, bond binds to R ⁸ marked with *. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. However, a bond marked with * is bonded to a carboxyl group. f and g are each an integer of 1 to 10. e is an integer of 0-3. However, when e is 2 or more, R ⁷ and R ⁸ may be the same or different.

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

（式中、Ｑは炭素数１〜１０の鎖状又は環状のアルキル基、炭素数１〜１０の鎖状又は環状のアルコキシ基、フッ素原子又はシアノ基である。ｆは、式（２）と同義である。）

(In the 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 the formula (2) Synonymous.)

  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, (i) a compound having a benzene ring skeleton substituted with a halogen atom under basic conditions is reacted with acrylic acid in the presence of a transition metal catalyst to produce a specific cinnamic acid derivative. And (ii) reacting a cinnamic acid in which a hydrogen atom of a benzene ring is substituted with a halogen atom under a basic condition and a compound having a benzene ring skeleton substituted with a halogen atom in the presence of a transition metal catalyst. The method etc. which make a specific cinnamic acid derivative are mentioned.

  [A] As a part derived from at least one selected from the group consisting of polyorganosiloxane contained in the photoalignable polyorganosiloxane as a main chain, a hydrolyzate thereof and a condensate of the hydrolyzate, As long as it has a portion derived from the structure into which the photo-alignable group can be introduced, it is not particularly limited. [A] The photoalignable polyorganosiloxane is a portion derived from at least one selected from the group consisting of such polyorganosiloxane, a hydrolyzate thereof, and a condensate of the hydrolyzate, and the photoalignment property. And a group derived from a compound exhibiting

  Examples of the structure into which the photoalignable group can be introduced include a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a mercapto group, an ester group, and an amide group. Among these, an epoxy group is preferable in consideration of ease of introduction and preparation.

  [A] The photoalignable polyorganosiloxane is preferably a reaction product of a polyorganosiloxane having an epoxy group and a compound represented by the above formula (1) and / or (2). In the liquid crystal aligning agent, by utilizing the reactivity between the polyorganosiloxane having an epoxy group and the specific cinnamic acid derivative, the polyorganosiloxane as the main chain is derived from the specific cinnamic acid derivative having photo-alignment property. Groups can be easily introduced.

  The polyorganosiloxane having an epoxy group is not particularly limited as long as an epoxy group is introduced as a side chain into the polyorganosiloxane. The polyorganosiloxane having an epoxy group may be a hydrolyzate of a polyorganosiloxane having an epoxy group or a condensate of the hydrolyzate. The polyorganosiloxane having an epoxy group is at least one selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (3), a hydrolyzate thereof, and a condensate of the hydrolyzate. It is preferable that

（式（３）中、Ｘ^１はエポキシ基を有する１価の有機基である。Ｙ^１は水酸基、炭素数１〜１０のアルコキシ基、炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基である。）

(In 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 6 to 20 carbon atoms. Of the aryl group.)

  In addition, the hydrolysis condensate of the polyorganosiloxane having the structural unit represented by the above formula (3) is not only the hydrolysis condensate of the polyorganosiloxane but also the structural unit represented by the above formula (3). Hydrolysis condensate in the case where the polyorganosiloxane obtained by the branching or crosslinking of the main chain has the structural unit represented by the above formula (3) in the process of producing the polyorganosiloxane by the hydrolytic condensation of It is a concept that also includes

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 represented by the following formula (X ¹ -1) or (X ¹ -2).

（式（Ｘ^１−１）中、Ａは酸素原子又は単結合である。ｈは１〜３の整数である。ｉは０〜６の整数である。但し、ｉが０の場合、Ａは単結合である。
式（Ｘ^１−２）中、ｊは１〜６の整数である。
式（Ｘ^１−１）及び（Ｘ^１−２）中、＊はそれぞれ結合手であることを示す。）

(In Formula (X ¹ -1), A is an oxygen atom or a single bond. H is an integer of 1 to 3. i is an integer of 0 to 6. However, when i is 0, A is It is a single bond.
Wherein ^(X 1 -2), j is an integer from 1 to 6.
In formulas (X ¹ -1) and (X ¹ -2), * represents a bond. )

Furthermore, among the epoxy groups represented by the above formula (X ¹ -1) or (X ¹ -2), a group represented by the following formula (X ¹ -1-1) or (X ¹ 2-1) is preferable.

（式（Ｘ^１−１−１）又は式（Ｘ^１−２−１）中、＊は結合手であることを示す。）

(In formula (X ¹ -1-1) or formula (X ¹ -2-1), * indicates a bond)

In Y ¹ in the above formula (3),
Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group and an ethoxy group;
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. Group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl Group, etc .;
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of polyorganosiloxane having an epoxy group is preferably 500 to 100,000, more preferably 1,000 to 10,000, 1,000 to 5,000 are particularly preferred.

In addition, Mw in this specification is a polystyrene conversion value measured by GPC having the following specifications.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 6.8 MPa

  Such a polyorganosiloxane having an epoxy group is preferably 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, water and a catalyst. Can be synthesized by hydrolysis or hydrolysis / 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.

For example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5844, X-21-5844, X-21-5845, X -21-5848, 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-41-1 053, 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, Shin-Etsu Chemical Co., Ltd.);
Glass resin (Showa Denko);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning);
FZ3711, FZ3722 (above, Nippon Unicar Company);
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, Chisso);
Methyl silicate MS51, Methyl silicate MS56 (Mitsubishi Chemical Corporation);
Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Colcoat);
Examples include partial condensates such as GR100, GR650, GR908, GR950 (above, Showa Denko KK).

  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.

  The polyorganosiloxane having an epoxy group used in the present invention suppresses unintended side reactions caused by excessive introduction of epoxy groups while introducing a sufficient amount of side chains having photo-alignment properties. The epoxy equivalent is preferably 100 g / mol to 10,000 g / mol, more preferably 150 g / mol to 1,000 g / mol. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the use ratio of the silane compound having an epoxy group and another silane compound is prepared so that the epoxy equivalent of the obtained polyorganosiloxane is in the above range. It is preferable.

  Specifically, such other silane compound is preferably used in an amount of 0% by mass to 50% by mass with respect to the total of the polyorganosiloxane having an epoxy group and the other silane compound, and 5% by mass to 30% by mass. % Is more preferable.

  Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group 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. In addition, the amount of water used in producing the polyorganosiloxane having an epoxy group is preferably 0.5 times to 100 times mol, more preferably 1 time to 30 times mol, based on the total silane compounds. .

  As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
Examples include quaternary organic ammonium salts such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, etc. Quaternary organic ammonium salts such as methylammonium hydroxide are preferred.

  As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing side reactions such as ring opening of the epoxy group, resulting in stable production. It is preferable because of its excellent properties. In addition, the composition for aligning organic semiconductors of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a specific cinnamic acid derivative has storage stability. Is advantageous because it is extremely excellent.

  The reason is that, as pointed out in Chemical Reviews, Vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in a hydrolysis or condensation reaction, a random structure, a ladder structure or a cage structure is used. It is presumed that a structure is formed and a polyorganosiloxane having a low content of silanol groups is obtained. Since the content ratio of silanol groups is small, the condensation reaction between silanol groups is suppressed, and when the composition for aligning organic semiconductors of the present invention contains other polymers described later, silanol groups and Since the condensation reaction with other polymers is suppressed, it is presumed that the storage stability is excellent.

  As the catalyst, an organic base is particularly preferable. The amount of organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and can be set appropriately. The specific use amount of the organic base is, for example, preferably 0.01 times to 3 times mol, more preferably 0.05 times to 1 time mol, with respect to all silane compounds.

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

  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. A polyorganosiloxane having an epoxy group can be obtained.

  In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. As such a commercial item, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Chisso) etc. are mentioned, for example.

  [A] The photo-alignable polyorganosiloxane compound is a hydrolysis product obtained by hydrolyzing and condensing a portion derived from a hydrolyzate produced by hydrolysis of an epoxy group-containing polyorganosiloxane itself or an epoxy group-containing polyorganosiloxane. A portion derived from the condensate may be included. These hydrolysates and hydrolysis condensates which are constituent materials of the above-mentioned parts can also be prepared in the same manner as the hydrolysis or condensation conditions of polyorganosiloxane having an epoxy group.

<[A] Synthesis of photoalignable polyorganosiloxane>
The [A] photoalignable polyorganosiloxane used in the present invention can be synthesized, for example, by reacting the above-mentioned polyorganosiloxane having an epoxy group with a specific cinnamic acid derivative, preferably in the presence of a catalyst.

  Here, 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, more preferably 0.05 mol to 1 mol of the epoxy group of the polyorganosiloxane. Two moles are particularly preferred.

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

Examples of the curing accelerator 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 curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator 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;
An amine salt type latent curing accelerator;
Examples include latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators 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 polyorganosiloxane which has an epoxy group, 0.01 mass part-100 mass parts are more preferable, 0.1 mass part-20 mass parts are 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] The photoalignable polyorganosiloxane can be synthesized in the presence of an organic solvent, if necessary. 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%.

  Although it does not specifically limit as Mw of [A] photo-alignment polyorganosiloxane obtained in this way, 1,000-20,000 are preferable and 3,000-15,000 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. When Mw is less than the above lower limit, electrical characteristics such as voltage holding ratio of the formed liquid crystal alignment film may be deteriorated. On the other hand, when Mw exceeds the above upper limit, when the aligning agent is stored at a temperature of 0 ° C. or lower, polymer aggregates are likely to be generated, and clogging of the ink jet discharge head occurs, or the amount of ink jet ejection is low. It may become stable and cause poor coating.

  [A] The photoalignable polyorganosiloxane introduces a structure derived from a specific cinnamic acid derivative by ring-opening addition of a carboxyl group of the specific cinnamic acid derivative to the epoxy to the polyorganosiloxane having an epoxy group. This production 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.

  In the present invention, a part of the specific cinnamic acid derivative may be replaced with a compound represented by the following formula (4) as long as the effects of the present invention are not impaired. In this case, the synthesis of [A] photoalignable polyorganosiloxane compound is carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific cinnamic acid derivative and a compound represented by the following formula (4). Is called.

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 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 [A] photo-alignable polyorganosiloxane. 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) is polyorganosiloxane. 0.001 mol to 1.5 mol is preferable, 0.01 mol to 1 mol is more preferable, and 0.05 mol to 0.9 mol is particularly preferable with respect to 1 mol of the epoxy group contained in. 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] Other polymer>
The liquid crystal aligning agent can contain [B] another polymer as a suitable component. [B] Examples of the other polymer include at least one selected from the group consisting of polyamic acid, polyimide, ethylenically unsaturated compound polymer, and polyorganosiloxane having no photo-alignment group. When these [B] other polymers are contained, in the liquid crystal alignment film formed from the liquid crystal aligning agent, it is clear that polyorganosiloxane is unevenly distributed in the vicinity of the surface layer. For this reason, even if the content of the polyorganosiloxane in the liquid crystal aligning agent is decreased by increasing the content of other polymers, the polyorganosiloxane is unevenly distributed on the alignment film surface, so that sufficient liquid crystal alignment is obtained. It is done. Therefore, in this invention, it becomes possible to reduce content in the said liquid crystal aligning agent of the polyorganosiloxane with a high manufacturing cost, As a result, the manufacturing cost of the said liquid crystal aligning agent can be reduced.

[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, 3-amino-benzylamine and the following formulas (A-1) represented by the diamine compound, and the like.

（式（Ａ−１）中、Ｘ^Ｉは炭素数１〜３のアルキル基、＊−Ｏ−、＊−ＣＯＯ−又は＊−ＯＣＯ−である。但し、＊を付した結合手がジアミノフェニル基と結合する。ｒは０又は１である。ｓは０〜２の整数である。ｔは１〜２０の整数である。）

(In the formula (A-1), ^{X I} is an alkyl group having 1 to 3 carbon atoms, * - O -, * - . COO- or * -OCO- is provided that bond is di-aminophenyl group marked with * R is 0 or 1. s is an integer of 0 to 2. t is an integer of 1 to 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 .

  The amount of the organic solvent used (a) is 0.1% by mass to 50% with respect to the total amount (a + b) of the total amount (b) of the tetracarboxylic dianhydride and diamine compound and the amount of organic solvent used (a) % 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 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.

[Ethylenically unsaturated compound polymer]
[B] The ethylenically unsaturated compound polymer as the other polymer is obtained by polymerizing a known ethylenically unsaturated compound by a known method. For example, (a) an epoxy group-containing ethylenically unsaturated compound (hereinafter sometimes referred to as “(a) unsaturated compound”) and (b1) an ethylenically unsaturated carboxylic acid and / or a polymerizable unsaturated polyvalent carboxylic acid. An acid anhydride (hereinafter sometimes referred to as “(b1) unsaturated compound”), a polymerizable unsaturated compound other than (a) unsaturated compound and (b1) unsaturated compound (hereinafter referred to as “(b2) unsaturated”) It is obtained by polymerizing a copolymer (hereinafter sometimes referred to as “(A1) copolymer”).

  (A) As unsaturated compounds, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid 3,4 -Epoxybutyl, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl α-ethyl acrylate, and the like.

(B1) Examples of unsaturated compounds include (meth) acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, Unsaturated carboxylic acids such as mesaconic acid and itaconic acid;
Examples thereof include unsaturated polycarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride.

Examples of (b2) unsaturated compounds include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 2-hydroxypropyl;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate;
(Meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (hereinafter, Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl is referred to as “dicyclopentanyl”), 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. (Meth) acrylic acid alicyclic esters of
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Unsaturated dicarbonylimide derivatives such as maleimide propionate, N- (9-acridyl) maleimide;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene;
Indene derivatives such as indene and 1-methylindene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, and the like can be given.

  (A1) In the copolymer, the content of the structural unit derived from the unsaturated compound (a) is preferably 10% by mass to 70% by mass, and 20% by mass to 60% by mass with respect to all the structural units. More preferably, (b1) The total content of the structural units derived from the unsaturated compound is preferably 5% by mass to 40% by mass, more preferably 10% by mass to 30% by mass with respect to all the structural units. b2) As a content rate of the structural unit derived from an unsaturated compound, 10 mass%-70 mass% are preferable with respect to all the structural units, and 20 mass%-50 mass% are more preferable.

  (A1) A copolymer can synthesize | combine each unsaturated compound by radical polymerization in presence of a suitable solvent and a polymerization initiator, for example. As an organic solvent, the organic solvent similar to the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid, etc. are mentioned, for example.

Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile);
Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane;
hydrogen peroxide;
Examples thereof include a redox initiator composed of these peroxides and a reducing agent. These polymerization initiators can be used alone or in admixture of two or more.

[Polyorganosiloxane having no photo-alignment group]
The liquid crystal aligning agent may further contain [B] a polyorganosiloxane having no photoalignable group as another polymer, in addition to [A] photoalignable polyorganosiloxane. The polyorganosiloxane having no photo-alignment group is at least selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (5), a hydrolyzate thereof, and a condensate of the hydrolyzate. One is preferred. In addition, when the said liquid crystal aligning agent contains the polyorganosiloxane which does not have a photo-alignment group, most of the polyorganosiloxane which does not have a photo-alignment group is independent of [A] photo-alignment polyorganosiloxane. A part thereof may exist as a condensate with [A] photoalignable polyorganosiloxane.

In the above formula (5), ^{X 2} is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group having 6 to 20 carbon atoms having 1 to 6 carbon atoms. Y ² is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

  As the alkyl group having 1 to 20 carbon atoms, for example, linear or branched, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Examples include lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.

  Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.

  The polyorganosiloxane having no photo-alignment group is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as “raw material silane compound”). Preferably, it can be synthesized by hydrolysis or hydrolysis / condensation in a suitable organic solvent in the presence of water and a catalyst.

Examples of the raw material silane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Chlorosilane, etc .;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, Methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyl Trichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, etc .;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, etc .;
Examples include trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane.

  Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane are preferred. .

  Examples of organic solvents that can optionally be used when synthesizing a polyorganosiloxane having no photo-alignment group include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. . These can be used alone or in combination of two or more.

  The amount of water used in the synthesis of the polyorganosiloxane having no photo-alignment group is preferably 0.01 mol to 100 mol with respect to a total of 1 mol of alkoxy groups and halogen atoms of the raw material silane compound, 0.1 mol-30 mol is more preferable, and 1 mol-1.5 mol is especially preferable.

  Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane having no photo-alignment group include metal chelate compounds, organic acids, inorganic acids, organic bases, alkali metal compounds, alkaline earth metal compounds, and ammonia. These can be used alone or in combination of two or more.

  As a usage-amount of a catalyst, 0.001 mass part-10 mass parts are preferable with respect to 100 mass parts of raw material silane compounds, and 0.001 mass part-1 mass part are more preferable.

  Water added in the synthesis of the polyorganosiloxane having no photo-alignment group can be added intermittently or continuously in the raw material silane compound or in a solution obtained by dissolving the silane compound in an organic solvent. The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.

  The reaction temperature in the synthesis of the polyorganosiloxane having no photo-alignment group is preferably 0 ° C to 100 ° C, more preferably 15 ° C to 80 ° C. The reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 8 hours.

  When the liquid crystal aligning agent contains [B] other polymer, the content ratio of [B] other polymer varies depending on the type of [B] other polymer, but [A] photo-alignment property. The amount is preferably 10,000 parts by mass or less with respect to 100 parts by mass of the polyorganosiloxane.

<[C] Ester structure-containing compound>
By including the [C] ester structure-containing compound, the liquid crystal aligning agent can form a liquid crystal aligning film having excellent heat resistance and the like.

  [C] The ester structure-containing compound is selected from the group consisting of an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a t-butyl ester structure of a carboxylic acid in the molecule. It is a compound having two or more of at least one kind of structure. [C] The ester structure-containing compound may be a compound having two or more of the same kind of structures among these structures, or a compound having two or more of the different kinds of structures among these structures. There may be. Examples of the group containing an acetal ester structure of the carboxylic acid include groups represented by the following formulas (C-1) and (C-2).

（式（Ｃ−１）中、Ｒ^１３及びＲ^１４はそれぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜１０の脂環式基、炭素数６〜１０のアリール基又は炭素数７〜１０のアラルキル基である。
式（Ｃ−２）中、ｎ１は２〜１０の整数である。）

(In Formula (C-1), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or carbon. It is an aralkyl group of several 7 to 10.
In formula (C-2), n1 is an integer of 2-10. )

In R ¹³ in the above formula (C-1), the alkyl group having 1 to 20 carbon atoms is preferably a methyl group, the alicyclic group having 3 to 10 carbon atoms is preferably a cyclohexyl group, and the carbon group having 6 to 10 carbon atoms. The aryl group is preferably a phenyl group, and the aralkyl group having 7 to 10 carbon atoms is preferably a benzyl group. The alkyl group having 1 to 20 carbon atoms of R ¹⁴ is preferably an alkyl group having 1 to 6 carbon atoms, and the alicyclic group having 3 to 10 carbon atoms is preferably an alicyclic group having 6 to 10 carbon atoms. The aryl group having 6 to 10 carbon atoms is preferably a phenyl group, and the aralkyl group having 7 to 10 carbon atoms is preferably a benzyl group or a 2-phenylethyl group. As n1 in Formula (C-2), 3 or 4 is preferable.

  Examples of the group represented by the formula (C-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1- i-butoxyethoxycarbonyl group, 1-sec-butoxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1-norbornyloxyethoxycarbonyl group, 1-phenoxyethoxycarbonyl group, (Cyclohexyl) (methoxy) methoxycarbonyl group, (cyclohexyl) (cyclohexyloxy) methoxycarbonyl group, (cyclohexyl) (phenoxy) methoxycarbonyl group, (cyclohexyl) (benzyloxy) methoxycarbonyl group, Nyl) (methoxy) methoxycarbonyl group, (phenyl) (cyclohexyloxy) methoxycarbonyl group, (phenyl) (phenoxy) methoxycarbonyl group, (phenyl) (benzyloxy) methoxycarbonyl group, (benzyl) (methoxy) methoxycarbonyl group , (Benzyl) (cyclohexyloxy) methoxycarbonyl group, (benzyl) (phenoxy) methoxycarbonyl group, (benzyl) (benzyloxy) methoxycarbonyl group and the like.

  Examples of the group represented by the formula (C-2) include a 2-tetrahydrofuranyloxycarbonyl group and a 2-tetrahydropyranyloxycarbonyl group.

  Of these, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group are preferable.

  Examples of the group containing the ketal ester structure of the carboxylic acid include groups represented by the following formulas (C-3) to (C-5).

（式（Ｃ−３）中、Ｒ^１５は炭素数１〜１２のアルキル基である。Ｒ^１６及びＲ^１７はそれぞれ独立して、炭素数１〜１２のアルキル基、炭素数３〜２０の脂環式基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基である
式（Ｃ−４）中、Ｒ^１８は炭素数１〜１２のアルキル基である。ｎ２は２〜８の整数である
式（Ｃ−５）中、Ｒ^１９は炭素数１〜１２のアルキル基である。ｎ３は２〜８の整数である。）

(In Formula (C-3), R ¹⁵ is an alkyl group having 1 to 12 carbon atoms. R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 12 carbon atoms and a fat having 3 to 20 carbon atoms. In formula (C-4), which is a cyclic group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ¹⁸ is an alkyl group having 1 to 12 carbon atoms, and n2 is 2 to 8 In formula (C-5), R ¹⁹ is an alkyl group having 1 to 12 carbon atoms, and n3 is an integer of 2 to 8.)

In the above formula (C-3), the alkyl group having 1 to 12 carbon atoms of R ¹⁵ is preferably a methyl group, the alkyl group having 1 to 12 carbon atoms in R ¹⁶ is preferably a methyl group, and having 3 to 20 carbon atoms. The alicyclic group is preferably a cyclohexyl group, the aryl group having 6 to 20 carbon atoms is preferably a phenyl group, and the aralkyl group having 7 to 20 carbon atoms is preferably a benzyl group. The alkyl group having 7 to 20 carbon atoms in R ¹⁷ is preferably an alkyl group having 1 to 6 carbon atoms. The alicyclic group having 3 to 20 carbon atoms is preferably an alicyclic group having 6 to 10 carbon atoms. The aryl group having 6 to 20 carbon atoms is preferably a phenyl group. The aralkyl group having 7 to 20 carbon atoms is preferably a benzyl group or a 2-phenylethyl group. As the alkyl group having 1 to 12 carbon atoms of R ¹⁸ in the formula (C-4), a methyl group is preferable. n2 is preferably 3 or 4. As the alkyl group having 1 to 12 carbon atoms of R ¹⁹ in the formula (C-5), a methyl group is preferable. n3 is preferably 3 or 4.

  Examples of the group represented by the formula (C-3) include 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-n-propoxyethoxycarbonyl group, 1-methyl-1-n-butoxyethoxy. Carbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group, 1-methyl-1-sec-butoxyethoxycarbonyl group, 1-methyl-1-t-butoxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxy Ethoxycarbonyl group, 1-methyl-1-norbornyloxyethoxycarbonyl group, 1-methyl-1-phenoxyethoxycarbonyl group, 1-methyl-1-benzyloxyethoxycarbonyl group, 1-methyl-1-phenethyloxyethoxy Carbonyl group, 1-cyclohexyl-1-methoxyethoxycarbonyl group 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyl-1-phenoxyethoxycarbonyl group, 1-phenyl-1-methoxyethoxycarbonyl group, 1-phenyl-1-ethoxyethoxycarbonyl group, 1-phenyl-1 -Phenoxyethoxycarbonyl group, 1-phenyl-1-benzyloxyethoxycarbonyl group, 1-benzyl-1-methoxyethoxycarbonyl group, 1-benzyl-1-cyclohexyloxyethoxycarbonyl group, 1-benzyl-1-phenoxyethoxycarbonyl Group, 1-benzyl-1-benzyloxyethoxycarbonyl group and the like.

  Examples of the group represented by the formula (C-4) include a 2- (2-methyltetrahydrofuranyl) oxycarbonyl group and a 2- (2-methyltetrahydropyranyl) oxycarbonyl group.

  Examples of the group represented by the formula (C-5) include a 1-methoxycyclopentyloxycarbonyl group and a 1-methoxycyclohexyloxycarbonyl group.

  Of these, a 1-methyl-1-methoxyethoxycarbonyl group and a 1-methyl-1-cyclohexyloxyethoxycarbonyl group are preferable.

  Examples of the group containing a 1-alkylcycloalkyl ester structure of the carboxylic acid include a group represented by the following formula (C-6).

（式（Ｃ−６）中、Ｒ^２０は炭素数１〜１２のアルキル基である。ｎ４は１〜８の整数である。）

(In Formula (C-6), R ²⁰ is an alkyl group having 1 to 12 carbon atoms. N4 is an integer of 1 to 8.)

Examples of the alkyl group having 1 to 12 carbon atoms ^{R 20} in the above formula (C-6) is preferably an alkyl group having 1 to 10 carbon atoms.

  Examples of the group represented by the above formula (C-6) include 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group, 1-methylcyclodecyloxycarbonyl group, 1-ethylcyclobutoxycarbonyl group, 1-ethylcyclopentoxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcyclodecyloxycarbonyl group, 1- (iso) propylcyclo Propoxycarbonyl group, 1- (iso) propylcyclobutoxycarbonyl group, 1- (iso) propylcyclodecyloxycarbonyl group, 1- (iso) butylcyclobutoxycarbonyl group, 1- (iso) butylcyclopentoxycarbonyl group, 1- (iso) butyl Rohexyloxycarbonyl group, 1- (iso) butylcycloheptyloxycarbonyl group, 1- (iso) butylcyclodecyloxycarbonyl group, 1- (iso) pentylcycloheptyloxycarbonyl group, 1- (iso) pentyl Cyclooctyloxycarbonyl group, 1- (iso) hexylcyclopropoxycarbonyl group, 1- (iso) hexylcyclobutoxycarbonyl group, 1- (iso) hexylcyclopentoxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group 1- (iso) hexylcyclononyloxycarbonyl group, 1- (iso) hexylcyclodecyloxycarbonyl group, 1- (iso) octylcyclopropoxycarbonyl group, 1- (iso) octylcyclobutoxycarbonyl group, 1- ( Iso) octylcyclopentoxy Rubonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcycloheptyloxycarbonyl group, 1- (iso) octylcyclooctyloxycarbonyl group, 1- (iso) octylcyclodecyloxycarbonyl group Etc.

  The group containing the t-butyl ester structure of the carboxylic acid is a t-butoxycarbonyl group.

  As the [C] ester structure-containing compound in the present invention, a compound represented by the following formula (C) is preferable.

T _n R (C)
(In the formula (C), T is a group represented by any one of the above formulas (C-1) to (C-6) or a t-butoxycarbonyl group, n is 2, and R is a single bond. N is an integer of 2 to 10 and R is an n-valent group obtained by removing hydrogen from a heterocyclic compound having 3 to 10 carbon atoms or an n-valent hydrocarbon group having 1 to 18 carbon atoms .)

  n is preferably 2 or 3.

  In the above formula (C), R is a single bond, alkanediyl group having 1 to 12 carbon atoms, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group when n is 2. 2,6-naphthalenyl group, 5-sodium sulfo-1,3-phenylene group, 5-tetrabutylphosphonium sulfo-1,3-phenylene group and the like.

  When n is 3, examples of R include a group represented by the following formula and a benzene-1,3,5-triyl group.

  The alkanediyl group is preferably a straight chain.

  The [C] ester structure-containing compound represented by the above formula (C) can be synthesized by an organic chemistry standard method or an appropriate combination of organic chemistry standard methods.

For example, a compound in which T in the above formula (C) is a group represented by the above formula (C-1) (except when R ¹³ is a phenyl group) is preferably a compound in the presence of a phosphoric acid catalyst. R— (COOH) _n (wherein R and n are as defined above in formula (C)) and compound R ¹⁴ —O—CH═R ^{13 ′} (wherein R ¹⁴ is defined as formula (C-1) above) R ^{13 ′} can be synthesized by adding a group obtained by removing a hydrogen atom from the first carbon of R ^{13 in} the above formula (C-1).

The compound in which T in the formula (C) is a group represented by the formula (C-2) is preferably a compound R- (COOH) _n (wherein R and R in the presence of a p-toluenesulfonic acid catalyst). n is synonymous with the above formula (C)) and can be synthesized by adding a compound represented by the following formula.

（式中、ｎ１は上記式（Ｃ−２）と同義である。）

(In formula, n1 is synonymous with the said Formula (C-2).)

  The content of the [C] ester structure-containing compound in the liquid crystal aligning agent is not particularly limited as long as it is determined in consideration of required heat resistance and the like, but [A] with respect to 100 parts by mass of the photoalignable polyorganosiloxane. The [C] ester structure-containing compound is preferably 0.1 to 50 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass.

<Other optional components>
In addition to the above components, the liquid crystal aligning agent includes a curing agent, a curing catalyst, a curing accelerator, and a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”) as long as the effects of the present invention are not impaired. A functional silane compound, a surfactant, a photosensitizer, and the like. Hereinafter, these other optional components will be described in detail.

[Curing agent, curing catalyst and curing accelerator]
A curing agent and a curing catalyst can be contained in the liquid crystal alignment agent for the purpose of strengthening the crosslinking reaction of [A] photo-alignable polyorganosiloxane. 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. An acid anhydride, polyhydric carboxylic acid, etc. are mentioned.

  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, In addition to the compound represented by formula (6) and tetracarboxylic dianhydride generally used for the synthesis of polyamic acid, an alicyclic compound having a conjugated double bond such as α-terpinene and alloocimene and maleic anhydride The Diels-Alder reaction product and hydrogenated products thereof.

（式（６）中、ｐは１〜２０の整数である。）

(In Formula (6), p is an integer of 1-20.)

Examples of the curing catalyst include diazonium salts, iodonium salts, sulfonium salts, aluminum alcoholates, and aluminum chelates. Commercially available products include AMERICURE (BF ₄ ) (diazonium salt from ACC), ULTRASET (BF ₄ , PF ₆ ) (diazonium salt from Asahi Denka Kogyo), UVE series (iodonium salt from GE), Photoinitiator 2074 ((C ₆ F ₆ ) ₄ B) (Iodonium salt from Rhône-Poulenc), CYRACURE UVI-6974, CYRACURE UVI-6990 (above, sulfonium salt from UCC), UVI-508, UVI-509 (above, sulfonium from GE) Salt), OPTOMER SP-150, OPTOMER SP-170 (a sulfonium salt from Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (above, Sanshin Chemical Industries sulfonium salt), IRU GACURE 261 (metallocene compound of Ciba Geigy), aluminum chelate A (W) (Kawaken Fine Chemical Co., Ltd.) and the like can be mentioned. These curing catalysts may be used alone or as a mixture of two or more.

  The use ratio of the curing catalyst is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of [A] photo-alignable polyorganosiloxane. When the said liquid crystal aligning agent contains a curing catalyst, as the content rate, [B] above-mentioned photo-alignment polyorganosiloxane and [B] other polymer used arbitrarily with respect to a total of 100 mass parts 30 parts by mass or less is preferable, and 20 parts by mass or less is more preferable.

  Of these curing catalysts, sulfonium salts and aluminum chelates are preferable, and among the sulfonium salts, compounds containing antimony hexafluoride, phosphorus hexafluoride, and the like as anionic species are more preferable. Examples of these sulfonium salts include hexafluoroantimony salt of methylphenyldimethylsulfonium, hexafluoroantimony salt of ethylphenyldimethylsulfonium, hexafluorophosphate salt of methylphenyldimethylsulfonium, and the like. These sulfonium salts may be used alone or as a mixture of two or more. Commercially available products of these sulfonium salts include Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (above, Sanshin Chemical Industry Co., Ltd.), UVI-6990, UVI-6922, UVI-6974 (above, Union Carbide). Adekaoptomer SP-150, Adekaoptomer SP-170, Adeka Opton CP-66, Adeka Opton CP-77 (Asahi Denka Kogyo Co., Ltd.), IRGACURE 261 (Ciba Geigy) and the like.

Examples of curing accelerators 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;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as dicyandiamide, amine addition type accelerators such as adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator whose surface is covered with a polymer such as a quaternary phosphonium salt;
An amine salt type latent curing accelerator;
And 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, 10 mass parts or less are preferable with respect to 100 mass parts of [A] photo-alignment polyorganosiloxane.

  When the liquid crystal aligning agent contains a curing agent and a curing catalyst, the content ratio is 100 masses in total of [B] other polymers optionally used with the above-mentioned [A] photo-alignable polyorganosiloxane. 10 parts by mass or less is preferable with respect to parts, and 1 part by mass or less is more preferable.

[Epoxy compound]
An epoxy compound can be contained in the liquid crystal alignment agent for the purpose of further improving the adhesion of the liquid crystal alignment film to be formed to the substrate surface.

  Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol. Diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetra Glycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-dia Bruno diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane.

  As a content rate of an epoxy compound, 40 mass parts or less are preferable with respect to a total of 100 mass parts of [A] photo-alignment polyorganosiloxane and [B] other polymer arbitrarily contained, 0.1 Mass parts to 30 parts by mass are more preferable. In addition, when the said liquid crystal aligning agent contains an epoxy compound, you may use together basic catalysts, such as 1-benzyl-2-methylimidazole, in order to raise | generate a crosslinking reaction efficiently.

[Functional silane compounds]
The said functional silane compound can be used in order to improve the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed.

  Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Tetracarboxylic dianhydride and amino In addition to the reaction products of a silane compound having a are described in JP-A-63-291922, a reaction product of a silane compound having a tetracarboxylic dianhydride and an amino group.

  As a content rate of a functional silane compound, 50 mass parts or less are preferable with respect to a total of 100 mass parts of [A] photo-alignment polyorganosiloxane and the arbitrarily contained [B] other polymer, Less than the mass part is more preferable.

[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 said 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 polyorganosiloxane having an epoxy group with a mixture of a specific cinnamic acid derivative and a photosensitizer, the [A] photoalignable polyorganosiloxane contained in the liquid crystal aligning agent is a specific cinnamic acid. The photosensitive structure (cinnamic acid structure) derived from the derivative and the photosensitized structure derived from the photosensitizer are included. 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, 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 is preferable, and the acetophenone structure, benzophenone 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, for example, compounds represented by the following formulas (H-1) to (H-10). It is done.

（式中、ｑは１〜６の整数である。）

(Wherein q is an integer of 1 to 6)

  The photoalignable polyorganosiloxane compound used in the present invention is preferably combined with a photosensitizer in addition to the above polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, preferably in the presence of a catalyst, You may synthesize | combine by making it react in an organic solvent.

  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 the silicon atom of the polyorganosiloxane having an epoxy group. 0.05 mol to 2 mol is particularly preferred. The amount of the photosensitizer used is preferably 0.0001 mol to 0.5 mol, more preferably 0.0005 mol to 0.2 mol, relative to 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group. 0.001 mol to 0.1 mol is particularly preferable.

<Preparation of liquid crystal aligning agent>
As described above, the liquid crystal aligning agent contains, for example, [A] photo-alignable polyorganosiloxane, and may contain a suitable component and other optional components as necessary. Preferably, each component is organic. It is prepared as a solution-like composition dissolved in a solvent.

  As the organic solvent, those which dissolve [A] photo-alignable polyorganosiloxane and other optional components and do not react with these are preferable. The organic solvent that can be preferably used in the liquid crystal aligning agent varies depending on the type of other polymer that is optionally contained.

  As the preferable organic solvent in the case where the liquid crystal aligning agent contains [A] photo-alignable polyorganosiloxane and [B] other polymer, the organic solvents exemplified as those used for the synthesis of polyamic acid. Is mentioned. These organic solvents can be used alone or in combination of two or more.

  A preferred solvent used for the preparation of the liquid crystal aligning agent is obtained by combining one or more of the above-mentioned organic solvents according to whether or not other polymers are used and their types. In such a solvent, each component contained in the liquid crystal aligning agent does not precipitate at the following preferable solid content concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 mN / m to 40 mN / m.

  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, etc. Is 1% by mass to 10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the liquid crystal alignment film formed from the liquid crystal alignment agent is too small, and a good liquid crystal alignment film may not be obtained. 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 inkjet method, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, more preferably 3% by mass to 4% by mass, and the solution viscosity is preferably in the range of 3mPa · s to 15mPa · s. The range is more preferably 4 mPa · s to 10 mPa · s, and particularly preferably 5 mPa · s to 9 mPa · s.

  As temperature at the time of preparing the said liquid crystal aligning agent, 0 to 200 degreeC is preferable and 0 to 40 degreeC is more preferable.

<Method for producing cholesteric liquid crystal display>
The cholesteric liquid crystal display of the present invention can be manufactured, for example, as follows. The method for producing a cholesteric liquid crystal display of the present invention includes:
(1) A step of applying a radiation-sensitive liquid crystal aligning agent on a plurality of divided regions of at least one of the substrates to form a coating film,
(2) A step of forming a liquid crystal alignment film by irradiating the coating film with radiation, and (3) a step of filling a cholesteric liquid crystal in each divided region where the liquid crystal alignment film is formed. Hereinafter, the manufacturing method of the cholesteric liquid crystal display 1 of FIG. 1 will be described in detail as an example.

  Prior to step (1), patterned transparent electrodes 6a and 6b are formed on the surfaces (opposing surfaces) of both substrates 2a and 2b. Examples of the method for forming the transparent electrode include a method of forming a transparent conductive film without a pattern and then forming a pattern by photo-etching, a method of using a mask having a desired pattern when forming the transparent conductive film, and the like. It is done.

  Subsequently, the partition wall 5 is formed on the opposite surface side of the one substrate 2b. As a method for forming the partition walls 5, for example, a method using a photoresist can be cited. That is, after the photoresist material is applied to the entire surface on the opposite surface side of the substrate 2b (partially through the transparent electrode 6b), the photoresist material is exposed using a predetermined mask and developed to form the partition wall 5. Can be formed.

  Next, as a step (1), a radiation-sensitive liquid crystal aligning agent is applied onto a plurality of regions divided by the partition walls 5 on the surface (opposing surface) of the substrate 2b. Examples of the coating method include a spray coating method, a slit coating method, a roll coater method, a spinner method, a printing method, an ink jet method, and a vapor deposition method, but an ink jet method is preferably used. By applying by the inkjet method, the alignment agent can be efficiently applied onto the plurality of divided regions.

  As an application method by this ink jet method, as shown in FIG. 2, the liquid crystal aligning agent 4 is discharged from the ink jet discharge head 7 to each region divided by the partition wall 5 in the surface of the substrate 2b. It is done by following. The discharge head 7 is not particularly limited, and a known one can be used. When the liquid crystal aligning agent 4 is discharged from the discharge head 7, it is preferable that the liquid crystal aligning agent 4 has a low viscosity. The viscosity of the liquid crystal aligning agent 4 at the time of discharging is preferably 3 mPa · s to 15 mPa · s, more preferably 4 mPa · s to 10 mPa · s, and particularly preferably 5 mPa · s to 9 mPa · s. Further, in order to lower the viscosity of the liquid crystal aligning agent 4 at the time of ejection as described above, the ejection head 7 is preferably provided with a heating device.

  In addition, a radiation sensitive liquid crystal aligning agent is apply | coated to the whole surface (opposing surface) of the board | substrate 2a by one of the above-mentioned methods.

  Next, the coated surface is preheated (pre-baked) and then post-baked to form a coating film. As prebaking conditions, it is 0.1 minute-5 minutes in 40 to 120 degreeC, for example. As post-baking conditions, 120 to 300 ° C is preferable, 130 to 220 ° C is more preferable, 5 to 200 minutes is preferable, and 10 to 100 minutes is more preferable. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

  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 each layer forming the coating film and the coating film.

  Subsequently, as a process (2), the said coating film is irradiated with linearly polarized light, partially polarized radiation, or non-polarized radiation to impart liquid crystal alignment ability. As the radiation, for example, ultraviolet rays including light having a wavelength of 150 nm to 800 nm and visible light can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination thereof. May be. 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 ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source together with, for example, a filter, a diffraction grating, or the like.

The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more ^{10,000J / m 2, 10J / m} 2 ~3,000J / m 2 is more preferable. In addition, when providing the liquid crystal aligning ability by the photo-alignment method to the coating film formed from a conventionally known liquid crystal aligning agent, the above-mentioned liquid crystal aligning agent needs the irradiation dose of 10,000 J / m < ² > or more. Can provide good liquid crystal alignment ability even when the irradiation dose in the photo-alignment method is 3,000 J / m ² or less, and even 1,000 J / m ² or less, and the manufacturing cost of the cholesteric liquid crystal display can be reduced. Contribute to

  Subsequently, in the step (3), three kinds of cholesteric liquid crystals are sequentially repeated in a mosaic pattern in each divided region where the liquid crystal alignment film 4a is formed. The method of filling the cholesteric liquid crystal is not particularly limited, but a method using an ink jet method is preferable as with the liquid crystal aligning agent. By using the inkjet method, three types of liquid crystals can be efficiently and accurately filled in each divided region.

  Next, if necessary, the solvent contained in the cholesteric liquid crystal 3 is dried and cured by heating and / or non-deflection irradiation. In addition, this hardening process may be performed in air and you may carry out in inert gas atmosphere, such as nitrogen.

  After the cholesteric liquid crystal 3 is filled and cured, two substrates (a transparent electrode 6a and a liquid crystal alignment film 4a are stacked on the substrate 2a. A transparent electrode 6b and a liquid crystal alignment film 4b are stacked on the substrate 2b. Furthermore, the cholesteric liquid crystal display 1 can be obtained by bonding the cholesteric liquid crystal 3 divided and filled with the partition walls 5) with the surfaces on which the transparent electrodes and the like are laminated facing each other.

  In the cholesteric liquid crystal display thus obtained, the liquid crystal alignment film is imparted with a uniform and desired liquid crystal alignment capability by radiation irradiation. Therefore, the cholesteric liquid crystal display has high liquid crystal alignment uniformity and can exhibit excellent display performance.

  The cholesteric liquid crystal display of the present invention is not limited to the above embodiment. For example, the cholesteric liquid crystal display 1 of FIG. 1 may have a structure in which an absorption layer is provided on the back side of the liquid crystal alignment film 4b provided on the back side (lower side in FIG. 1) of the liquid crystal. In this way, according to the cholesteric liquid crystal display including the absorption layer, the contrast at the time of display can be further improved. Moreover, the electrode and the substrate (corresponding to the transparent electrode 6b and the substrate 2b in the cholesteric liquid crystal display 1) provided on the back side of the liquid crystal may not be transparent. For example, the liquid crystal alignment film 4a formed in a planar shape in the cholesteric liquid crystal display 1 of FIG. 1 may be formed using another general liquid crystal aligning agent instead of the radiation-sensitive liquid crystal aligning agent. Furthermore, the partition walls dividing the plurality of regions may be covered with the liquid crystal alignment film, or the plurality of divided regions may not be divided by the partition walls. Any of such structures can exhibit excellent display performance as a cholesteric liquid crystal display.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the required amount of the raw material compound and the polymer used in the following examples was ensured by repeating the synthesis of the raw material compound and the polymer on the synthetic scale shown in the following synthesis examples as necessary.

<Synthesis of polyorganosiloxane having epoxy group>
[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 and 10.0 g of triethylamine were added. 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 and washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to give a polyorgano having an epoxy group. Siloxane was obtained as a viscous clear liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, a peak based on the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. Mw of the obtained polyorganosiloxane having an epoxy group was 2,200, and the epoxy equivalent was 186 g / mol.

<Synthesis of specific cinnamic acid derivatives>
All synthetic reactions of specific cinnamic acid derivatives were carried out in an inert atmosphere.

[Synthesis Example 2]
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 compound represented by the following formula (K-1) (specific cinnamic acid derivative (K-1)).

[Synthesis Example 3]
Mixing 9.5 g of 4-vinylbiphenyl, 10 g of 4-bromocinnamic acid, 0.099 g of palladium acetate, 0.54 g of tris (2-tolyl) phosphine, 18 g of triethylamine, and 80 mL of dimethylacetamide in a 200 mL three-necked flask equipped with a condenser. did. This solution was heated and stirred at 120 ° C. for 3 hours, and after completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 500 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. By recrystallizing these precipitates with a 1: 1 solution of dimethylacetamide and ethanol, 11 g of a compound represented by the following formula (K-2) (specific cinnamic acid derivative (K-2)) was obtained.

<[A] Synthesis of photoalignable polyorganosiloxane>
[Synthesis Example 4]
In a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1, 26 g of methyl isobutyl ketone, 3 g of the specific cinnamic acid derivative (K-1) obtained in Synthesis Example 2 and a quaternary amine salt ( 0.10 g of Sun Apro, UCAT 18X) was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed with water three times, and then the solvent was distilled off, whereby [A] photo-alignable polyorganosiloxane was obtained. 6.3 g of (S-1) was obtained as a white powder. The photoalignable polyorganosiloxane compound (S-1) had a weight average molecular weight Mw of 3,500.

[Synthesis Example 5]
A white powder of [A] photo-alignable polyorganosiloxane (S-2) was prepared in the same manner as in Synthesis Example 4 except that 3 g of the specific cinnamic acid derivative (K-2) obtained in Synthesis Example 2 was used. 7.0 g was obtained. The weight average molecular weight Mw of the photoalignable polyorganosiloxane compound (S-2) was 4,900.

<[B] Synthesis of other polymer>
[Synthesis Example 6]
22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexanebis (methylamine) were dissolved in 329.3 g of NMP at 60 ° C. The reaction was performed for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 32 g of polyamic acid (PA-2).

  17.5 g of this (PA-2) was taken, 232.5 g of NMP, 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto, and the mixture was reacted at 120 ° C. for 4 hours to perform imidization. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide (PI-1).

[Synthesis Example 7]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether (DEGME). Subsequently, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, 30 parts by mass of methacrylic acid, and 20 parts by mass of cyclohexylmaleimide 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 a poly (meth) acrylate copolymer (MA-1). The solid content concentration of the obtained polymer solution was 33.1% by mass. The number average molecular weight of the obtained polymer was 7,000.

<Synthesis of [C] ester structure-containing compound>
An ester structure-containing compound (C-1-1) was synthesized according to the following scheme.

[Synthesis Example 8]
A 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube was charged with 21 g of trimesic acid, 60 g of n-butyl vinyl ether and 0.09 g of phosphoric acid, and reacted at 50 ° C. with stirring for 30 hours. After completion of the reaction, the organic layer obtained by adding 500 mL of hexane to the reaction mixture was separated and washed successively with 1M aqueous sodium hydroxide solution twice and water three times. Then, 50g of ester structure containing compounds (C-1-1) were obtained as a colorless and transparent liquid by distilling a solvent off from an organic layer.

<Preparation of liquid crystal aligning agent>
[Example 1]
[B] The amount of the solution containing the polyimide (PI-1) obtained in Synthesis Example 6 as another polymer in terms of 1,000 parts by mass in terms of the polyimide (PI-1) contained therein Then, 100 parts by mass of [A] photo-alignable polyorganosiloxane (S-1) obtained in Synthesis Example 4 was added thereto, NMP and diethylene glycol methyl ethyl ether (DEGME) were further mixed, and the solvent composition was NMP: DEGME = 90: 10 (mass ratio) and a solid content concentration of 3.5% by mass was used. The liquid crystal aligning agent (A-1) according to Example 1 was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

[Example 2]
[B] A poly (meth) acrylate copolymer (MA) contained in the solution containing the poly (meth) acrylate copolymer (MA-1) obtained in Synthesis Example 7 as another polymer. -1) in an amount corresponding to 1,000 parts by mass, and 100 parts by mass of [A] photo-alignable polyorganosiloxane (S-2) obtained in Synthesis Example 5 was added thereto, and NMP and Ethylene glycol monobutyl ether (EGMB) was mixed to obtain a solution having a solvent composition of NMP: EGMB = 50: 50 (mass ratio) and a solid content concentration of 3.5 mass%. The liquid crystal aligning agent (A-2) according to Example 2 was prepared by filtering this solution through a filter having a pore diameter of 1 μm.

<Manufacture of cholesteric liquid crystal display>
A cholesteric liquid crystal display was produced by the following method using the liquid crystal aligning agent prepared in the above synthesis example.

[Example 3]
Striped transparent electrodes (ITO electrodes) were formed on each side of the two transparent glass substrates a and b by the following procedure. Using an ITO target (ITO filling rate of 95% or more, In ₂ O ₃ / SnO ₂ = 90/10 mass ratio) with a high-speed sputtering apparatus SH-550-C12 manufactured by Nippon Vacuum Technology Co., Ltd. at 60 ° C. ITO sputtering was performed. The atmosphere at this time was a pressure of 1.0 × 10 ⁻⁵ Pa, an Ar gas flow rate of 3.12 × 10 ⁻³ m ³ / Hr, and an O ₂ gas flow rate of 1.2 × 10 ⁻⁵ m ³ / Hr. The substrate after sputtering was heated in a clean oven at 240 ° C. for 60 minutes for annealing.

  A grid-like partition wall was formed on the surface of the transparent glass substrate b provided with the stripe-like transparent electrodes in accordance with the transparent electrodes. The partition walls were formed by applying a photoresist material (product name: Optomer NN777 manufactured by JSR), exposing through a mask, developing, and curing.

A liquid crystal aligning agent (A-1) was applied to each region formed by the partition walls by an ink jet method, pre-baked on a hot plate at 80 ° C. for 1 minute, and then heated in an oven with nitrogen purged in an oven. The film was post-baked at 30 ° C. for 30 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.

  A similar liquid crystal alignment film was formed on the entire surface of the transparent glass substrate (b) by the same method as described above except that the roll coating method was used.

Nematic liquid crystal material E7 (manufactured by Merck) was mixed with 40% by mass of chiral agent CB15 (manufactured by Merck) and filtered through a filter having a pore size of 0.2 μm to prepare a cholesteric liquid crystal. Each region of the transparent glass substrate (a) where the liquid crystal alignment film was formed was filled with the cholesteric liquid crystal using a pipette. Next, after baking for 1 minute on a hot plate at 60 ° C., the liquid crystal was cured by irradiating non-polarized ultraviolet rays of 30,000 J / m ² containing a 365 nm emission line using an Hg—Xe lamp.

  The surface of the glass substrate (a) on which the liquid crystal is filled is overlapped with the surface of the glass substrate (b) on the side of the liquid crystal alignment film, and then bonded together to form the cholesteric liquid crystal display of Example 3. Obtained.

[Example 4]
In Example 3, the cholesteric liquid crystal display of Example 4 was obtained in the same manner as in Example 3 except that the liquid crystal aligning agent (A-2) was used instead of the liquid crystal aligning agent (A-1).

<Evaluation>
The manufactured cholesteric liquid crystal display was evaluated by the following method.

[Orientation]
In Examples 3 and 4 above, the liquid crystal alignment film portion on the substrate (a) side before the final bonding of the substrate (a) and the substrate (b) was observed with a polarizing microscope for the presence of abnormal domains. The case where it was not observed was evaluated as liquid crystal alignment “A”, and the case where an abnormal domain was observed was evaluated as liquid crystal alignment “B”. Both Examples 3 and 4 were liquid crystal alignment “A”.

  Further, in both Example 3 and Example 4, the liquid crystal alignment film could be uniformly formed by the ink jet method without application failure or coating unevenness.

  According to the present invention, it is possible to provide a cholesteric liquid crystal display having excellent uniformity of liquid crystal alignment and excellent display performance. This cholesteric liquid crystal display can be used for various liquid crystal display devices, and can be particularly suitably used for flexible displays such as electronic paper.

DESCRIPTION OF SYMBOLS 1 Cholesteric liquid crystal display 2, 2a, 2b Substrate 3 Cholesteric liquid crystal 4 Liquid crystal aligning agent 4a, 4b Liquid crystal aligning film 5 Partition 6a, 6b Transparent electrode 7 Discharge head

Claims (11)

A pair of opposing substrates,
A cholesteric liquid crystal display comprising: a cholesteric liquid crystal disposed in a plurality of regions between each substrate and a substrate divided in a vertical direction; and a liquid crystal alignment film laminated between each of the substrates and the cholesteric liquid crystal. ,
A cholesteric liquid crystal display, wherein the liquid crystal alignment film on at least one side is formed of a radiation-sensitive liquid crystal aligning agent.   2. The cholesteric liquid crystal display according to claim 1, wherein the plurality of regions are divided by partition walls formed in a lattice shape. The radiation-sensitive liquid crystal aligning agent is
[A] The cholesteric liquid crystal display according to claim 1 or 2, which contains a polyorganosiloxane having a photoalignable group.   The cholesteric liquid crystal display according to claim 3, wherein the photo-alignment 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). 4. A cholesteric liquid crystal display according to 4.

(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 or cyclohexylene group are It may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom, a fluorine atom or a cyano group, and R ² is a single bond, having 1 to 1 carbon atoms. 3 is an alkanediyl group, an oxygen atom, a sulfur atom, —CH═CH—, —NH— or —COO—, a is an integer of 0 to 3, provided that when a is 2 or more, each R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, and b is an integer of 0 to 4.
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, 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. R ⁷ is an oxygen atom, —COO— * or —OCO— *. However, bond binds to R ⁸ marked with *. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. However, a bond marked with * is bonded to a carboxyl group. f and g are each an integer of 1 to 10. e is an integer of 0-3. However, when e is 2 or more, R ⁷ and R ⁸ may be the same or different. )   [A] The polyorganosiloxane is an epoxy group-containing polyorganosiloxane and at least one selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2). The cholesteric liquid crystal display according to claim 3, 4 or 5, which is a reaction product. The radiation-sensitive liquid crystal aligning agent is
[B] At least one polymer selected from the group consisting of polyamic acid, polyimide, ethylenically unsaturated compound polymer, and polyorganosiloxane having no photo-alignment group is further contained. The cholesteric liquid crystal display according to any one of 6. The radiation-sensitive liquid crystal aligning agent is
[C] at least one structure selected from the group consisting of an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a t-butyl ester structure of a carboxylic acid. The cholesteric liquid crystal display according to any one of claims 3 to 7, further comprising a compound having at least one. A pair of opposing substrates, a cholesteric liquid crystal disposed in a plurality of regions between the substrates divided in the vertical direction, and a liquid crystal alignment film stacked between the substrates and the cholesteric liquid crystal, respectively. A method of manufacturing a cholesteric liquid crystal display,
(1) A step of applying a radiation-sensitive liquid crystal aligning agent on a plurality of divided regions of at least one of the substrates to form a coating film,
(2) A method for producing a cholesteric liquid crystal display, comprising: a step of forming a liquid crystal alignment film by irradiating the coating film with radiation; and (3) a step of filling a cholesteric liquid crystal in each divided region where the liquid crystal alignment film is formed. .   The method for producing a cholesteric liquid crystal display according to claim 9, wherein the coating is performed by an inkjet method. A pair of opposing substrates, a cholesteric liquid crystal disposed in a plurality of regions between the substrates divided in the vertical direction, and a liquid crystal alignment film stacked between the substrates and the cholesteric liquid crystal, respectively. A liquid crystal aligning agent for the liquid crystal alignment film in a cholesteric liquid crystal display,
A liquid crystal aligning agent characterized by having radiation sensitivity.

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