JPWO2012020628A1 - Light directivity control unit and manufacturing method thereof, 2D / 3D switchable display module, and liquid crystal aligning agent - Google Patents

Abstract

The present invention is formed by a transparent substrate, a lenticular layer having a lenticular lens array disposed on the back side of the transparent substrate and facing the front side of the transparent substrate, and a radiation-sensitive liquid crystal aligning agent laminated on the back side of the lenticular layer. The light directivity control unit includes a liquid crystal alignment film and a liquid crystal lens layer laminated on the back side of the lenticular layer via the liquid crystal alignment film. It is good to provide the other liquid crystal aligning film laminated | stacked on the back surface of the said liquid-crystal lens layer, and formed with a radiation sensitive liquid crystal aligning agent.

Description

  The present invention relates to a light directivity control unit and a manufacturing method thereof, a 2D / 3D switchable display module, and a liquid crystal aligning agent.

  2. Description of the Related Art In recent years, as a liquid crystal display device that performs stereoscopic three-dimensional (3D) display, an autostereoscopic (autostereoscopic) module that recognizes 3D images without using visual aids such as special glasses on the viewer side Has been developed. As an example of such an autostereoscopic display module, a two-dimensional (2D) mode and a three-dimensional (3D stereoscopic) mode are provided with an array of elongated lenticular elements extending in a vertical direction and in parallel on a two-dimensional liquid crystal display panel. Has been proposed (see Patent Literature 1 and Non-Patent Literature 1).

  In the 2D / 3D switchable display module described above, the lenticular element is generally formed of liquid crystal. However, in order to ensure good display, it is necessary to increase the uniformity of the alignment of the liquid crystal. Therefore, conventionally, a liquid crystal alignment film is formed around the liquid crystal formation space, and after the rubbing treatment, the liquid crystal is formed to enhance the alignment of the liquid crystal.

  The rubbing treatment is usually performed by using a rubbing cloth affixed to the outer peripheral surface of the roller, contacting the rubbing cloth with the surface of the liquid crystal alignment film while rotating the roller, and rubbing the surface on which the liquid crystal alignment film is formed. . When such a rubbing process is performed on a surface having fine irregularities such as a concave lenticular, the direction of the process tends to be uneven. Therefore, the uniformity of alignment of the liquid crystal to be formed cannot be increased, and as a result, there is a disadvantage that the resolution of the display obtained is lowered.

Special table 2009-528565

IDW, Vol. 11, pp. 1495-1496,2004

  The present invention has been made to solve the above-described disadvantages. That is, the main object of the present invention is to provide a light directivity control unit capable of obtaining a good display such as resolution by including a liquid crystal lens layer having excellent alignment uniformity, and 2D including the light directivity control unit. A 3D switchable display module is provided. Another object of the present invention is to provide a method for manufacturing such a light directivity control unit.

The invention made to solve the above problems is
A transparent substrate;
A lenticular layer disposed oppositely on the front side of the transparent substrate and having a lenticular lens array on the back side;
A liquid crystal alignment film laminated on the back surface of the lenticular layer and formed of a radiation-sensitive liquid crystal alignment agent;
The light directivity control unit includes a liquid crystal lens layer laminated on the back side of the lenticular layer via the liquid crystal alignment film.

  The light directivity control unit of the present invention has the above-described configuration, and a lenticular layer and a liquid crystal lens layer oriented in a certain direction are laminated. The refractive index of the liquid crystal varies depending on the angle formed by the vibration direction of polarized light passing through the unit and the liquid crystal alignment direction of the liquid crystal lens layer. That is, the refractive index of the lenticular layer and the liquid crystal lens layer is the same for polarized light that vibrates in a predetermined direction, and the refractive index of the lenticular layer and the liquid crystal lens layer is different for polarized light having a different vibration surface. It can be configured as follows. Therefore, according to the light directivity control unit, the directivity of light can be switched depending on whether light is simply transmitted or refracted in the liquid crystal lens layer. Moreover, since the said liquid crystal aligning film is formed of a radiation sensitive liquid crystal aligning agent, the said light directivity control unit is excellent in the alignment uniformity of the alignment film compared with the liquid crystal aligning film which performed the conventional rubbing process. Thereby, in the light directivity control unit, the alignment uniformity of the liquid crystal lens layer formed through the liquid crystal alignment film is increased. As a result, the display module that can switch between the two-dimensional mode and the three-dimensional mode provided with the light directivity control unit can improve the display quality.

  The light directivity control unit may include another liquid crystal alignment film laminated on the back surface of the liquid crystal lens layer and formed of a radiation sensitive liquid crystal alignment agent. In addition to the front side of the liquid crystal lens layer, the back side is also laminated with a liquid crystal alignment film formed of a radiation sensitive liquid crystal aligning agent, so that the alignment uniformity of the liquid crystal lens layer in the light directivity control unit further increases. Rise. As a result, the display quality of the 2D / 3D switchable display module including the light directivity control unit can be further improved.

  The light directivity control unit may include a pair of transparent electrode layers stacked on both sides of the liquid crystal lens layer. According to the light directivity control unit, by having a pair of transparent electrode layers laminated on both sides of the liquid crystal lens layer, the orientation of the liquid crystal in the liquid crystal lens layer is determined depending on whether voltage is applied between the transparent electrode layers. The light directivity can be switched by changing.

  The light directivity control unit may include a liquid crystal layer superimposed on the transparent substrate and a pair of transparent electrode layers disposed on both sides of the liquid crystal layer. In the combination of the liquid crystal layer and the pair of transparent electrode layers disposed on both sides of the liquid crystal, the orientation of the liquid crystal layer between the transparent electrode layers changes depending on whether or not voltage is applied between the pair of transparent electrode layers. This constitutes a liquid crystal switch that can change the rotation angle of the polarization plane of the traveling polarized light. Therefore, the light directivity control unit can further switch the light directivity depending on whether or not voltage is applied between the pair of transparent electrode layers by further including such a liquid crystal switch.

  The radiation-sensitive liquid crystal aligning agent may contain [A] a polyorganosiloxane having a photo-alignment group (hereinafter sometimes 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 lens layer formed through the liquid crystal alignment film 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 photoalignable group, introduction of the photoalignable group into polyorganosiloxane in the liquid crystal aligning agent is facilitated, and A liquid crystal alignment film formed from a liquid crystal aligning agent has higher optical alignment performance. As a result, the alignment uniformity of the liquid crystal lens layer in the light directivity control unit 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、ターフェニレン基及びシクロヘキシレン基の水素原子の一部又は全部は、フッ素原子を有していてもよい炭素数１〜１０のアルキル基若しくは炭素数１〜１０のアルコキシ基、フッ素原子又はシアノ基で置換されていてもよい。Ｒ^２は、単結合、炭素数１〜３のアルカンジイル基、酸素原子、硫黄原子、−ＣＨ＝ＣＨ−、−ＮＨ−、−ＣＯＯ−又は−ＯＣＯ−である。ａは０〜３の整数である。但し、ａが２以上の場合、複数のＲ^１及びＲ^２はそれぞれ同一であっても異なっていてもよい。Ｒ^３は、フッ素原子又はシアノ基である。ｂは０〜４の整数である。
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。このフェニレン基及びシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０の鎖状若しくは環状のアルキル基、炭素数１〜１０の鎖状若しくは環状のアルコキシ基、フッ素原子又はシアノ基で置換されていてもよい。Ｒ^５は、単結合、炭素数１〜３のアルカンジイル基、酸素原子、硫黄原子又は−ＮＨ−である。ｃは、１〜３の整数である。但し、ｃが２以上の場合、複数のＲ^４及びＲ^５はそれぞれ同一であっても異なっていてもよい。Ｒ^６は、フッ素原子又はシアノ基である。ｄは、０〜４の整数である。Ｒ^７は、酸素原子、−ＣＯＯ−又は−ＯＣＯ−である。Ｒ^８は、２価の芳香族基、２価の脂環式基、２価の複素環式基又は２価の縮合環式基である。Ｒ^９は、単結合、−ＯＣＯ−（ＣＨ_２）_ｆ−＊又は−Ｏ（ＣＨ_２）_ｇ−＊である。＊は、カルボキシル基との結合部位を示す。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、複数のＲ^７及びＲ^８はそれぞれ同一であっても異なっていてもよい。）The group having a cinnamic acid structure is at least one group 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). Good.

(In the formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group. Some or all of the hydrogen atoms of the phenylene group, biphenylene group, terphenylene group and cyclohexylene group are And may be substituted with an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group, and R ² is a single bond or a carbon number. 1 to 3 alkanediyl groups, oxygen atom, sulfur atom, —CH═CH—, —NH—, —COO—, or —OCO—, where a is an integer of 0 to 3, provided that a is 2 or more. A plurality of R ¹ and R ² may be the same or different from each other, 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. Some or all of the hydrogen atoms of the phenylene group and the cyclohexylene group may be 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. May be substituted. R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or —NH—. c is an integer of 1 to 3. However, when c is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group. d is an integer of 0-4. R ⁷ is an oxygen atom, —COO— or —OCO—. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. * Indicates a binding site with 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, the plurality of R ⁷ and R ⁸ may be the same or different. )

  By using a 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, and as a result, the liquid crystal lens layer in the light directivity control unit can be improved. The alignment uniformity can be further improved.

  [A] The polyorganosiloxane having a photo-alignment group is selected from the group consisting of a polyorganosiloxane having an epoxy group, a compound represented by the above formula (1), and a compound represented by the above formula (2). The reaction product with at least one compound is preferred. In the light directivity control unit, by utilizing the reactivity between the polyorganosiloxane having an epoxy group and the specific cinnamic acid derivative, the specific cinnamic acid derivative having a photoalignment group on the polyorganosiloxane as the main chain Side chain groups derived from can be easily introduced.

  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 one or two or more structures, and when this structure is one, a plurality of compounds (hereinafter sometimes 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 in the baking step (post-bake), and the generated acid promotes the crosslinking of [A] polyorganosiloxane. The heat resistance of the obtained light directivity control unit can be improved.

  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 “ It is preferable to further contain [B] other polymer ”. Even if the content of the photoalignable polyorganosiloxane in the liquid crystal aligning agent is reduced by adding another polymer to the liquid crystal aligning agent, the photoalignable polyorganosiloxane is unevenly distributed on the surface of the liquid crystal aligning layer. The optical alignment performance of the liquid crystal alignment film can be increased, and as a result, the alignment uniformity of the liquid crystal in the liquid crystal lens layer can be maintained high. Therefore, the content of the photoalignable polyorganosiloxane having a high production cost in the liquid crystal aligning agent can be reduced, and as a result, the production cost of the light directivity control unit can be reduced.

The 2D / 3D switchable display module of the present invention is
A display panel;
The light directivity control unit.

  Since the 2D / 3D switchable display module includes the above-described light directivity control unit that excels in liquid crystal alignment uniformity of the liquid crystal lens layer, it almost reduces the level of 2D and 3D display quality. Therefore, a favorable display can be provided to the viewer.

The manufacturing method of the light directivity control unit of the present invention is as follows.
A transparent substrate, a lenticular layer disposed on the front side of the transparent substrate and having a lenticular lens array on the back surface, a liquid crystal alignment film laminated on the back surface of the lenticular layer, and a lenticular layer via the liquid crystal alignment film A light directivity control unit comprising a liquid crystal lens layer laminated on the back side of
(1) A step of applying a radiation-sensitive liquid crystal aligning agent to the back surface of the lenticular layer to form a coating film,
(2) forming a liquid crystal alignment film by irradiating the coating film with radiation; and (3) forming a liquid crystal lens layer between the liquid crystal alignment film and the transparent substrate.

In addition, the step (3)
(3-1) A step of disposing the liquid crystal alignment film and the transparent substrate to face each other and forming a space between them, and (3-2) filling the space with a liquid crystal material to form a liquid crystal lens layer. It is preferable to have the process to do.

Furthermore, the step (3-2)
(3-2-1) It is more preferable to have a step of sucking polymerizable liquid crystal into this space, and (3-2-2) a step of polymerizing this polymerizable liquid crystal to form a liquid crystal lens layer.

In addition, the step (3)
(3-1 ′) a step of applying a liquid crystal material on the back side of the liquid crystal alignment film to form a liquid crystal lens layer; and (3-2 ′) a step of disposing a transparent substrate on the back side of the liquid crystal lens layer. It is preferable to have.

Further, the step (3-1 ′)
(3-1′-1) a step of applying a polymerizable liquid crystal on the back side of the liquid crystal alignment film, and (3-1′-2) a step of polymerizing the polymerizable liquid crystal to form a liquid crystal lens layer. It is more preferable.

  According to the manufacturing method of the present invention, a light directivity control unit excellent in alignment uniformity of a liquid crystal lens layer can be efficiently manufactured, and improvement in productivity and reduction in manufacturing cost can be promoted.

The liquid crystal aligning agent of the present invention is
A liquid crystal aligning agent for aligning a liquid crystal lens layer of a 2D / 3D switchable display module,
It has a radiation sensitivity.

  According to the liquid crystal aligning agent of the present invention, the orientation of the liquid crystal alignment film laminated on the liquid crystal lens layer of the light directivity control unit of the 2D / 3D switchable display module can be improved. The alignment uniformity can be improved.

  According to the light directivity control unit of the present invention, the alignment uniformity of the liquid crystal lens layer can be improved, and as a result, the display accuracy such as the resolution of a 2D / 3D switchable display module using the liquid crystal lens layer can be improved. it can.

It is sectional drawing of the light directivity control unit which concerns on 1st Embodiment of this invention. It is sectional drawing of the light directivity control unit which concerns on 2nd Embodiment of this invention. It is sectional drawing of the light directivity control unit which concerns on 3rd Embodiment of this invention. It is sectional drawing of the light directivity control unit which concerns on 4th Embodiment of this invention. It is a 2D / 3D switchable display module sectional view of a 1st embodiment of the present invention. It is 2D / 3D switchable display module sectional drawing of 2nd Embodiment of this invention. It is 2D / 3D switchable display module sectional drawing of 3rd Embodiment of this invention. It is 2D / 3D switchable display module sectional drawing of 4th Embodiment of this invention.

<Light directivity control unit>
First, the light directivity control unit according to the first embodiment will be described below with reference to FIG. The light directivity control unit 1 includes a pair of transparent substrates 11 and 12, a lenticular layer 13, a liquid crystal lens layer 14, and two liquid crystal alignment films 15 and 16. This light directivity control unit 1 is in a case where the extraordinary refractive index of the liquid crystal lens layer 14 (the refractive index for polarized light oscillating in the direction parallel to the optical axis of the liquid crystal) is larger than the refractive index of the lenticular layer 13. . In the light directivity control unit of FIG. 1, one transparent substrate 12 side is the back side, that is, the side on which light from the display panel is incident, and the other transparent substrate 11 side is the front side, that is, the light is emitted toward the viewer. The side to do.

  The pair of transparent substrates 11 and 12 are disposed to face each other, and the other transparent substrate 11 is disposed substantially parallel to the surface side of the one transparent substrate 12. A lenticular layer 13 is laminated on the back surface of the transparent substrate 11. The lenticular layer 13 has a concave lenticular lens array on the back surface. The ridge line direction of the lenticular lens layer 13 is configured to be one direction. A liquid crystal alignment film 15 is stacked on the surface of the concave lenticular lens array on the back surface of the lenticular layer 13, and a liquid crystal alignment film 16 is stacked on the surface of one transparent substrate 12. The liquid crystal lens layer 14 is formed between the two liquid crystal alignment films 15 and 16.

  The two liquid crystal alignment films respectively formed on the back surface of the lenticular layer 13 and the surface of the transparent substrate 12 have the liquid crystal alignment ability in the same direction, that is, both in the z direction by irradiation with radiation.

  The liquid crystal lens layer 14 is composed of a liquid crystal filled between the two liquid crystal alignment layers 15 and 16, and as a result, the liquid crystal lens layer 14 has a lenticular lens having irregularities opposite to the lenticular layer 13 on its surface. Has an array. The liquid crystal of the liquid crystal lens layer 14 is aligned in the z direction according to the liquid crystal alignment ability of the liquid crystal alignment films 15 and 16. Therefore, the refractive index of the liquid crystal lens layer 14 is high for polarized light whose vibration direction is the z direction, while it is low for polarized light whose vibration direction is the x direction, and has a refractive index substantially equal to that of the lenticular layer 13. doing.

  In the light directivity control unit 1, since the alignment direction of the liquid crystal forming the liquid crystal lens layer 14 is the z direction, the liquid crystal lens layer is used when the oscillation direction of polarized light incident on the light directivity control unit 1 is the z direction. 14 and the lenticular layer 13 are different in refractive index, and the refractive index of the liquid crystal lens layer 14 is larger. Therefore, the combination of the liquid crystal lens layer 14 and the lenticular layer 13 functions as a lenticular lens having the shape of the liquid crystal lens layer 14. The light directivity control unit 1 provides a refractive light directivity function. On the other hand, when the direction of polarized light incident on the light directivity control unit 1 is the x direction, the refractive index of the liquid crystal lens layer 14 and that of the lenticular layer 13 are substantially the same. In the combination, the light is simply transmitted without being refracted, and the light directivity control unit 1 provides a passing light directivity function. The liquid crystal alignment ability of the two liquid crystal alignment films may be the x direction in addition to the z direction, but the z direction is preferable.

  The light directivity control unit 2 according to the second embodiment of the present invention will be described below with reference to FIG. The light directivity control unit 2 includes a pair of transparent substrates 11 and 12, a lenticular layer 13, a liquid crystal lens layer 14, two liquid crystal alignment films 15 and 16, a transparent substrate (switch transparent substrate) 21, and a pair of Transparent electrode layers (switch transparent electrodes) 22 and 23 and a liquid crystal layer (switch liquid crystal layer) 24 are provided. The combination of the switch transparent substrate 21, the pair of switch transparent electrode layers 22 and 23, and the switch liquid crystal layer 24 forms the switch liquid crystal layer 24 depending on whether voltage is applied between the pair of switch transparent electrode layers 22 and 23. It functions as a “liquid crystal switch” in which the rotation of the circularly polarized light changes between 0 ° and 90 ° by changing the alignment direction of the liquid crystal. That is, the light directivity control unit 2 has a configuration in which a liquid crystal switch is added to the configuration of the light directivity control unit 1 of the first embodiment. In FIG. 2, the same configurations as those of the light directivity control unit 1 of the first embodiment are denoted by the same reference numerals and description thereof is omitted. In the present specification, the transparent substrate, the transparent electrode layer, and the liquid crystal layer constituting the liquid crystal switch are also referred to as a switch transparent substrate, a switch transparent electrode layer, and a switch liquid crystal layer, respectively.

  In the light directivity control unit 2, a switch transparent substrate 21 is disposed on the surface side of the transparent substrate 11 so as to face the transparent substrate 11. A pair of transparent electrode layers 22 and 23 are arranged with a certain gap on the opposing surfaces of the transparent substrate 11 and the switch transparent substrate 21, and a switch liquid crystal layer 24 is disposed between the pair of transparent conductive layers 22 and 23. Is done.

  In addition to the configuration of the light directivity control unit 1, the light directivity control unit 2 further includes the configuration of the liquid crystal switch. Therefore, depending on whether voltage is applied between the transparent electrode layers 22 and 23, the liquid crystal lens layer The polarized light in the desired vibration direction incident on 14 can be switched so as to be emitted from the light directivity control unit 2. That is, according to the light directivity control unit 2, incident light polarized in the z direction can be refracted by the liquid crystal lens layer 14 and the lenticular layer 13, and then polarized in a desired direction by the liquid crystal switch and emitted. In addition, incident light polarized in the x direction can be simply transmitted through the liquid crystal lens layer 14 and the lenticular layer 13, and then polarized in a desired direction by the liquid crystal switch to be emitted. Therefore, according to the light directivity control unit 2, it is possible to switch between the transmission type and the refraction type light directivity functions for the outgoing light having a desired vibration direction.

  The light directivity control unit 3 according to the third embodiment of the present invention will be described below with reference to FIG. The light directivity control unit 3 includes a pair of transparent substrates 11 and 12, a lenticular layer 13, a liquid crystal lens layer 14, two liquid crystal alignment films 15 and 16, a switch transparent electrode substrate 25, a transparent electrode layer 26, And a switch liquid crystal layer 24. The switch transparent electrode substrate 25 is obtained by laminating a transparent electrode layer on the back side of the transparent substrate. That is, the light directivity control unit 3 has a structure in which a liquid crystal switch including a switch transparent electrode substrate 25, a transparent electrode layer 26, and a switch liquid crystal layer 24 is added to the structure of the light directivity control unit 1 of the first embodiment. doing. In FIG. 3, the same components as those of the light directivity control unit 1 of the first embodiment are denoted by the same reference numerals and description thereof is omitted.

  The light directivity control unit 3 includes a switch transparent electrode substrate 25, a switch liquid crystal layer 24, and a transparent electrode layer 26 between the liquid crystal alignment film 16 and the one transparent substrate 12 in the light directivity control unit 1 of the first embodiment. It has a configuration arranged in this order. The switch transparent electrode substrate 25 and the transparent electrode layer 26, and the switch liquid crystal layer 24 sandwiched therebetween function as a liquid crystal switch as described above. Therefore, similarly to the light directivity control unit 2 of the second embodiment, the light directivity control unit 3 has a desired vibration direction depending on whether or not voltage is applied between the switch transparent electrode substrate 25 and the transparent electrode layer 26. With respect to the incident light, it is possible to switch between the transmissive and refractive light directivity functions. That is, according to the light directivity control unit 3, incident light polarized in a specific direction on the xz plane is converted into z-polarized light by the liquid crystal switch and refracted by the liquid crystal lens layer 14 and the lenticular layer 13 to be emitted. In addition, incident light polarized in a specific direction on the xz plane can be converted into polarized light in the x direction by the liquid crystal switch, and can be simply transmitted through the liquid crystal lens layer 14 and the lenticular layer 13 to be emitted.

  The light directivity control unit 4 according to the fourth embodiment of the present invention will be described below with reference to FIG. The light directivity control unit 4 includes a pair of transparent substrates 11 and 12, a lenticular 13, a liquid crystal lens layer 14, two liquid crystal alignment films 15 and 16, and a pair of transparent electrode layers 27 and 28. . That is, the light directivity control unit 4 has a configuration in which a pair of transparent conductive layers 27 and 28 are added to the configuration of the light directivity control unit 1 of the first embodiment. In FIG. 4, the same configurations as those of the light directivity control unit 1 of the first embodiment are denoted by the same reference numerals and description thereof is omitted.

  In the light directivity control unit 4, transparent electrode layers 27 and 28 are laminated on the pair of transparent substrates 11 and 12 on the opposing surface sides, respectively. A lenticular layer 13 is laminated on the back surface of one transparent electrode layer 27. A liquid crystal alignment film 16 is laminated on the surface of the other transparent electrode layer 28. In the light directivity control unit 4, the orientation direction of the liquid crystal forming the liquid crystal lens layer 14 disposed between the pair of transparent electrode layers 27 and 28 can be changed depending on whether or not the voltage is applied between the pair of transparent electrode layers 27 and 28. Therefore, according to the light directivity control unit 4, the lens function by the combination of the liquid crystal lens layer 14 and the lenticular layer 13 can be switched with respect to incident light in a predetermined vibration direction, so that the light directivity of transmission type and refraction type can be switched. You can switch functions.

  Examples of the transparent substrates 11 and 12 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.

  As a material for forming the lenticular layer 13, the refractive index thereof is preferably about the same as the ordinary refractive index of the liquid crystal lens layer 14. Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate Resins such as acrylic, polycarbonate, polyvinyl chloride, polyolefin and the like are preferably used.

  The back surface of the transparent substrate may have a convex or concave lenticular shape, and the transparent substrate and the lenticular layer may be integrated.

<Liquid crystal alignment film>
In any of the above-described light directivity control units, the liquid crystal alignment films 15 and 16 are provided. The liquid crystal alignment film has a function of regulating the alignment direction of the liquid crystal formed adjacent to the liquid crystal alignment layer and improving the alignment. In the present invention, the liquid crystal alignment film 15 laminated on the front surface of the liquid crystal lens layer 14, that is, the back surface of the lenticular layer 13, is required to be a liquid crystal alignment film formed of a radiation-sensitive liquid crystal aligning agent. The radiation-sensitive liquid crystal aligning agent uses polarized light in a predetermined vibration direction instead of the usual rubbing treatment to enhance the alignment of alignment film forming molecules and enhance the liquid crystal alignment performance. By using a radiation-sensitive liquid crystal aligning agent, it is possible to form a liquid crystal aligning film having excellent orientation even on the fine uneven surface on the back of the lenticular layer, which is difficult to rub, and the resulting liquid crystal The alignment uniformity of the lens layer can be improved.

  Further, the liquid crystal alignment film 16 formed on the back surface side of the liquid crystal lens layer 14, that is, on the surface of the transparent substrate 12 is preferably formed of a radiation-sensitive liquid crystal alignment agent. By forming the liquid crystal alignment film laminated on the back surface of the liquid crystal lens layer 14 with a radiation-sensitive liquid crystal aligning agent, the alignment uniformity of the liquid crystal lens layer 14 can be further improved, and as a result, the light directivity control is performed. The display accuracy such as the resolution of the 2D / 3D switchable display module including the unit can be further improved.

<Radiation sensitive liquid crystal aligning agent>
The liquid crystal alignment film 15 is formed from a radiation-sensitive liquid crystal aligning agent (hereinafter also simply referred to as “liquid crystal aligning agent”). By forming from a radiation-sensitive liquid crystal aligning agent, the liquid crystal alignment film 15 that is formed on the fine uneven surface of the lenticular layer and is considered difficult to improve the alignment by rubbing treatment is also an alignment film forming molecule. As a result, the alignment uniformity of the obtained liquid crystal lens layer 14 can be improved. Therefore, the display accuracy such as the resolution of the 2D / 3D switchable display module including the light directivity control unit can be further improved. The liquid crystal alignment film 16 can also be formed from a radiation sensitive liquid crystal aligning agent. When both of the pair of liquid crystal alignment films 15 and 16 laminated on both sides of the liquid crystal lens layer 14 are aligned using the radiation sensitive liquid crystal aligning agent and the same polarized radiation, both the pair of liquid crystal alignment films 15 and 16 are aligned. It is preferable because the alignment direction of the alignment film forming molecules in the film can be matched at a high level, and as a result, the alignment uniformity of the liquid crystal lens layer 14 to be obtained can be further improved.

  The liquid crystal aligning agent is not particularly limited as long as it is radiation sensitive, and various liquid crystal aligning agents can be used. For example, the liquid crystal aligning agent contains a specific polyimide resin described in JP-A-9-297313. And those containing a polymer having a molecular unit capable of causing photochemical isomerization / dimerization described in JP-A-6-287453.

  As said liquid crystal aligning agent, the liquid crystal aligning agent containing the inorganic polymer which has a photo-alignment group is preferable. By using a liquid crystal aligning agent containing an inorganic polymer having a photo-alignment group, a liquid crystal alignment film having excellent liquid crystal alignment performance and thermal stability can be formed.

  Moreover, the liquid crystal aligning agent containing the polyorganosiloxane which has [A] photo-alignment group among the liquid crystal aligning agent containing the inorganic polymer which has the said photo-alignment group is more preferable. When the liquid crystal aligning agent contains [A] photo-alignable polyorganosiloxane, it is possible to form a liquid crystal alignment film having excellent transparency, and the light irradiation amount necessary for alignment due to high-sensitivity photo-alignment. Can be reduced. Since the firing temperature can be lowered, the range of selection of the substrate to be used can be widened, and furthermore, since a heating step during and after radiation irradiation is unnecessary, a liquid crystal alignment film can be formed efficiently.

  [A] The liquid crystal aligning agent containing the photo-alignable polyorganosiloxane preferably contains [B] other polymer and [C] ester structure-containing compound, and the other, as long as the effects of the present invention are not impaired. These optional components may be contained. 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 Examples thereof include a group having a structure, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, and a coumarin-containing group having coumarin or a derivative thereof 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 the phenylene group, biphenylene group, terphenylene group and cyclohexylene group may have a fluorine atom, or an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon 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—, —COO— or —OCO—. a is an integer of 0-3. However, when a is 2 or more, the plurality of R ¹ and R ² may be the same or different. R ³ is a fluorine atom or a cyano group. b is an integer of 0-4.

  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, the plurality of R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group. d is an integer of 0-4. R ⁷ is an oxygen atom, —COO— or —OCO—. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. * Indicates a binding site with 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, the plurality of 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 the 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, 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.

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

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

  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. Further, the radiation-sensitive liquid crystal aligning agent 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 extremely high storage stability. It is convenient because it is 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. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by Chisso).

  [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] Method for Synthesizing Photo-Orienting 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.

  [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 the photoalignable polyorganosiloxane is unevenly distributed in the vicinity of the surface layer. For this reason, even if the content of the photoalignable polyorganosiloxane in the liquid crystal aligning agent is reduced by increasing the content of other polymers, the photoalignable polyorganosiloxane is unevenly distributed on the alignment film surface. Liquid crystal orientation can be obtained. Therefore, in this invention, it becomes possible to reduce content in the said liquid crystal aligning agent of photoalignment 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 JP 2010-97188 A.

  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, aromatic diamine, and diaminoorganosiloxane. 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 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.)

  Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in JP 2010-97188 A.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[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”) And is sometimes referred to as “compound”). (The copolymer obtained by this copolymerization may be hereinafter referred to as “(B1) 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.

  In the copolymer (B1), 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.

  (B1) A copolymer can synthesize | combine each unsaturated compound, for example by radical polymerization in presence of a suitable solvent and a polymerization initiator. 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, more preferably 5,000 parts by mass or less, and still more preferably 2,000 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. Further, by adding the [C] ester structure-containing compound to the liquid crystal aligning agent, the liquid crystal aligning film can be baked at a lower temperature, so that the selection range of the substrate on which the liquid crystal aligning film is formed is expanded.

  [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. In the case where the structure is one kind or more, the compound is plural. That is, the [C] ester structure-containing compound may be a compound having two or more of the same kind of structures among these structures, and has two or more of the different kinds of structures among these structures. It may be a compound. 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. A cyclic group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
In formula (C-4), R ¹⁸ represents an alkyl group having 1 to 12 carbon atoms. n2 is an integer of 2-8.
In formula (C-5), R ¹⁹ represents an alkyl group having 1 to 12 carbon atoms. n3 is an integer of 2-8. )

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, 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 allocymene, 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 made by ACC), ULTRASET (BF ₄ , PF ₆ ) (diazonium salt made by Asahi Denka Kogyo), UVE series (iodonium salt made by GE), Photoinitiator 2074 ((C ₆ F ₆ ) ₄ B) (iodonium salt made by Rhone-Poulenc), CYRACURE UVI-6974, CYRACURE UVI-6990 (above, sulfonium salt made by UCC), UVI-508, UVI-509 (above, sulfonium made by GE) Salt), OPTOMER SP-150, OPTOMER SP-170 (a sulfonium salt manufactured by Asahi Denka Kogyo), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (above, a sulfonium salt manufactured by Sanshin Chemical Industry), IRU GACURE 261 (metallocene compound manufactured by Ciba Geigy), aluminum chelate A (W) (manufactured by Kawaken Fine Chemicals) 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 (manufactured by Sanshin Chemical Industry), UVI-6990, UVI-6922, UVI-6974 (and above, Union Carbide). Adekaoptomer SP-150, Adekaoptomer SP-170, Adeka Opton CP-66, Adeka Opton CP-77 (manufactured by Asahi Denka Kogyo), 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 Another reaction product of the silane compound having, is 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.

<Method for preparing 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 ink jet method, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, and thereby the solution viscosity is preferably in the range of 3 mPa · s to 15 mPa · s.

  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 of manufacturing light directivity control unit>
The light directivity control unit of the present invention can be manufactured, for example, as follows. The manufacturing method of the light directivity control unit of the present invention is as follows.
A transparent substrate, a lenticular layer disposed on the front side of the transparent substrate and having a lenticular lens array on the back surface, a liquid crystal alignment film laminated on the back surface of the lenticular layer, and a lenticular layer via the liquid crystal alignment film A light directivity control unit comprising a liquid crystal lens layer laminated on the back side of
(1) A step of applying a radiation-sensitive liquid crystal aligning agent to the back surface of the lenticular layer to form a coating film,
(2) forming a liquid crystal alignment film by irradiating the coating film with radiation; and (3) forming a liquid crystal lens layer between the liquid crystal alignment film and the transparent substrate.

  In steps (1) and (2), a liquid crystal alignment film is formed with a radiation-sensitive liquid crystal aligning agent.

<Method for forming liquid crystal alignment film>
In the light directivity control unit, the liquid crystal alignment films 15 and 16 may be formed by, for example, radiation sensitive on the surface of the back surface of the lenticular layer 13 on which the lenticular lens array is formed and on the surface of the transparent substrate 12. The method of forming the coating film of a crystalline liquid crystal aligning film, and then providing liquid crystal alignment ability to this coating film by the photo-alignment method is mentioned.

  The liquid crystal alignment film can be produced, for example, by the following method using the liquid crystal alignment agent. The liquid crystal aligning agent is applied to the substrate by an appropriate application method such as a spray coating method, a slit coating method, a roll coater method, a spinner method, a printing method, an ink jet method, or a vapor deposition method. 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.

  Next, liquid crystal alignment ability is imparted by irradiating the coating film with linearly or partially polarized radiation or non-polarized radiation. 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 liquid crystal display element is reduced. Contribute to

  In the step (3), a liquid crystal lens layer is formed between the liquid crystal alignment film 15 and the transparent substrate 12 (between the liquid crystal alignment films 15 and 16). (3) As a method of performing the step, for example, (A) a liquid crystal alignment film 15 and the transparent substrate 12 are joined to form a space, and a liquid crystal material is filled in the space to form the liquid crystal lens layer 14. Examples thereof include (B) a method of forming a liquid crystal lens layer 14 using a liquid crystal material adjacent to the liquid crystal alignment film 15 and then disposing the transparent substrate 12.

In the case of the method (A), the step (3)
(3-1) A step of disposing the liquid crystal alignment film and the transparent substrate to face each other and forming a space between them, and (3-2) filling the space with a liquid crystal material to form a liquid crystal lens layer. The process of carrying out.

  In the step (3-1), the liquid crystal alignment film 15 and the transparent substrate 12 are disposed so as to face each other, and are bonded to each other between the liquid crystal alignment film 15 and the transparent substrate 12 (between the liquid crystal alignment films 15 and 16). A sandwiched space is formed.

  The method for joining the lenticular layer 13 and the transparent substrate 12 is not particularly limited, and examples thereof include a method using an adhesive, a method using a pressure-sensitive adhesive, a heat sealing method, and a method using excimer UV. As the adhesive, an acrylic adhesive or the like is preferably used.

  In the step (3-2), a liquid crystal material is filled in the space between the liquid crystal alignment films 15 and 16 to form the liquid crystal lens layer 14.

  Examples of the liquid crystal material include liquid polymer liquid crystals, polymerizable liquid crystals, and non-polymerizable liquid crystals. When a polymerizable liquid crystal is used as the liquid crystal material, it is necessary to polymerize the polymerizable liquid crystal as will be described later.

  As a method of filling the liquid crystal material, for example, the space between the liquid crystal alignment films 15 and 16 is reduced in pressure, the liquid crystal material is sucked, the space between the liquid crystal alignment films 15 and 16 is immersed in the liquid crystal material, and the capillary tube Examples thereof include a method of filling a liquid crystal material by a phenomenon or the like, a method of injecting a liquid crystal material into a space between the liquid crystal alignment films 15 and 16, and the like.

In the case of the method (B), the step (3)
(3-1 ′) a step of applying a liquid crystal material on the back side of the liquid crystal alignment film to form a liquid crystal lens layer; and (3-2 ′) a step of disposing a transparent substrate on the back side of the liquid crystal lens layer. Have

  In (3-1 ′) above, a liquid crystal material is applied to the back side of the liquid crystal alignment film 15 to form the liquid crystal lens layer 14. As this liquid crystal material, the example of the liquid crystal material used at the said (3-1) process etc. are mentioned, for example.

  Examples of the method of applying the liquid crystal material to the back side of the liquid crystal alignment film 15 include a method of dropping using a pipette, a method of using a brush, a method of spray coating, a method of roll coating, and the like.

  In (3-2 ′) above, the transparent substrate 12 is disposed on the back side of the liquid crystal lens layer 14 formed above, and, for example, the lenticular layer 13 and the transparent substrate 12 are bonded. Examples of the bonding method include an example of a method of bonding the lenticular layer 13 and the transparent substrate 12 in the step (3-1 ′).

In the steps (3-2) and (3-1 ′), when a polymerizable material is used as the liquid crystal material, the polymerizable liquid crystal is polymerized by heating and / or non-polarized radiation irradiation. That is, in this case
The above step (3-2)
(3-2-1) a step of sucking polymerizable liquid crystal into this space; and (3-2-2) a step of polymerizing the polymerizable liquid crystal to form a liquid crystal lens layer.
In addition, the step (3-1 ′)
(3-1′-1) a step of applying a polymerizable liquid crystal on the back side of the liquid crystal alignment film, and (3-1′-2) a step of polymerizing the polymerizable liquid crystal to form a liquid crystal lens layer. .

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

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

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

  The polymerization of the polymerizable liquid crystal may be performed in the air or in an inert gas atmosphere such as nitrogen, and conditions suitable for the polymerizable group and initiator of the polymerizable liquid crystal to be used can be selected.

  In the light directivity control unit thus obtained, the polymerizable liquid crystal can be fixed in a highly uniform alignment state. Therefore, since the obtained light directivity control unit is excellent in the alignment uniformity of the liquid crystal lens layer, the 2D / 3D switchable display module including the light directivity control unit can improve display accuracy such as resolution. .

<2D / 3D switchable display module>
The present invention suitably includes a switchable display module including the light directivity control unit.

  A 2D / 3D switchable display module 71 including the light directivity control unit 1 according to the first embodiment of the present invention will be described below with reference to FIG. The 2D / 3D switchable display module 71 includes the light directivity control unit 1, the display panel 31, and the liquid crystal switch unit 41 described above. The display panel 31 includes an incident light polarizer 61 and an outgoing light polarizer 62 in addition to a normal display device (display panel body) using liquid crystal or the like.

  The display panel 31 (display panel body) is disposed on the back side (opposite the viewer) of the light directivity control unit 1, and an incident light polarizer 61 is attached to the back side of the display panel body. Yes. The display panel 31 is normally used in a liquid crystal display device, and includes, for example, a liquid crystal panel that can control transmission of light from a backlight provided on the back side for each pixel.

  The liquid crystal switch unit 41 is disposed on the surface side (viewer side) of the light directivity control unit 1. In addition, the liquid crystal switch unit 41 includes a pair of switch transparent substrates 51 and 52 arranged to face each other, a pair of transparent electrode layers 53 and 54 arranged to face each other adjacent to the inside of these transparent substrates, and the transparent conductive layers. And a switch liquid crystal layer 55 sandwiched inside.

  The liquid crystal switch unit 41 can switch the rotation of circularly polarized light between 0 ° and 90 ° depending on whether or not voltage is applied between the pair of transparent electrode layers 53 and 54.

  The incident light polarizer 61 is disposed so as to allow only polarized light whose vibration direction is the x direction to pass therethrough. Further, the outgoing light polarizer 62 is arranged so as to allow only polarized light whose vibration direction is the x direction to pass therethrough. The outgoing light polarizer 62 is disposed on the viewer side of the liquid crystal switch unit 41.

  Since the 2D / 3D switchable display module has the above-described configuration, when the voltage is not applied to the pair of transparent electrode layers 53 and 54 of the liquid crystal switch unit 41, the polarization plane is rotated in the liquid crystal switch unit 41. Therefore, polarized light that vibrates in the x direction and enters the light directivity control unit 1 from the display panel 31 is emitted from the outgoing light polarizer 62. For this polarized light, the light directivity control unit 1 exhibits a pass-type light directivity, so that the display module can be used for 2D display. Further, when a voltage is applied to the pair of transparent electrode layers 53 and 54 of the liquid crystal switch unit 41, the polarization plane of the liquid crystal switch unit 41 can be rotated by 90 °. Therefore, polarized light that vibrates in the z direction and enters the light directivity control unit 1 from the display panel 31 is emitted from the outgoing light polarizer 62. For this polarized light, the light directivity control unit 1 exhibits a refractive light directivity, so that the display module can be used for 3D display. As described above, according to the 2D / 3D switchable display module 71, 2D and 3D display can be switched and displayed.

  A 2D / 3D switchable display module 72 including the light directivity control unit 2 of the second embodiment of the present invention will be described below with reference to FIG. The 2D / 3D switchable display module 72 includes the above-described light directivity control unit 2 and the display panel 31. The display panel body is on the back side of the light directivity control unit 2, the incident light polarizer 61 that is a part of the display panel is on the back side of the display panel body, and the outgoing light polarizer 62 is on the light directivity control unit. 2 are disposed on the surface side of the two. In addition, description is abbreviate | omitted when it is the same code | symbol.

  A 2D / 3D switchable display module 73 including the light directivity control unit 3 according to the third embodiment of the present invention will be described below with reference to FIG. The 2D / 3D switchable display module 73 includes the light directivity control unit 3 and the display panel 31 described above. The display panel 31 is disposed on the back side of the light directivity control unit 3. The incident light polarizer 61 and the outgoing light polarizer 62 included in the display panel 31 are respectively disposed on the back side and the front side of the display panel 31 (display panel body).

  A 2D / 3D switchable display module 74 including the light directivity control unit 4 of the fourth embodiment of the present invention will be described below with reference to FIG. The 2D / 3D switchable display module 74 includes the light directivity control unit 4 and the display panel 31 described above. The display panel 31 is disposed on the back side of the light directivity control unit 4. The incident light polarizer 61 included in the display panel 31 is disposed on the back side of the display panel 31 (display panel body).

  In the 2D / 3D switchable display modules 72, 73, and 74 according to the second, third, and fourth embodiments, as in the case of the first embodiment, whether or not voltage is applied between a pair of transparent electrode layers, 2D and 3D display can be switched and displayed.

  According to these 2D / 3D switchable display modules 71 to 74, since the light directivity control unit 1, 2, 3 or 4 having excellent liquid crystal alignment uniformity of the liquid crystal lens layer is provided, two-dimensional display in the display panel is provided. In addition, a good display can be provided to the viewer with almost no decrease in the quality level of the three-dimensional display.

  The light directivity control unit of the present invention is not limited to the above embodiment. For example, as the lenticular layer, the refractive index of the material constituting the lenticular layer and the magnitude of the abnormal refractive index of the liquid crystal lens layer are small. Depending on the relationship, a convex type can be used instead of the concave type. Further, the 2D / 3D switchable display module of the present invention is not limited to the above-described embodiment, and for example, a plasma display can be used as a display panel instead of a 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 San 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 4.0% 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 4.0 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.

[Example 3]
In Example 1, the liquid crystal according to Example 3 was the same as Example 1, except that 50 parts by mass of (C-1-1) obtained in Synthesis Example 8 was added as the [C] ester structure-containing compound. An aligning agent (A-3) was prepared.

<Manufacture of light directivity control unit>
The light directivity control unit was manufactured by the following method using the liquid crystal aligning agent prepared in the said Example.

[Example 4]
A polymethylmethacrylate substrate having a concave lenticular shape is bonded to one side of the transparent glass substrate (a), and the liquid crystal aligning agent (A-1) prepared in Example 1 is spray-coated on the concave surface. After coating and prebaking on an 80 ° C. hot plate for 1 minute, it was post-baked at 150 ° C. for 30 minutes in an oven in which the inside of the cabinet was replaced with nitrogen 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 one surface of the transparent glass substrate (b) by the same method as described above except that the roll coating method was used.

Polymeric liquid crystal (Merck, RMS03-013C) was filtered with a filter having a pore size of 0.2 μm into the concave portion of the concave lenticular shaped substrate where the liquid crystal alignment film was formed, and then dropped and filled using a pipette. Next, after baking on a hot plate at 60 ° C. for 1 minute, the surface filled with polymerizable liquid crystal was irradiated with non-polarized ultraviolet rays of 30,000 J / m ² containing a 365 nm emission line using an Hg—Xe lamp. Formed.

  The surface on the liquid crystal side of the transparent glass substrate on which the liquid crystal alignment film is formed is overlaid on the surface on the liquid crystal side of the concave lenticular substrate on which the liquid crystal is formed, and then the two are bonded together. The unit was manufactured.

[Example 5]
In Example 4, instead of the transparent glass substrate (a), liquid crystal switch element (I) (on both sides of a pair of ITO (indium-tin-oxide) transparent electrode layers sandwiching a TN (Twisted Nematic) type liquid crystal) The light directivity control unit of Example 5 is the same as Example 4 except that a concave lenticular substrate is bonded to one transparent glass substrate. Manufactured.

[Example 6]
In Example 4, instead of the transparent glass substrate (b), a liquid crystal switch element (II) (one transparent glass substrate bonded to one outer side of a pair of ITO transparent electrode layers sandwiching a TN liquid crystal) Used, except that a liquid crystal alignment layer was formed on the surface of the ITO transparent electrode layer, and (A-2) prepared in Example 2 was used instead of (A-1) as the liquid crystal alignment agent. The light directivity control unit of Example 6 was manufactured in the same manner as Example 4.

[Example 7]
In Example 4, instead of the transparent glass substrate (a) and the transparent glass substrate (b), a pair of transparent glass substrates to which the ITO electrode layers were joined were used, and both substrates had a liquid crystal alignment film formed on the ITO electrode layer side. Manufactured the light directivity control unit of Example 7 in the same manner as Example 4.

[Example 8]
In Example 7, (A-3) prepared in Example 3 was used instead of (A-1) as the liquid crystal aligning agent, and non-polymerizable liquid crystal (Merck, A light directivity control unit of Example 8 was produced in the same manner as Example 7 except that MLC-7028) was used.

[Example 9]
A polymethylmethacrylate substrate having a concave lenticular shape is adhered to one side of the transparent glass substrate (c), and the liquid crystal aligning agent (A-3) prepared in Example 3 is sprayed on the concave surface by a spray coating method. After coating and pre-baking on an 80 ° C. hot plate for 1 minute, it was post-baked at 150 ° C. for 30 minutes in an open atmosphere in which the inside of the cabinet was replaced with nitrogen 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 Glanteller prism to form a liquid crystal alignment film. A similar liquid crystal alignment film was formed on one surface of the transparent glass substrate (d) by the same method as described above except that the roll coating method was used.

The surface on the concave side where the liquid crystal alignment film of the concave lenticular shaped substrate was formed and the surface on the liquid crystal alignment film side of the liquid crystal alignment film-forming transparent glass substrate were overlapped, and then both were joined. Next, the polymerizable liquid crystal was injected under reduced pressure into the cavity between the substrates. Then, using the Hg-Xe lamp, non-polarized ultraviolet rays containing 365 nm emission line of 30,000 J / m ² are irradiated from the liquid crystal alignment film-forming transparent glass substrate side to form a liquid crystal, whereby the light directing of Example 9 is achieved. A sex control unit was manufactured.

[Comparative Example 1]
A substrate made of polymethyl methacrylate having a concave lenticular shape is adhered to one surface of the transparent glass substrate (a), and a liquid crystal aligning agent (manufactured by JSR, AL3046) is applied on the concave surface by a spray coating method, After pre-baking on a hot plate for 1 minute, it was post-baked at 150 ° C. for 30 minutes in an oven in which the interior was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Next, rubbing treatment was performed by rubbing the surface of the coating film while rotating a roller around which a nylon cloth was wound. A similar liquid crystal alignment layer was also formed on one surface of the transparent glass substrate (b) by the same method as described above except that it was rubbed after being applied using the roll coating method. Thereafter, the light directivity control unit of Comparative Example 1 was manufactured by the same method as in Example 4.

[Comparative Examples 2 to 6]
In Examples 5 to 9, instead of forming a liquid crystal alignment film on a substrate having a concave lenticular shape, and on a glass substrate or an ITO electrode layer, a liquid crystal alignment that was rubbed by the same method as in Comparative Example 1 The light directivity control units of Comparative Examples 2 to 6 were produced in the same manner as in Comparative Example 1 except that the layer was formed.

[Evaluation of liquid crystal alignment uniformity]
For the light directivity control units manufactured in Examples 4 to 9 and Comparative Examples 1 to 6, the liquid crystal lens layer is obtained by cutting and polishing the liquid crystal lens layer along a plane perpendicular to the thickness direction through the center in the thickness direction. The cross section was observed with a polarizing microscope. The liquid crystal alignment uniformity “A” was evaluated when the liquid crystal alignment uniformity was found to be high, and the liquid crystal alignment uniformity “B” was evaluated when the liquid crystal alignment uniformity was found to be low. The evaluation results are shown in Table 1 below.

<Manufacture of 2D / 3D switchable display module>
[Example 10]
The 2D / 3D switchable display module of Example 10 was manufactured by joining the light directivity control unit, the display panel, and the liquid crystal switch unit (I) of Example 4 to each other in the arrangement shown in FIG. .

[Example 11]
The 2D / 3D switchable display module of Example 11 was manufactured by joining the light directivity control unit of Example 5 and the display panel to each other in the arrangement shown in FIG.

[Example 12]
The 2D / 3D switchable display module of Example 12 was manufactured by joining the light directivity control unit of Example 6 and the display panel to each other in the arrangement shown in FIG.

[Example 13]
The 2D / 3D switchable display module of Example 13 was manufactured by joining the light directivity control unit of Example 7 and the display panel to each other in the arrangement shown in FIG.

[Example 14]
The 2D / 3D switchable display module of Example 14 was manufactured by joining the light directivity control unit of Example 8 and the display panel to each other in the arrangement shown in FIG.

[Example 15]
The 2D / 3D switchable display module of Example 15 was manufactured by joining the light directivity control unit of Example 9 and the display panel to each other in the arrangement shown in FIG.

[Comparative Examples 7-12]
In Examples 10-15, instead of using the light directivity control units of Examples 4-9, the light directivity control units of Comparative Examples 1-6 were used in the same manner as in Examples 10-15, respectively. The 2D / 3D switchable display modules of Comparative Examples 7-12 were manufactured.

[Evaluation of display quality of 2D / 3D switchable display module]
With respect to the 2D / 3D switchable display modules manufactured in Examples 10 to 15 and Comparative Examples 7 to 12, the display quality in the two-dimensional mode was visually evaluated. When a discontinuous portion was not found in the display, “A” was evaluated, and when a discontinuous portion was found in the display, “B” was evaluated. The evaluation results are shown in Table 1.

  From the results of Table 1, the light directivity control unit having the liquid crystal alignment film has a uniform liquid crystal alignment of the liquid crystal lens layer, and the 2D / 3D switchable display module including such a light directivity control unit is Was shown to be good. On the other hand, a light directivity control unit that does not have a liquid crystal alignment film formed from a radiation-sensitive liquid crystal alignment agent and has a liquid crystal alignment film that has been subjected to a rubbing treatment has low uniformity of liquid crystal alignment. The 2D / 3D switchable display module with the sex control unit has been shown to be poorly displayed.

  According to the present invention, the uniformity of liquid crystal alignment is good, the light directivity control unit capable of displaying with excellent resolution even in the two-dimensional mode, the manufacturing method thereof, and the 2D / 3D including the light directivity control unit. A switchable display module can be provided.

1 light directivity control unit (first embodiment)
2 Light directivity control unit (second embodiment)
3 Light directivity control unit (third embodiment)
4. Light directivity control unit (fourth embodiment)
DESCRIPTION OF SYMBOLS 11 Transparent substrate 12 Transparent substrate 13 Lenticular layer 14 Liquid crystal lens layer 15 Liquid crystal alignment film 16 Liquid crystal alignment film 21 Switch transparent substrate 22 Transparent electrode layer 23 Transparent electrode layer 24 Switch liquid crystal layer 25 Switch transparent electrode substrate 26 Transparent electrode layer 27 Transparent electrode layer 28 transparent electrode layer 31 display panel 41 liquid crystal switch unit 51 switch transparent substrate 52 switch transparent substrate 53 transparent electrode layer 54 transparent electrode layer 55 switch liquid crystal layer 61 incident light polarizer 62 outgoing light polarizer 71 2D / 3D switchable display module ( First embodiment)
72 2D / 3D switchable display module (second embodiment)
73 2D / 3D switchable display module (third embodiment)
74 2D / 3D switchable display module (fourth embodiment)

Claims (17)

A transparent substrate;
A lenticular layer disposed oppositely on the front side of the transparent substrate and having a lenticular lens array on the back side;
A liquid crystal alignment film laminated on the back surface of the lenticular layer and formed of a radiation-sensitive liquid crystal alignment agent;
A light directivity control unit comprising: a liquid crystal lens layer laminated on the back side of the lenticular layer through the liquid crystal alignment film.   The light directivity control unit according to claim 1, further comprising another liquid crystal alignment film that is laminated on a back surface of the liquid crystal lens layer and is formed of a radiation-sensitive liquid crystal alignment agent.   The light directivity control unit according to claim 1, further comprising a pair of transparent electrode layers stacked on both sides of the liquid crystal lens layer.   The light directivity control unit according to claim 1, further comprising: a liquid crystal layer superimposed on the transparent substrate; and a pair of transparent electrode layers disposed on both sides of the liquid crystal layer. The radiation-sensitive liquid crystal aligning agent is
[A] The light directivity control unit according to claim 1, comprising a polyorganosiloxane having a photoalignment group.   The light directivity control unit according to claim 5, wherein the photo-alignment group is a group having a cinnamic acid structure. The group having a cinnamic acid structure is at least one group 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) The light directivity control unit according to claim 6.

(In the formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group. Some or all of the hydrogen atoms of the phenylene group, biphenylene group, terphenylene group and cyclohexylene group are And may be substituted with an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group, and R ² is a single bond or a carbon number. 1 to 3 alkanediyl groups, oxygen atom, sulfur atom, —CH═CH—, —NH—, —COO— or —OCO—, where a is an integer of 0 to 3, provided that a is 2; In the above case, the plurality of 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. Some or all of the hydrogen atoms of the phenylene group and the cyclohexylene group may be 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. May be substituted. R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or —NH—. c is an integer of 1 to 3. However, when c is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group. d is an integer of 0-4. R ⁷ is an oxygen atom, —COO— or —OCO—. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — *. * Indicates a binding site with 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, the plurality of R ⁷ and R ⁸ may be the same or different. ) [A] A polyorganosiloxane having a photo-alignment group is
A reaction product of a polyorganosiloxane having an epoxy group and at least one compound selected from the group consisting of a compound represented by the above formula (1) and a compound represented by the above formula (2) Item 8. The light directivity control unit according to Item 7. The radiation-sensitive liquid crystal aligning agent is
[C] One or more selected from the group consisting of an acetal ester structure of 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 The light directivity control unit according to claim 5, further comprising a compound having a structure and, when the structure is one kind, a plurality of compounds. The radiation-sensitive liquid crystal aligning agent is
[B] The polymer according to claim 5, further comprising at least one polymer selected from the group consisting of polyamic acid, polyimide, ethylenically unsaturated compound polymer, and polyorganosiloxane having no photo-alignment group. Light directivity control unit. A display panel;
A 2D / 3D switchable display module comprising the light directivity control unit according to claim 3. A transparent substrate, a lenticular layer disposed on the front side of the transparent substrate and having a lenticular lens array on the back surface, a liquid crystal alignment film laminated on the back surface of the lenticular layer, and a lenticular layer via the liquid crystal alignment film A light directivity control unit comprising a liquid crystal lens layer laminated on the back side of
(1) A step of applying a radiation-sensitive liquid crystal aligning agent to the back surface of the lenticular layer to form a coating film,
(2) A method for producing a light directivity control unit, comprising: a step of forming a liquid crystal alignment film by irradiation of radiation to the coating film; and (3) a step of forming a liquid crystal lens layer between the liquid crystal alignment film and the transparent substrate. . Step (3) above is
(3-1) A step of disposing the liquid crystal alignment film and the transparent substrate to face each other and forming a space between them, and (3-2) filling the space with a liquid crystal material to form a liquid crystal lens layer. The manufacturing method of the light directivity control unit of Claim 12 which has a process to carry out. (3-2)
The light according to claim 13, comprising: (3-2-1) a step of sucking a polymerizable liquid crystal into the space; and (3-2-2) a step of polymerizing the polymerizable liquid crystal to form a liquid crystal lens layer. Manufacturing method of directivity control unit. Step (3) above is
(3-1 ′) a step of applying a liquid crystal material on the back side of the liquid crystal alignment film to form a liquid crystal lens layer; and (3-2 ′) a step of disposing a transparent substrate on the back side of the liquid crystal lens layer. The manufacturing method of the light directivity control unit of Claim 12 which has these. The step (3-1 ′)
(3-1′-1) a step of applying a polymerizable liquid crystal on the back side of the liquid crystal alignment film, and (3-1′-2) a step of polymerizing the polymerizable liquid crystal to form a liquid crystal lens layer. The manufacturing method of the light directivity control unit of Claim 15. A liquid crystal aligning agent for aligning a liquid crystal lens layer of a 2D / 3D switchable display module,
A liquid crystal aligning agent characterized by having radiation sensitivity.

Images