TW201235751A - A method for producing a liquid crystal orientation membrane and a phase difference film, and a liquid crystal orientation agent, the liquid crystal orientation membrane and the phase difference film - Google Patents

Abstract

The present invention relates to a method for producing a liquid crystal orientation membrane and a phase difference film, and a liquid crystal orientation agent, the liquid crystal orientation membrane and the phase difference film. Its target is about providing a production method which can be processed under lower temperature and heat for a short time to produce the liquid crystal orientation membrane having a membrane hardness and excellent wringing fit efficiently with high productivity. The production method of the liquid crystal orientation membrane aforementioned comprises: (1) a step of coating the liquid crystal orientation agent on the transparent film to form a coated membrane; (2) a step of exposing the coated membrane aforementioned with radiation to cure the coated membrane; (3) a step of exposing the cured coated membrane aforementioned with radiation to gain a ability of liquid crystal orientation.

Description

201235751 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment, a method for producing an an and a retardation film, and a liquid daily alignment agent, a liquid crystal r 4 , ^ ^ % gate film and a phase Poor film. [First-class technology] Liquid crystal displays (LCDs) are widely used. # AI f D μ π is applied to televisions and various monitors. The display elements used as LCDs have been TNri ^ thousand known as STN (Super Twisted Nematic), TN (Twisted Nematic), Ip, Bucky) , VA (vertical alignment) type, PSA (polymer continuous alignment and D » V曰_ Temple (see Shakes Patent Documents 1 and 2). s Hai liquid is not used in various TL parts. , in this case, based on the purpose of eliminating display coloring and eliminating the change of display color according to the angle of view

For the purpose of viewing angle dependence such as color and contrast, a retardation film is used (refer to Patent Documents 3 and 4). & 4 I As the retardation film, the current extension step of the earth-shaped/adhesive film is manufactured by 'phase-difference liquid crystal hardening having more complicated optical properties. In this method, in order to make polymerizable liquid crystal

The method in which the molecules are aligned with respect to the substrate surface in a predetermined direction, and the B B ash is provided on the surface of the substrate to align the film on the surface of the liquid. The liquid crystal alignment film is formed by a friction method in which a material such as nylon is rubbed in a certain direction to form a surface of the substrate. However, if the rubbing treatment is carried out, ~ dust or static electricity is easily generated in the step, so that dust adheres to the surface of the liquid crystal alignment film, which may cause deterioration. In addition, in the rubbing treatment, 'there are many restrictions due to the manufacturing steps', it is difficult to control the liquid crystal alignment direction in an arbitrary direction. 201235751 Therefore, as a method different from the rubbing treatment, there is known a photo-alignment method in which a photosensitive film such as polyvinyl cinnamate on the surface of a ten earth plate is irradiated and a liquid crystal alignment ability is imparted (see Patent 5 to 15). . According to this light alignment method, dust or static electricity is not generated, uniform liquid crystal alignment can be achieved, and the alignment direction of the liquid crystal can be precisely controlled as compared with the rubbing treatment. Further, by using a light mask or the like at the time of radiation irradiation, a plurality of regions having different alignment directions can be arbitrarily formed on one substrate. However, in the prior art, it is necessary to heat the radiation and to have a large cumulative exposure (see Patent Document 16). On the other hand, as a method of producing a retardation film more efficiently, it is known to continuously produce a roll-to-roll (roll-to-roU) method in which a phase difference is formed on a long-length base film (see Patent Document 17). ). In the roll-to-roll method, the winding step of the retardation film is included, and the liquid crystal alignment film must have a film hardness and a close contact with the substrate, and the deformation of the substrate film is prevented, so that the film is formed in the alignment film. The necessary heat treatment temperature is carried out at as low a temperature as possible. From the viewpoint of cost and productivity at the time of manufacture, it is desirable to have a shorter heat treatment interval. In recent years, technologies for displaying 3D images have become popular, and displays that are also popular in homes and can view 3D images. As an explicit expression of a 3D image, for example, a method of arranging polarized glasses using an image in which an image having a different polarization state can be seen in an image of the left and right eyes is described (see Patent Literature 18). The stereoscopic image obtained by the method is not flickering 'by wearing light-weight polarized glasses', the observer can observe the stereoscopic image. By illuminating the literature, the directional ray liquid crystal is realized, and the light storage amount of the film is formed by the nature, and the time is gradually displayed. The right eye s is only displayed in an inexpensive image, and the image is superimposed by the translucent by making the pixel. Different images are unaided, which is unfavorable for the right eye using the graph technique, and the axes are positive with each other, .201235751

At, as the prior art of the image for the right eye and the image of the left eye, the image of the two is projected on the screen for the projection projector; or the combination of the two for the direct view display The image of the display device or the polarized light of the polarizing film on the surface is transmitted through the shaft pair. However, in order to make the polarizing axes different, it is necessary to use two display devices or projection devices. A conventional method of forming an image having a different polarization state in an image in one display device: a polarizing polarizing layer between adjacent pixels is attached to one display device and wearing polarized glasses can be observed A stereoscopic image as a polarizing film in which a micron-order pattern must be formed as the polarizing layer. As such a patterned retardation film, for example, Patent Document 19 (9) which irradiates polarized light to a photosensitive polymer layer is known. However, the thermal stability of the film that requires a large amount of polarized light irradiation cannot sufficiently satisfy the requirements. In view of such a problem, it has been desired to develop a production method capable of efficiently producing a film hardness and a film-attached film under conditions of further heat treatment, a method for producing a retardation film excellent in liquid crystal alignment, and a liquid crystal distribution. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. SHO 56-9 No. 1277 discloses the formation of a polarizing mode in which two stereoscopic mirrors are formed or disposed on a substrate, and are often simultaneously displayed on the substrate. In the case of the household and the left eye, there is a liquid crystal and a heat stabilizer which are excellent in low-temperature and short-time properties by a method of producing a patterned phase by a mosaic observer. Japanese Patent Laid-Open No. Hei 4-258923 (Patent Document No. 4) Japanese Patent Application Laid-Open No. Hei No. Hei-4-258923 (Patent Document 5) Japanese Patent Laid-Open No. Hei 6-287453 [Patent Document 6] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. ] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-319510 (Patent Document 11) Japanese Patent Laid-Open Publication No. Hei No. Hei. [Patent Document 13] Japanese Laid-Open Patent Publication No. Hei 2 No. Hei 2 No. Hei. [Patent Document No. 1] Japanese Laid-Open Patent Publication No. Hei. No. 2000-86786 (Patent Document No. 1). [Problem to be Solved by the Invention] The present invention has been made based on the above problems, and an object thereof is to provide an article which can be effectively dried under conditions of lower temperature and short-time heat treatment. A method for producing a liquid crystal alignment film having high productivity of a liquid crystal alignment film having excellent film hardness and adhesion, and a method for producing phase # excellent in liquid crystal alignment and thermal stability. 201235751 [Means for Solving the Problem] In order to solve the above problems The proposed invention is A method for producing a liquid crystal alignment film, comprising the steps of: (1) applying a liquid crystal alignment agent to a transparent film, forming a coating film (hereinafter referred to as step (1)); (2) irradiating the coating film a step of irradiating the film to cure the coating film (hereinafter referred to as step (2)); and (3) a step of irradiating the coating film after the curing with radiation and imparting a liquid crystal alignment ability (hereinafter referred to as step (3)). According to this production method, it is possible to produce a liquid crystal alignment film excellent in the fineness of the film and the adhesion with low productivity and high productivity. Even if the film hardening step is performed by irradiation with a photosensitive wavelength, the liquid crystal alignment ability lost by the obtained liquid crystal alignment film can be suppressed. Therefore, the production method is directed to a liquid crystal alignment film for producing a retardation film excellent in liquid crystal alignment. Very suitable. The radiation in the above step (2) is a non-polarized ultraviolet ray from the viewpoint of the irradiation rate, and is preferably an ultraviolet ray which is polarized by the discharge line in the above step (3). The method for producing a retardation film of the present invention has the following steps: (1) coating a thin film on a transparent film; a step of forming a coating film by a skin sputum daily dosing agent > (2) applying the above coating film The step of irradiating the radiation, the spring, and curing the coating film; (3) the step of irradiating the coating film after the curing, and applying the radiation to the liquid crystal; 201235751 a part of the coating polymerization step ( Hereinafter, it is referred to as a step (4) in the liquid crystal alignment film to the liquid crystal (hereinafter referred to as step (4)); (5) the polymerizable liquid crystal is cured (5)). The above-mentioned liquid crystal alignment film can be manufactured in a large size, and the process can be further carried out in steps (4) and (5) to produce a phase difference. In the present invention, a retardation film having a θ································ As a method for producing the same, in the above step (3), there are the steps of: (3-i) a step of irradiating the first radiation on part or all of the cured coating film; and (3-2) hardening. The step of irradiating the second radiation having an incident direction or a polarization direction different from the first radiation is irradiated onto the portion of the subsequent coating film. Further, as another method for producing a retardation film including a liquid crystal alignment film having a region in which the liquid crystal alignment ability is different, the step (3-2) is (3-2') at least the cured coating film is not in the first a step of irradiating the first radiation on a portion irradiated with radiation. A film produced by a method for producing a retardation film having a liquid crystal alignment film having a different direction of liquid crystal alignment capability is suitable for use in 3D image applications. b Liquid crystal alignment agent used in the production method of the present invention, _# [A] polyorganosiloxane having a photo-alignment group (hereinafter referred to as "[AJ photo-aligned polyorganismite X) and [ B) Photohardening catalyst β M 由 由 The liquid crystal alignment agent contains [A] photo-aligned polyorganosiloxane, which can reduce the light-irradiation necessary for alignment due to the optical alignment of the ancient In addition, 201235751 has this crystal line but the compatibility is due to the use of polyorganosiloxane, so the film of the night B曰 alignment film of the liquid crystal alignment agent is excellent in film hardness and adhesion, and the retardation film It has excellent thermal stability. a 1^, because the liquid crystal alignment agent contains a [B] photocuring catalyst, it is possible to irradiate the radiation by a liquid crystal alignment film containing a photosensitive wavelength. 1 m Since the existing photo-alignable liquid crystal alignment agent contains a photosensitive material, the liquid alignment loss of the coating film formed by the liquid crystal alignment agent is generally prevented from being caused by the radiation film imparting liquid crystal alignment ability. The more illuminating step of lauric acid, Yu, I &a Mp; & 曰 曰 被 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 是 是 涂 涂 是 是 是 是 是 涂 涂 涂 是 是 是 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂(Before this step (3)), [even if the coating film hardening step (ie, the above step (2)) is performed by irradiation with a light-sensitive line containing light-sensitive waves ^: b suppresses the liquid crystal alignment of the liquid crystal alignment film which is paid In the manufacturing method, the coating film is cured by radiation irradiation of the photo-alignable liquid crystal alignment and the photosensitive wavelength, and the heat treatment in the step (1) is low temperature and short. Under the condition of time, the liquid crystal alignment film can be produced at a low cost and with high productivity. In the liquid crystal alignment agent, a group of the photo-alignment group dermatonic acid structure is used as a photo-alignment group, or a derivative thereof. The group of the cinnamic acid structure as the basic skeleton is composed of a phase alignment which is easily introduced and formed by the liquid crystal alignment agent, /, 〃, in the liquid daily alignment agent, having a group of the upper oxime鲂 is from the following formula (1) At least: 丄 < -10 - 201235751 selected from the group consisting of the groups of the compound represented by the group of the compound, and the compound and the formula represented by the following formula (i) are also referred to as " Specific cinnamic acid derivatives"), x (2)

OH H_^.R4__R5

COOH (2) (In the formula (1), Ri is a phenyl group, a biphenyl group, or a tricyclohexyl group. The phenyl group, the phenyl group 7 or a hydrogen atom may be partially or wholly. ::Cyanocyl group:: The number of carbon atoms is - Substituent 2 is a single bond, a chain having a carbon number of i~3. A sulfur atom, -CH=CH_, ·, -C〇〇4 0C0 .a疋0 An integer of ~3. Among them, the & is 2 to ht〇C〇- R2 can be the same, or can be different. To the dice ^ base multiple R1 and integer. Kyoko or chaotic base. b is 〇 ~ 4), R is a chain- or soil-like alkyl group or a carbon atom of a hydrogen atom or a r(tetra) radical or a ring of a ring extending to a ring or a ring: The number of carbon atoms in the sheath is 1 to 10, which is substituted by an alkoxy group, a gas atom or a nitrogen group. On a ~10 (four) or cyclic chain of dibasic, oxygen? , sulfur atom or: bond, stone anti-atomic number is b 3 . Among them, when 4 2 or more, more than one; C is an integer from 1 to 3. R and 115 can be the same or different from -11 to 201235751. R6 is a fluorine atom or a cyano group. d is 〇~4 integer. R7 is an oxygen atom, -COO- or -0C0-. R8 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group. R9 is a single bond '-OCO-(CH2)f-* or _0(CH2)〆. Among them, the connection key with "*" is connected with the slow base. f and g are each an integer of biO. e is an integer of 〇~3. Here, when e is 2 or more, R7 and r8 may be the same or different. As a group having the above-mentioned cinnamic acid structure, by using a group derived from the above specific cinnamic acid derivative, the photoalignment property can be further improved. In the far liquid crystal alignment agent, the photoalignment polyorganosiloxane is preferably used. At least one selected from the group consisting of polyorganosiloxanes, hydrolyzates thereof, and hydrolyzate thereof, and a compound represented by the above formula () and the above formula (2) A reaction product of at least one of the group consisting of the compounds shown. In the liquid crystal alignment agent, by utilizing the reactivity between the polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, it is easy to have a light alignment in a polyorganism as a main chain. a side chain group derived from a specific cinnamic acid derivative: the liquid crystal alignment agent preferably further comprises [c] a polymer composed of polyglycine, a compound of ethyl fluorinated unsaturated compound, and no photo-alignment: two organic When the group selects at least one type of polymer, ": Cj other polymer"). In the liquid crystal alignment film containing the surface layer 2 and the alignment agent formed thereon, a polyorganosiloxane is uniformly present in the crucible. Therefore, -12- 201235751, by increasing the content of other polymers, even if the content of polyorganosiloxane in the liquid crystal alignment agent is reduced, the polyorganosiloxane is unevenly present on the surface of the aligning meal, so that it can be obtained Adequate liquid crystal alignment. Therefore, in the present invention, the content of the polyorganosiloxane having a high production cost in the liquid crystal alignment agent can be reduced, and as a result, the production cost of the liquid crystal alignment agent can be lowered. The liquid crystal alignment agent can be suitably used for forming a liquid crystal alignment film by a photo-alignment method, in particular, a liquid crystal alignment film used for the production of a retardation film. Further, it is also applicable to a step of excellent mass productivity such as a roll-to-roll method. Further, in the present invention, it is also applicable to a liquid crystal alignment film including a region in which the direction of liquid crystal alignment is different, and a retardation film having the same. Further, these retardation films are also applicable to liquid crystal display elements for 3D image. [Effect of the Invention] According to the present invention, it is possible to provide a method for producing a liquid crystal alignment film having high productivity, a method for producing a retardation film excellent in liquid crystal alignment property and thermal stability, and in the production of the above-described highly productive liquid crystal alignment film. In the method, 'the light can be aligned even when a small amount of radiation is irradiated, and a liquid crystal alignment film excellent in film hardness and adhesion can be efficiently produced under a lower temperature and a short heat treatment condition. Further, the liquid crystal alignment agent is also suitable for a step which is excellent in mass productivity such as a roll-to-shun method. Further, the liquid crystal alignment agent is also applicable to a liquid crystal alignment film having a region in which the liquid crystal alignment ability is different in directions such as 3D image use. [Embodiment] [Formation for Carrying Out the Invention] -13-201235751 <Method for Producing Liquid Crystal Alignment Film> The method for producing a liquid crystal alignment film of the present invention comprises the following steps (1) applying a liquid crystal on a transparent film (Step of forming a coating film) (2) a step of irradiating the coating film with radiation to cure the coating film; and (3) a step of irradiating the coating film after the curing with radiation and imparting a liquid crystal alignment ability. The steps are described in detail below. [Step (1)] In this step, a liquid crystal alignment agent is coated on the transparent film to form a coating. The coating method may, for example, be a suitable coating method such as a roll coating method, a spin coating method, a printing method, or a spray coating method. Next, the second: / good = inside, thereby forming a coating film. The temperature for the heat treatment is preferably from 0.1 to 15 minutes, more preferably from 5 minutes to 8 minutes, and the film thickness of the film is 'best' and the knives are as 〇.5μηι.土马μ.〇〇5μηι~ As the material of the above transparent film, cellulose (TAC), poly(p-benzoic acid), bovine 1 such as triethyl sulfonyl group J, 1 g-ester, poly-p- 酗, A transparent substrate of a plastic substrate such as polyethersulfone, polyamine, polyimide, or polybutylene dicarbonate. Specially methyl diacrylate,

In general, TAc plays an important role in the LCD phase difference film in most cases, and the protective layer of the film is used. The membrane must be used without precise control. The phase-to-polarization 氺 氺 氺 & 氺 々 - - - - 2012 2012 2012 2012 357 357 357 357 357 357 357 357 357 357 2012 357 357 357 357 357 357 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 In addition, it is better to apply the coating liquid to the film, and it is possible to apply a salt or the like. [Step (2)] This step is as follows: The violet of the light is non-polarized: the optical property is bonded to each other. In the TAC illuminating alignment method, the liquid crystal can be aligned to the film 'in order to exhibit the desired optical property f, and the liquid crystal can be formed to form a retardation film. If so, the existing J phase difference can be saved. The bonding step of the film contributes to improvement in productivity, contributes to the compactness and weight reduction of the LCD material, and is also suitable for the user. However, the TAC film can be used when forming a film with poor solvent resistance. The solvent has p艮, NMp such a dissolving agent cannot be used 〇J; 卜冰, Δ Δ P Λ In addition, the TAC film has the characteristics of low heat resistance and the alignment film cannot be treated at a high temperature. The haihai liquid aB alignment agent is applied to For example, a radiation irradiation step on Lcd such as a color filter or an optical film including a polarizing plate or a retardation film can be used as a liquid crystal alignment film. On the phase difference film manufactured using the liquid crystal alignment agent, the crystal alignment agent is repeated. In the same procedure, when the liquid crystal alignment agent is used as the liquid crystal, the coating film is irradiated with radiation to preliminarily apply a functional decane compound or titanic acid to the substrate in order to bond the substrate and the coating film. For the hardened step beam, for example, an outer line and a visible light line having a wavelength of 150 nm to 800 nm can be used, and among them, ultraviolet light containing light of 300 nm to wavelength is preferable. The radiation may be polarized light or the polarized light may be linearly polarized or partially polarized. In the case of -15-201235751, it is preferable to use partial polarized light from the viewpoint of irradiation efficiency, and "non-polarized light" in the present specification means that light which is divided into polarized light is also included in the case of substantially non-polarized light. The irradiation of the radiation may be performed from the direction of the vertical substrate surface from the oblique direction, or may be combined as an angle of light which is preferably used from a direction close to the direction of the vertical substrate surface, and for example, a low pressure mercury lamp, a heavy hydrogen lamp, a metal can be used. A halide lamp, an argon resonance lamp, a mercury-xenon lamp (Hg-Xe lamp), and the like. The ultraviolet light of the above-mentioned direct polarized light can be obtained by a mechanism for using the above-mentioned light source together with, for example, a grating or the like. The irradiation amount of the radiation is preferably u/m2 to J/m, more preferably loj/j^qojooj/^, and particularly preferably J/m2. [Step (3)] This step 照射 irradiates the above-mentioned hardened coating film with a step of discharging the liquid crystal alignment ability. As the radiation, ultraviolet rays of light having a wavelength of from 1 5 Å to 800 nm and ultraviolet rays of light having a wavelength of from 300 nm to 400 nm are visible. For linear or partial polarization, the reflection can be made from the vertical direction, the pretilt angle can be given by $, or it can be combined from the tilter. In the case of non-biased illumination, the direction of illumination must be oblique. In addition, the pretilt angle j 疋 means that the liquid crystal molecules are parallel to the substrate surface. Preferably, the liquid crystal molecules are non-polarized. (1) The occurrence of the - part is included in the "non-polarization direction, and the method can be performed." The silver light, high-pressure water, xenon lamp, quasi-line polarized light or partial light, diffracted light - less than 1 inch, 〇0〇50&quot;m2~5, X-ray, and is applied in a direction in which, for example, a light-containing substrate surface containing light, preferably used, or a light-emitting green light is used, -16 - 201235751 As the light source used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, a mercury-xenon lamp (Hg-Xe lamp), or the like can be used. Ultraviolet light in a preferred wavelength region can be obtained by a mechanism for using the light source together with, for example, a filter, a diffraction grating, etc. The irradiation amount of radiation is more preferably U/m1 to less than 1 〇〇〇〇. J/m1 1〇J/m2~2 3 4, 〇〇〇J/m2. In addition, when the liquid crystal alignment ability is imparted to a coating film formed of a conventionally known liquid crystal alignment agent by a photo-alignment method, 10,000 J is required. Radiation exposure above /m1, but When the liquid crystal alignment agent to be described later is used, the radiation irradiation amount of the photo-alignment method is not less than 3,000 J/m1, and further, it is lesso/w or less, and the liquid crystal alignment ability can be imparted. The present invention is also suitable for a retardation film comprising a liquid crystal alignment film formed by the method for producing a liquid crystal alignment crucible. The method for producing the liquid crystal alignment film includes: (1) Step of coating a liquid crystal alignment agent on a transparent film and forming a coating film -17-1 a step of irradiating the coating film with radiation to cure the coating film; 2 irradiating the coating film after the curing with radiation, and imparting liquid crystal alignment ability to form a liquid crystal alignment a step of applying a polymerizable liquid crystal to at least a part of the liquid crystal alignment film; and a step of curing the polymerizable liquid crystal; and the method for producing the liquid crystal alignment film further includes the step (4) and the step (4) 5) Thereby, a retardation film can be produced. Step (丨) to step (3) and the method for producing the above liquid crystal alignment film The detailed description will be omitted. Hereinafter, the step (4) and the step (5) will be described in detail. [Step (4)] This step is to apply a polymerizable liquid crystal to at least a part of the liquid crystal alignment film formed. The method of the liquid crystal is, for example, a suitable coating method such as a roll coating method, a spin coating method, a printing method, or a spray coating method. The polymerizable liquid crystal is a compound which is polymerized by heating and/or irradiation. Further, it is particularly limited. For example, it may be a UV-curable rubber liquid crystal and its application (refer to liquid crystal, vol. 3, pp., 1999, pp. 34-42). It may also be a mixture with a plurality of compounds. Further, a known photopolymerization initiator or thermal polymerization initiator may be contained. These polymerizable liquid crystal compounds or a mixture thereof can be used by dissolving in a suitable solvent. Further, by adding a chiral agent or the like, it is possible to use a twisted nematic liquid crystal which is twisted in the vertical direction on the substrate, and it is also possible to use a cholesterol liquid crystal or a dish liquid crystal. [Step (5)] In the step, the solvent contained in the polymerizable liquid crystal is dried by heating and/or irradiation of non-polarized radiation or the like to cure the polymerizable liquid crystal. Further, the polymerization step may be carried out under air or in an inert gas atmosphere such as nitrogen to select an appropriate condition depending on the polyvalent group and the initiator of the polymerizable liquid crystal to be used. The film thus obtained is capable of curing the polymerizable liquid crystal in a predetermined alignment state, and can be used as a phase difference. -18·201235751 A temperature at which a good alignment is obtained as a temperature at the time of heating the polymerizable liquid crystal. In the case of using the polymerizable liquid crystal RMS03-013C manufactured by Merck, it is selected in the range of 4 to 8 (TC). Examples of the radiation when the radiation is irradiated include, for example, non-polarized ultraviolet rays. The irradiation amount is preferably l, 〇〇〇J/m2~l〇〇, 〇〇〇j/m2, 10&gt; 〇〇〇J/m2~5〇5〇〇〇J/m2〇 film thickness of the polymerizable liquid crystal Selecting a film thickness that can obtain the optical property of the user. When the ι/2 wavelength plate of visible light having a wavelength of 540 nm is produced, the phase difference of the phase difference film formed is selected to be a film thickness of 24 〇 nm to 3 〇〇 nm. In the case of an i/4 wavelength plate, a film thickness having a phase difference of i2 〇 nm to i5 〇 nm is selected. The film thickness at which the target phase difference is obtained varies depending on the optical properties of the polymerizable liquid crystal to be used. For example, using Merck In the case of a polymerizable liquid crystal (RMS03-013C), the film thickness for producing a quarter-wave plate is selected from the range of 0.6 μm to 1.5 μm, and the liquid crystal alignment film having a region containing different directions of liquid crystal alignment is selected. Phase difference film and method of producing the same&gt; The present invention also includes a phase having a liquid crystal alignment film In the film, the retardation film includes a region in which the directions of liquid crystal alignment are different. The retardation film can be suitably used for 3D image use, etc. The above step (3) of the method for producing a retardation film has the following steps: (3-1) a step of irradiating the first radiation on a part or all of the cured coating film; and (3-2) irradiating a portion having a different incident direction or a polarization direction from the first radiation on a part of the cured coating Step 2 of the second radiation - 201235751 In addition, as another method of manufacturing a retardation film having a liquid crystal alignment film including a liquid crystal alignment capability, the above step (3-2) is (3-2') at least hardening. a step of irradiating the second radiation on the portion where the subsequent coating film is not irradiated by the first enemy. As the second incident direction or the #direction in the steps (3-2) and (3 _2'), as long as it is Step (3-1) or (3-1,) irradiating the radioactive beer; the first incident direction or the polarizing direction of the night direction capability is different, and is not particularly limited. It is preferably 70° to 1 10°, more preferably 85. ~95., the best for. As in The means for irradiating the radiation in the incident direction may be a method of irradiating the radiation. The photomask is preferably formed in a rectangular shape in such a manner that the portion and the light-shielding portion are alternately arranged. <Liquid alignment agent> For use in the present invention The liquid crystal alignment agent of the manufacturing method is characterized by [A] photoalignment polyorgano-oxygen and [B] photo-curing catalyst. The liquid crystal alignment agent contains [A] photo-aligned polyorganosiloxane, due to sensitivity The light alignment, therefore, can reduce the light irradiation necessary for the alignment. In addition, since the main chain adopts polyorganosiloxane, the liquid crystal alignment film formed of the liquid crystal agent is excellent in film hardness and adhesion, and the film has Excellent thermal stability. Further, the liquid crystal alignment agent [B] photocuring catalyst can be cured by radiation such as the liquid crystal alignment film light wavelength as described above, and the heat treatment in the coating film formation step is low. The short-time conditions can produce a liquid crystal alignment film at low cost and high productivity. The liquid crystal alignment agent preferably contains [C] other polymer, and may also contain other optional components without impairing the effects of the present invention. The area escapes the line of light, the crystal side, the other crystals, the other 9〇° mask, the light transmission, and the use of the Southminometer. The alignment thin contains a sensory effect, as long as the following -20- 201235751 [A] photo-aligned polyorganosiloxane, [B] photo-curing catalyst, [c] /, other compounds and other optional components are detailed Description. &lt;[△] Photoalignment Polyorganooxane> [A] Photoalignment Polyorganosiloxane is a fraction from at least one of a polyorganosiloxane, a hydrolyzate thereof and a hydrolyzate thereof as a main chain In the above-mentioned alignment group, in the sensitivity of light alignment, the liquid crystal alignment property is excellent. In addition, the main chain is excellent in the degree of alignment and adhesion of the liquid crystal, and the phase difference is as a photo-alignment group, and a group of various compounds can be cited, and the azobenzene-containing substance having a basic skeleton can be cited as a basic skeleton. An anthracene-containing derivative having a cinnamium-containing sinusoidal organism as a basic skeleton as a basic skeleton or a derivative thereof as a basic skeleton, or a derivative thereof, is preferably a photo-alignment group. A group containing cinnamic acid or a cinnamic acid structure. a group having a cinnamic acid structure, a derivative thereof as a basic skeleton, and a light-introducing group selected from the group consisting of a stretched biphenyl group, a stretched biphenyl group or an excipient of the above specific cinnamic acid derivative . By the luminosity being good, low light irradiation can be achieved. The film hard film of the liquid crystal alignment film formed using the polyorganosiloxane is excellent in thermal stability. A group derived from, for example, an azobenzene or a derivative thereof, a structure containing cinnamic acid or a derived acid thereof, a ketone or a thiol group, a benzophenone or a benzophenone, is used. a group, a coumarin-containing coumarin-containing group, a polyfluorene-containing polyfluorene-containing amine structure, and the like. The structure having a high alignment ability and a introduced derivative as a basic skeleton is preferably a cinnamic acid or a particularly limited one. Further, R1 is a phenyl group or a hexyl group. The phenyl group is a part of a hydrogen atom of a biphenyl group or a cyclohexylene group, or an alkyl group having a carbon number of 1 to 1 fluorene, and a carbon atom having a fluorine atom. 〜10 alkoxy, fluorine or cyano substituted. R2 is a single bond, an alkanediyl group having a number of 1 to 3, an oxygen atom, a sulfur atom, -CH=CH-, -COO- or -OCO-. a is an integer from 0 to 3. Among them, when a shoulder, a plurality of R1 and R2 may be the same or different. R3 ;! Sub or cyano. b is an integer from 0 to 4. The compound represented by the above formula (1) may, for example, be a compound represented by &quot;7. The number of atoms can be atomic -NH-2 to fluorine. -22- 201235751

(1-4) (1-5) (1-6)

(1.19) (1 - 20) Among these, R1 is preferably an unsubstituted phenyl group or a phenyl group substituted by a fluorine atom or an alkyl group having 1 to 3 carbon atoms. R2 is preferably a single -23-201235751 bond, an oxygen atom or -CH2 = CH2-. b is preferably 0 to 1. When a is 1 to 3, b is particularly preferably 0. In the above formula (2), R4 is a phenylene group or a cyclohexyl group. A part or all of the hydrogen atom of the phenylene group or the cyclohexyl group may be a chain or a cyclic alkyl group having 1 to 10 carbon atoms, a chain or a ring having 1 to 10 carbon atoms. Alkoxy, fluorine or cyano substituted. R5 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 from 1 to 3. However, when c is 2 or more, a plurality of R4 and R5 may be the same or different. R6 is a fluorine atom or a cyano group. d is an integer from 0 to 4. R7 is an oxygen atom, -C00- or -0C0-. R8 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group. R9 is a single bond, -OCO-(CH2)f-* or -0(CH2)g-*, where the connection key with "*" is connected to the rebel base. f and g are each an integer of 1 to 1 〇. e is an integer from 0 to 3. However, when e is 2 or more, R7 and R8 may be the same or different. Examples of the compound represented by the above formula (2) include compounds represented by the following formulas (2-1) to (2-2).

CO —CH —CH

0C0-(-CH2^-C00H (2-2) (wherein Q is a chain or cyclic alkyl group having 1 to 1 carbon atom, or a chain or ring having 1 to 1 carbon atom; Alkoxy group, fluorine atom or cyano group. f is the same as defined in formula (2). -24- 201235751 Benzene is taken from a sufficient white to form a good oxygen to a specific cinnamic acid The synthesis step of the derivative is not particularly limited, and is carried out by a combination of a conventionally known method. As a representative synthesis step, for example, (1) a compound having a halogen-substituted five-coating skeleton and an acrylic acid in a transition metal under basic conditions are listed. a method for obtaining a specific cinnamic acid derivative in the presence of a catalyst; (ii) a cassia acid in which a hydrogen atom of a benzene ring is substituted with a halogen atom under basic conditions, and a compound having a benzene ring skeleton having an atomic group in a transition metal catalyst a method of forming a specific cinnamic acid derivative, etc. in the presence of a cinnamate derived from a polyorganosiloxane, a hydrolyzate thereof, and a hydrolyzate thereof as a main chain in [A] a photo-aligned polyorganosiloxane. At least one selected from the group There is no particular limitation as long as it has a structure derived from a structure capable of introducing the above-mentioned photo-alignment group itself. [A] Photo-aligned polyorganosiloxane contains such an organic polyoxane, and its hydrolysis At least one selected from the group consisting of a condensate of a substance and a hydrolyzate thereof, and a group derived from a compound exhibiting the above phototropism. &quot; As a structure capable of introducing the photo-alignment group, it can be enumerated For example, among the hydroxyl group, the epoxy group, the amine group, the fluorenyl group, the cyclyl group, the ester group, the fluorene group, etc., if the ease of introduction and preparation is considered, the light-aligned polyorganosiloxane is preferable. At least one selected from the group consisting of a condensation poly 2 of a cyclopolyorganosiloxane, a hydrolyzate thereof, and a hydrolyzate thereof (hereinafter, sometimes referred to as "based polyorganosiloxane"), a reaction product of the formula (1) and/or (2). In the liquid crystal alignment agent, a polyorganic compound as a main chain is derived by using a polyorgano- and a specific cinnamic acid having a -25 - .201235751 group. In the case of Shixi oxygen burning, it is easy to guide the two alignment a group of a cinnamic acid derivative. The above-mentioned epoxy group-containing polyorganomethoxy alkoxy oxane is introduced into the epoxy group as a side oxime, and the above-mentioned 1 A A a is further limited to H methoxy group. a group consisting of a polyorgano oxime represented by a polyorgano oxime (7) and a condensate of a sulphide of at least "X1 1 m

Si—Ο Ι Y1 i (In the formula (3), fluorene is a monovalent organic having an epoxy group; an oxy group having 1 to 10 carbon atoms; an alkyl group having a carbon number or a carbon number of 6 to 20; Aryl). Further, in the structural unit having the above formula (7), the calcined hydrolyzed condensate is not only intrusive: ': but also contains a structure of the structure represented by the above formula (3) to form a polyorganismite. The process of the polyorganisms and the chain pores obtained by the process of the same process also has the concept of a hydrolysis condensate in the case of the above formula. The oxime in the above formula (3) is not particularly limited as long as it has an epoxy group, and examples thereof include %, glycidyloxy group, epoxy group, '^, +., γ1 oxyhexanyl group. The group and so on. The reactivity represented by the following formula (X _1) or (χ^) has a photopolymerization. As follows, the following formula and its hydrolysis (3). Υ1 is a 1 to 20 cerium oxygen condensation condensation hydrolytic shrinkage or cross-linking monoorganic glyceryl group is preferably -26- 201235751

(Χ1-2) (In the formula (X^1), Α is an oxygen atom or a single bond. h is an integer of 1 to 3. i is an integer of 0 to 6. Among them, when i is 0, Α is a single bond In the formula (X)-2), j is an integer of 1 to 6. In the formulas (X^l) and (X, 2), "*" represents a linkage key). Further, among the epoxy groups represented by the above formulae (X1-:!) and (X^2), a group represented by the following formula (X^11) or formula (X1-]-:!) is preferred. ,

(In the formula (X^l-l) or the formula (X1-〗-:!), "*" indicates a connection key). In the above-mentioned formula (3), the alkoxy group having 1 to 10 carbon atoms may, for example, be a methoxy group or an ethoxy group; and the alkyl group having 1 to 20 carbon atoms may be enumerated. For example, fluorenyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl-n-decyl, n-decyl, n-dodecyl, n-tridecyl , the fourteen-burning base, the fifteen-burning base, the positive sixteen base, the positive seventeen base, the eighteenth base, the nineteen base, the twenty-burning base, etc.; -27- as a carbon atom The aryl group having a number of 6 to 20, which can be exemplified by the polystyrene oxide having an epoxy group of 201235751, has a polystyrene-equivalent weight average molecular weight of 500 to 1 〇 0,000 as measured by GPC. It is 1 〇〇〇 to 1 〇〇〇〇, and is 5,000 〇. In addition, Mw in this specification is a polystyrene-converted value by the following. Tube column, manufactured by Shucao Co., Ltd., TSKgelGRCXUl Solvent: tetrahydrofuran temperature: 40 ° C pressure: 6.8 MPa The mixture of hydrazine or hydrazine having an epoxy group is preferably capable of being hydrolyzed or hydrolyzed in the presence of a suitable a decane compound having a cyclodecyl group, an etheroxy group, a bis-methoxy decane, an oxy decane, a 3' glycidyl ether, an oxyglycidyloxypropyl propyl ethoxy propyl oxy dimethyl methoxy group: The amount of permeation chromatography (M w ) such as methyl ethoxy decane, 2-(34, pyrene, hydrazine, 4 epoxycyclohexyl)ethyl such as phenyl is preferably 1,000 Å GPC. The above-mentioned decane-based fossil-burning compound and catalyst as an upper 3-glycidylpropyltriethoxy zeoxime, 3-glycidoxypropyltrimethoxy oxime will have an epoxy compound and other Machine solvent, water synthesis. For example, 280-201235751, such as glycidyloxy fluorenyl decyloxy decane, 3-glycidylcyclohexyl)ethyloxy decane, etc., as the above other decane compound, for example, tetrachlorosteel Methoxy decane, tetraethoxy decane, tetra-n-propoxy oxime, tetraisopropoxy decane, tetra-n-butoxy decane, tetra-butoxy decane, dichlorite, trioxane Base decane, triethoxy decane, tri-n-propoxy oxalate, diisopropoxy decane, tri-n-butoxy oxa sulphate, tri-second-butoxy sulphate, fluorotrichloro decane, fluorotrimethoxy矽 、, fluorotriethylene ketone, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy oxan, fluorotri-tert-butoxy decane, decyl trioxane, Methyl trimethoxy decane, methyl triethoxy decane, decyl tri-n-propoxy oxalate, methyl triisopropoxy decane, decyl tri-n-butoxy decane, methyl tri-second Oxydecane, 2-(trifluoromethyl)ethyltrioxane, 2-(trifluoromethyl)ethyltrimethoxy decane, 2-(three Ethyl triethoxy oxalate, 2-(trifluoromethyl)ethyl tri-n-propoxy oxalate, 2-(trifluoromethyl)ethyl triisopropoxy oxime, 2- (Trifluorodecyl)ethyltri-n-butoxy-oxane, 2-(trifluoromethyl)ethyltri-t-butoxydecane, 2-(all gas-n-hexyl)ethyltrioxane, 2- (Perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyldi-n-propoxylate, 2-(all) Gas n-hexyl) ethyl triisopropoxy zebra, 2-(perfluoro-n-hexyl)ethyltri-n-butoxy decane, 2-(perfluoro-n-hexyl)ethyltri-t-butoxy decane, 2 -(perfluoro-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2-( Perfluoro-n-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-butoxydecane , 2-(perfluoro-n-octyl)ethyltri-t-butoxydecane'-hydroxymethyltrichloromethane, hydroxymethyltrimethoxy矽, 乙乙-29- 201235751 三三methoxy石 夕 p = a « 凡, hydroxymethyl di-n-propoxy decane, hydroxymethyl butyl hexane, hydroxymethyl tri-n-butoxy ruthenium 9, hydroxyl Methyl-based decane, 3-(meth) propylene methoxy propyl trioxane, 4: propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene 醯 β : soil - B Oxydecane, 3-(meth)acryloxypropyltri-n-propyl::decane, 3·(:methyl)propenyloxypropyltriisopropoxydecane, 3-(:)propoxy Propyl tri-n-butoxy decane, 3 · (fluorenyl) propylene oxime J propyl: second butoxy oxysulfan, 3 - benzyl propyl trichlorite, % propyl propyl: methoxy矽 矽, 3巯 propyl propyl triethoxy decane ' 3 _ benzyl propyl tri-n-propoxy oxa sulphate, 3, propyl propyl triisopropoxy sulphate, 3- syl propyl = 1; Oxygen: ^2; Office (^ soil-n-butyl decyl decane, 3-mercaptopropyl three second butoxy oxan k-mercapto-dimethoxy oxalate, Wei-methyl methyl triethoxy oxalate: ethylene Trioxane, vinyl trimethoxy oxalate, ethylene tris Ethyl lactate, vinyl tri-n-propoxy alcohol, vinyl triisopropoxy sulphur, vinyl tri-n-butoxy alcohol, ethylene tris, second butoxy decane, allyl trichloro decane , allyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, allyl Base three second butoxy alkane, phenyl trichloromethane, phenyl trimethoxy oxalate, phenyl triethoxy shi xiyuan, phenyl tri-n-propoxy zexi, phenyl triisopropyl Oxime, phenyl tri-n-butoxy decane, phenyl tri-n-butoxy decane, methyl dichlorite, methyl dimethoxy #, methyl diethoxy money, methyl Di-n-propoxy decane, decyl diisopropyl decyl decyl, decyl di-n-butyl decyl sulphate, fluorenyl di-n-butoxy oxa sulphate, dimethyl dichloro sulphate, dimethyl dimethyl曱 methoxy decane, dimercapto diethoxy decane, dimercapto bis- 30-.201235751 n-propoxy oxalate, dimethyl diisopropoxy zebra, dimercapto di-n-butoxy decane Dimethyldi-2-butoxydecane, (methyl)[2_(perfluoro-n-octyl)ethyl]dioxane, (indenyl)[2-(perfluoro-n-octyl)ethyl]dimethyl Oxydecane, (indenyl) [2-(perfluoro-n-octyl)ethyl]diethoxydecane, (vinyl ethyl carbylmethyl) [2-(all-gas n-octyl)ethyl] N-propoxy oxalate, (fluorenyl) [2_(Wang-fluoro-n-octyl)ethyl]diisopropoxy zebra, (mercapto)[2_(completely-n-octyl)ethyl]di-n-butoxy Baseline, (methyl)[2_(perfluoro-n-octyl)ethyl]di-butoxybutane, (indenyl)(3·mercaptopropyl)dioxane, (methyl)(3-indenyl) Propyl) decyloxydecane, (fluorenyl) (3-mercaptopropyl) diethoxy sulphur, (indenyl) (3-disyl propyl) di-n-propoxy oxalate, (methyl (3-mercaptopropyl)diisopropoxydecane, (methyl)(3-mercaptopropyl)di-n-butoxydecane, (methyl)(3-mercaptopropyl)di-butoxy Decane, (fluorenyl) (vinyl) dichlorodecane, (fluorenyl) (vinyl) dimethoxy decane, (fluorenyl) (vinyl)diethoxydecane, (fluorenyl)(vinyl)di-n-propoxydecane, (methyl)(vinyl)diisopropoxydecane, (mercaptovinyl)di-n-butyl Oxydecane, (meth) (vinyl) di-butoxy decane, divinyl dichloro decane, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-butyl Propoxy decane, isopropoxy decane, divinyl di-n-butoxy decane, a dimethyl dimethoxy decane, diphenyl diethoxy decane, diphenyl di-n-propoxy decane, two Phenyldiisopropoxy decane, diphenyldi-n-butoxy fluorene- _ _ - I I di-butoxy decane, chlorodidecyl decane, decyloxy dimethyl oxime, ethoxy Dimethyl decane, gas tridecyl decane, bromotrimethyl decane, iodonium tridecyl decane, decyloxytrimethyl decane, ethoxylated trimethyl sulphate, second butoxy oxime, diphenyl Dioxane, second stupid -31- 201235751, n-propoxy tridecyl decane, isopropoxy trimethyl decane, n-butoxy samaryl sulphate, first Butoxy sulphate, third butoxy sulphate, (gas) (vinyl) dimethyl sulphur, (decyloxy) (ethlyl) dimethyl decane, (Ethoxy)(vinyl)dimethyl decane, (air)(indenyl)diphenyldecane, (decyloxy)(methyl)diphenylnonane, (ethoxy)(methyl) A stone-ceramic compound having one stone atom or the like, such as diphenyl stone. The product name can be exemplified by, for example, KC-8 9, KC-89S, Χ-21-3 153, X-21-5 84, X-21-5 842, X-21-5843, X-21- 5844, X-21-5845, X-21-5846, X-21-5847 'X-21-5848 ' X-22-160AS ' X-22-170B ' X-22-1 70BX, 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, KR523 0, KR523 5, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.);

Glass Resin (Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Corning); FZ371 1, FZ3722 (above, Japan Unicar) Company); -32- 201235751 DMS-S12 'DMS-S15 'DMS-S21 'DMS-S27 OMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS_5025 (above, CHISSO);

Methyl silicate MS51, Methyl silicate MS56 (above, Mitsubishi Chemical Corporation); ethyl silicate 28 'ethyl silicate 40, ethyl silicate 48 (above, Colcoat); GR100, GR650, GR908, GR950 (above, Showa Denko) Things. Among these other decane compounds, from the viewpoint of the alignment property and chemical stability of the obtained liquid crystal alignment film, tetramethoxy decane, tetraethoxy decane, decyl tridecyloxy decane, decyl triethyl ethane is preferable. Oxydecane, 3-(methyl)propenyloxypropyltrimethoxyoxydecane, 3-(methyl)propanyloxypropyltriethoxysulfonium, ethylenetrimethoxysulfate, Vinyl diethoxy sulphur, propyl propyl trimethoxy sulphate, allyl triethoxy sulphur, phenyl trimethoxy decane, phenyl triethoxy decane ' 3 巯 propyl propyl trimethoxy Baseline, 3-mercaptopropyltriethoxydecane, decylmercaptotrimethoxydecane, mercaptomethyltriethoxydecane, dimercaptodimethoxydecane or dimethyldiethoxydecane . The polyorganosiloxane having an epoxy group used in the present invention is used as a solvent for introducing a sufficient amount of a side chain having photo-alignment properties, and in order to prevent the introduction amount of the epoxy group from being excessive, suppressing side reactions and the like. The equivalent weight is preferably from 100 g/m 〇1 to 10,000 g/mol, more preferably such that when synthesizing polyorgano oxyhydrogen having an epoxy group, the ruthenium compound having a fluorene group is set to -33 - 201235751 And the use of the i &amp; . eclipse &amp; octane compound is such that the resulting condensed ring enthalpy equivalent is in the above range. Specifically, such other decane compound is preferably in a mass with respect to the total amount of the epoxy polysiloxane and other decane compounds. /. ~50 quality. /. More preferably, it is used in an amount of 5% by mass to 3% by mass. The organic energy can be exemplified by, for example, a hydrocarbon compound, a ketone compound, an acetonate, a compound of a surface, or the like. Alcohol compounds and the like. - Examples of the above-mentioned stimulating compound include, for example, methyl benzoate and dimethyl: examples of the ketone include methyl ethyl ketone, methyl ketone ketone, diethyl ketone, cyclohexanone, hexanone, and the like. As the above, it is exemplified by, for example, acetic acid, acetic acid, MUU, 曰, acetic acid, isophthalic acid methyl...S, 3, methoxybutyl acetic acid, brewing milk: alcohol, as the above ether For example, ethylene glycol dimethyl sulphate-ethyl ether, tetrahydrofuran, dimethine, and the like are listed, for example, hexanol/upper alcoholic ethylene glycol, ▼ base _2 _@@, Early ethyl ether, ethylene glycol mono-n-propyl ether, ethylene dioxime, core ^ 早 早 J £ - alcohol monomethyl ether, propylene glycol monoethyl ether, ether ether, ^ ^ ^. Among the hydrazines and the like, it is preferably water-insoluble. This is @倾, 4, 2, +, or |曰 Relative to 100 parts by mass of all the stone smelting compounds, there is a ΐ 0 mass f, η ^ 〜1. . .曰:: The mass part is 'better 5' and the negative is 1 gram. In addition, the amount of water used as the polyi=alkane having an epoxy group is preferably L m〇l~l00 times relative to the total decane compound. M〇1, more preferably i times m〇i~ times 茁〇1. The ratio of the base is 0, the compound is stupid, the butyl group is described as lg' acid B, B, can shout, butyl-n-propene agent Quantitative machine Shi Xi ^ 0.5 -34- .201235751 As the above-mentioned test, the compound is used as the above-mentioned potassium hydroxide, methyl, etc. as the above-mentioned ethylamine, two primary to secondary amines; triethylamine, sulfhydryl hydrazine Hydroxide 4, taking into account the stable amine, tri-n-butyl amine; hydrogen peroxide as a production of an alkali metal base as a catalyst, with a high 'so that the production of a stable alkali metal compound polyorganisms The reason for the reason is as follows. For the reason of the catalyst, for example, an alkali metal compound, an organic compound, a wrong compound or the like can be used. Examples of the alkali metal compound include sodium hydroxide, sodium oxyhydroxide and decyloxy group. Potassium, sodium ethoxylate, potassium ethoxide organic test, can For example, ethylamine, pheromone, britylene, etc., organic n-n-propylamine, tri-n-butylamine, pyridine, 4-dioxadiazacycloundecene, etc. Tertiary amine; organic quaternary ammonium salt such as guanyl ammonium, etc. The viewpoint of carrying out the reaction in these organic bases is preferably triethylamine, tri-n-propylamine, pyridinium, 4-didecylaminopyridine, etc. Organic tritetramethyl-specific organic quaternary salt. Catalyst, compound or organic base in the presence of an epoxy group-containing polyorganosiloxane. By using an alkali metal or organic, it can be opened without generating an epoxy group. It is preferred that the side reaction is hydrolyzed and the condensation rate is excellent, and the polyorganosiloxane is excellent in the definition. Further, it contains an epoxy group-containing and specific cinnamic acid derivative synthesized using a catalyst or an organic base as a catalyst. The composition for alignment of the present invention of the reactant is extremely excellent in storage stability.

Chemical Reviews, Vol. 95, pp. 4〇9, 'presumably if a metalloid compound or organic test is used as a catalyst in hydrolysis, condensation reaction-35-201235751, a random structure, ladder structure or cage is formed. The plastic structure does not provide a polyorganosiloxane having a small content of a stanol group. It is presumed that the content of the decyl alcohol group is small, the condensation reaction between the stanol groups is suppressed, and when the organic semiconductor alignment composition of the present invention contains another polymer described later, the stanol group and other polymers are inhibited. The condensation reaction is excellent in storage stability. Particularly preferred as the catalyst is an organic base. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions, and the like, and can be appropriately set. The specific amount used as the organic test, for example, relative to the whole calcined compound, is preferably 倍·01 times moles to 3 times the molars. More preferably 0.05 times the moles to 1 times the molars. When the polyorganosiloxane is used-----^ q ^ 7 pores 兀a in the jujube or hydrolysis, condensation reaction is preferably ώi 芍 由 将 将 将 将 将 将 将 将 将 将 将The organic solvent is carried out by heating, for example, an oil bath. . ...solution, when the condensation reaction is desired, the heating temperature of the oil bath is preferably &quot;0., 4rc~lorc, preferably heated 〇 5 hours~12 Temple is better for 孰1孰 日 s r. 4 mixed liquid, can also be used. When heated, it can be mixed and placed under reflux.

At the end of the reaction, and the solvent layer of the I machine. 4 The washing is carried out from the reaction liquid. In the case of easy washing operation, it is preferred to wash by 3 water having a small amount of salt, for example, a ruthenium solution. Wash ±. The left and right ammonium nitrate water is required to be used as the target with anhydrous acid acid # \ I&quot;, neutral, and then the root "drying the organic solvent layer after dipping the drying agent -36-201235751" Ancient - machine. In the present invention, a commercially available product is used as polyepitacil iff &quot;σΓ Γ2 having an epoxy group. As such a product, an example can be cited, DMS-E12, DMS-E21, and EMS-32 (above, 〇, 丄, etc., CHlsSO). [A] Photoalignable polyorgano oxysulfide compound may have epoxy The polyorganosiloxane of the group itself hydrolyzes 4, and the portion derived from the polyorgano core having an epoxy group into a portion of the hydrolysis condensate. The partially decomposed hydrolysate and the hydrolyzed condensate may be prepared in the same manner as the hydrolysis and condensation conditions of these oxygen calories having a ring =. &lt;'&quot;Polyorganisms&lt;[Α] Synthesis of photo-aligned polyorganosiloxanes]: The invention uses the [Α] photo-aligned polyorganosiloxane compound to have the above ring The polyorgano group of the oxy group is preferably reacted in the presence of a catalyst. The amount of the specific cinnamic acid derivative to be concentrated is preferably from the epoxy group which is contained in the 1-=oxygen. —. 1 is O.Olmol~5m〇1, and particularly preferably 〇〇5 is 卜2 卜化人: It is known that the above catalyst can be used as a so-called hardening accelerator for promoting an organic test or an epoxy reaction. The above-mentioned organic test can be exemplified as the organic test described above. Examples of the hardening accelerator include: j dimethylamine and 2,4,6-tris(dimethylaminomethyl). Tertiary-methylamine, triethanolamine and other tertiary amines; -37- 201235751 2 -methyl σ m. Sitting, 2 - positive heptyl 0.圭, 2 -正十一烧基Β米唾, 2-phenylimidazole, 2-.phenyl-4-mercaptoimidazole, 1-benzyl-2-mercaptoimidazole, 1-benzyl-2-benzene Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-mercaptoimidazole, 1-(2-cyanoethyl)-2-mercaptoimidazole, 1-(2-cyanoethyl) -2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-mercaptoimidazole, 2 -phenyl-4-methyl-5-hydroxydecylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4 ,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole rust trimellitate, 1-(2 -Cyanoethyl)-2-phenylimidazole rust benzoate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium benzoate, 2,4 -diamino-6-[2'-methylimidazolyl-(oxime)]ethyl-s-triterpene, 2,4-diamino-6-(2-n-undecylimidazolyl)ethyl -s-triterpene, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(l')]ethyl-s-triphthyl, 2-mercaptoimidazole Isocyanuric acid adduct, isocyanuric acid addition of 2-phenylimidazole and 2,4-diamino group Imidazole compound such as -6-[2'-mercaptoimidazolyl-(fluorene)]ethyl-s-three-pilled isocyanuric acid adduct; diphenylphosphine, triphenylphosphine, triphenyl phosphite And other organophosphorus compounds; gasified benzyl triphenyl scale, tetra-n-butyl bromide, bismuth bromide triphenyl scale, ethyl bromide bromide, n-butyl bromide scale, Tetraphenyl bromide, ethyl triphenyl scale iodide, ethyl triphenyl sulfonium acetate, tetra-n-butyl fluorene, 0-diethylphosphonium dithiosulfate, tetra-n-butyl scale a quaternary salt such as benzotriazole salt, tetraphenyl quaternary tetraphenyl borate, tetra-n-butyl quaternary tetrafluoroborate, tetra-n-butyl quaternary tetraphenyl borate; 201235751 1,8-diaza Cyclo [5.4.0] undecene-7 and azobicycloalkene; zinc octoate, tin octoate, acetoacetate aluminum complex; tetraethyl bromide, desertified tetra-n-butyl, chlorination Four-stage salt, such as tetra-n-butyl, etc.; metallization such as tri-sulfonate, tribasic acid, etc., such as zinc oxide and tin chloride; - a murine-amine and amine and oxime* Heart-like type accelerator, high melting point, dispersive type, potential hardening The imidazole compound and the organophosphorus compound are formed by using a polymer to cover the surface of the promoter to form a micro-promoting agent; an amine salt type latent hardening accelerator; Lewis acid salt, Bronsted acid (Bronsted solution type thermal cationic polymerization) Among these catalysts, such as a latent hardening accelerator, the ammonium chloride and vaporized tetraethylammonium are preferably used as a catalyst for the use of tetraethylammonium chloride or tetra-n-butylammonium chloride as a catalyst. The oxane, the parts by mass to 100 parts by mass, preferably has a reaction temperature of °C. The reaction time is preferably from 4 hours to 20 hours. Preferably, it is preferably 100 parts by mass of an organic metallized tetraethylammonium or the like which is particularly preferably 0.1 parts by mass of 〇〇C 〜200 〇C, 0 · 1 hour to 5 0, such as an organic acid salt; An amine addition agent such as a product; and a hard-capsule type hard acid such as a fourth scale salt; a salt such as a high-temperature component such as a high-temperature fraction, and a four-stage salt such as a desertification tetra-n-butyl. The amount of the epoxy group is more preferably 〇.〇1 to 20 parts by mass. More preferably, it is 50 ° C to 150 J, and more preferably 0.5 201235751 [A] Light-matching polyorganismite Xi He Yuan is synthesized according to the need of 16 in the presence of an organic solvent. The organic solvent may, for example, be a hydrocarbon compound, an ether compound, a vinegar compound, a ketone compound, a guanamine compound or an alcohol compound. Among these, the oxime compound, the vinegar compound, and the _ compound are preferred from the viewpoints of solubility of the raw material and the product, and ease of purification of the product. The concentration of the solid component (the ratio of the mass of the component other than the solvent in the reaction solution to the total mass of the solution) is preferably 5% by mass or more, 70% by mass or less, more preferably 5% by mass or more, and 5% by mass. The following quantities are used. The MW of the [A] photo-aligned polyorganosiloxane thus obtained is not particularly limited, and is preferably "Ο..~2〇〇〇〇, more preferably $3, 〇〇〇~15,000. By this molecular weight range, it is possible to ensure good alignment and stability of the liquid crystal alignment film. [A] Photoalignment polyorganosiloxane is a carboxy fluorenyl group to epoxy by a specific cinnamic acid derivative. a ring-opening addition of a group, and a structure derived from a specific cinnamic acid derivative is introduced into a polyoxyl group having an epoxy group. The production method is simple, and the introduction of a structure derived from a specific cinnamic acid derivative can be improved. In the present invention, it is possible to use a compound represented by the following formula (4) in place of the above-mentioned specific cinnamic acid derivative in the range which does not impair the effects of the present invention. At this time, the synthesis of the [A] photoalignment polyorganooxime compound can be carried out by a mixture of a polyorganosiloxane having an epoxy group and a specific cinnamic acid and a compound represented by the following formula (4). En R10 — R11—R12 (4) -40- 201235751 as The type of towel R1., PA + 0^ ' is preferably a fluorenyl group having a carbon number of 8 to 20 or an alkoxy group or a ruthenium group. The original decane is 4 to 21 fluorocarbon. Or a fluoroalkoxy " 乂丨 2 horse early bond to cyclohexyl or 1,4 _ phenyl. R is preferably a carboxyl group. Examples of the compound represented by the above formula (4) include compounds represented by the following formulas (4-1) to (4-3). Cf3—0-

COOH CF3 〇3^6-ο

COOH (4-1) (4-2) c2f5 — c3h6—〇

COOH (4-3) The compound represented by the above formula (4) can inactivate the active site of the [A] photoalignment polyorganosiloxane, and contributes to improvement of the stability of the liquid crystal alignment agent. In the present invention, when a specific cinnamic acid derivative is used together with the compound represented by the above formula (4), the total use ratio of the specific cinnamic acid derivative and the compound represented by the above formula (4) is relative to 1 m ο 1 The polyoxymethane has an epoxy group of preferably from 1 mol to 1.5 mol', more preferably from 1 mol% to 1 mol, further preferably from 5 mol to 0.9 mol. In this case, the amount of the compound represented by the above formula (4) is preferably 50 m〇l% or less, more preferably 25 mol〇/o or less, relative to the total amount of the specific cinnamic acid derivative. When the use ratio of the compound represented by the above formula (4) exceeds 50 mol%, the problem of lowering the alignment property in the liquid crystal alignment film may occur. -41-201235751 &lt;[B] Photocuring catalyst&gt; The liquid crystal alignment agent contains the purpose of making the crosslinking reaction of the crosslinkable functional group of the [A] photoalignment polyorganosiloxane more robust. [B] Photohardening catalyst. Since the liquid crystal alignment agent contains the [B] photocuring catalyst, the coating film can be hardened by the radiation irradiation of the liquid crystal alignment film containing the photosensitive wavelength as described above, and as a result, the heat treatment in the coating film forming step is low. The liquid crystal alignment film can be produced at low cost and with high productivity under a short period of time. The photohardening catalyst is not particularly limited as long as it can react with the crosslinkable functional group of the photoalignable polyorganosiloxane of [A], and a known photocuring catalyst can be used. Regarding the absorption wavelength of the [B] photohardening catalyst, a compound having an arbitrary absorption wavelength can be selected, preferably ultraviolet light having a wavelength of 150 nm to 800 nm and absorption wavelength in the visible light region, more preferably 3 nm nm. The ultraviolet region of light having a wavelength of 4 〇〇 nm has an absorption wavelength. In the case of the above-mentioned [B] photocuring catalyst, when the crosslinkable functional group contains a vinyl group or a (meth) propyl group or the like, a radically polymerized [B] photocuring catalyst is preferred, and crosslinkability is obtained. When the functional group contains an epoxy group, an alicyclic epoxy group, a vinyl ether or an oxetane ring structure, it is preferably a cationically polymerized [B] photocuring catalyst. These [tantalum (four) chemicals may be used alone or in combination of two or more. : 乍 = the free-cure catalyst of the radical polymerization type, which can be listed as a ketone such as sulfhydryl or diethyl fluorenyl ketone; benzoin methyl ether, benzoin ethyl ether, thiophene ketone, 2 4_-......n propyl ketal as heart* ~homoxan-4-sulfonic acid-42- 201235751 A fluorenone 4,4-1,3-(monomethylamino)benzophenone, 4,4 ,-bis(diethylamino)diphenylhydrazine g equivalent dibenzophenones; acetophenone, p-didecylaminoacetophenone, 4-(α,α,_dimethoxyacetoxy Benzo) benzophenone, 2,2,-dimethoxy-2-phenyl acetophenone, p-methoxyacetophenone, 2-mercapto-2_ porphyrin-1-(4-indole thiobenzene Base ) 丨 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮Etching; benzoquinone, tribromomethylphenylsulfone, tris(trichloromethyl)_s_triphthyl and other compounds; 2,4,6-trimethylbenzimidium diphenylphosphine oxide, two Oxidation of (2,6-dimethoxybenzhydrazide)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimercaptophenylhydrazine)phenylphosphine oxide Phosphine; di-tert-butyl Peroxide compounds and the like. As a commercial product of the [B] photocuring catalyst of the radical polymerization type, for example, IRGACURE-124, IRGACURE-149, IRGACURE-] 84, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE- 907, IRGACURE-1000, IRGACURE-1700, IRGACURE-1800, IRGACURE-1 850, IRGACURE-2959, Darocur-1116, Darocur-1173, Darocur-1664, Darocur-2959,

Darocur-4043 (above, Ciba Specialty Chemicals), KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, KAYACURE-OA (above, 曰本化药), LUCIRIN TPO (BASF), VICURE- 10. VICURE-55 (above, STAUFFER), TRIGONALPl (AKZO), SANDORAY 1000 (SANDOZ), DEAP (APJOHN), QUANTACURE-PDO, -43- 201235751 QUANTACURE-ITX, QUANTACURE-EPD (above, Ward BLEKINSOP company) and so on. The use ratio of the [B] photocuring catalyst which is a radical polymerization type is preferably 0.5 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 1 part by mass of the [A] photoalignable polyorganosiloxane. In the above-mentioned cationically polymerized [B] photocuring catalyst, an iodonium salt such as a diphenyliodonium salt or a sulfonium salt such as a trisyl sulfonium salt or a hydrazine sulfonic acid sulfonic acid is exemplified. Sulfonic acid, etc., such as salt. Among them, 'the moth salt and the salt are preferred. : is: The ion species is more preferably a compound such as a boron compound or phosphorus hexafluoride. Further, the compound containing ruthenium hexafluoride as an anionic species is excellent in curability, and is excellent in hardenability under temperature conditions, but it is harmful to hexamidine: it is a safety problem for producing πσ0. The above moth salt or sparse salt may be used alone or in a mixture of two or more.乍 is a specific cationic polymerization type of [Β] photo-curing catalyst = two ... three ... continuous acid salt, diphenyl moth nine said: 兀 only - 夂 orphan, a base of perfluoro iodine n-octane sulfonate, two (a) _ tert-butylphenyl) fluorene trifluorocarbonate, bis(4_t-butylphenyl) moth: gasate, bis(4_t-butylphenyl) Sustained acid super-two-based saponin, it is an acid, triphenyl, hexafluoro-n-butyl sulphate, acid, diphenyl fluorene perfluoro-n-octane sulfonate, cyclohexyl 2-oxycyclohexyl锜Difluoromethanesulfonate, dicyclohexyl-2-oxycyclohexyl decanoate, 2-oxycyclohexyl dimethyl benzoate L-yl-1-nyl-methyl oxime Gas methane sulfonate, 4 hydroxy q off: gas. Sulfur evolution three gas a calcination acid salt, 4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Hydrogen-sulfur-filled total gas positive-44- .201235751 alkane sulfonate, 1-(1-naphthylethylidenemethyl)tetrahydrothiobromide trifluorosulfonate, 1-(1-naphthyl) Ethylmethyl)tetrahydrothiobrominated nonafluoro-n-butane sulfonate, 1-(1-naphthylethylidenemethyl)tetrahydrothiobrominated perfluoro-positive Alkane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiobromide trifluorodecane, 1 -(3,5-diindenyl-4-hydroxyl Phenyl) tetrahydrothiobrominated nonafluoro-n-butane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiobrominated perfluoro-n-octyl sulphonate, Trifluoromethane is indeed bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate imine, nonafluoro-n-butanesulfonylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxylate imine, perfluoro-n-octanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid quinone imine, N-hydroxysuccinimide three t / decane sulfonate, N-hydroxyl permeamide nonafluoro-n-butane sulfonate, N-hydroxy succinylamine perfluoro-n-octane sulfonate, 1,8-naphthalenedicarboxylic acid hydrazine Fluoromethanesulfonate and the like. As a commercial product of the cationically polymerized [B] photocuring catalyst, IRGACURE 250 (Ciba-Geigy Co., Ltd.), WPI-1 1 3, WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336 can be cited. , WPAG-367 (above, Wako Pure Chemical Industries, Inc.), ADEKA OPTOMER SP-1 50, SP-1 70, SP-300 (above, ADEKA), CPI-100P, CPI-100A, CPI-200K, CPI- 210S (above, SAN-APRO company) and so on. The ratio of use of the [B] photocuring catalyst of the cationic polymerization type is preferably 0.01 parts by mass to 30 parts by mass, more preferably 〇.% by mass based on 1 part by mass of the [A] photoalignable polyorganosiloxane. 5 parts by mass to 2 parts by mass. When a radical polymerization type [B] photocuring catalyst is used, a radically reactive monomer can be used in combination. The radical reactive group is not particularly limited as long as it is a radical-initiated superposition reaction, and is preferably a group having a polymerizable unsaturated bond from the viewpoint of the anti-45-.201235751. The group 'having a polymerizable unsaturated bond' is preferably an ethylene group, and the (fluorenyl) acrylonitrile group is particularly preferably a (fluorenyl) acryl group. From the viewpoint of reactivity, a monomer having two or more unsaturated bonds is preferred. As the radically reactive monomer which can be used for this purpose, a bifunctional or higher (meth)propionic acid g is used. Examples of the bifunctional (meth)propionic acid vinegar include ethylene glycol acrylate, ethylene glycol methacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dioxime. Acrylate, iota, 9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate vinegar, tetraethylene glycol dimercapto acrylate 'polypropylene ethylene II Alcohol diacrylate, polypropylene glycol dimethacrylate, diphenoxyethanol hydrazine diacrylate, diphenoxyethanol second methacrylate, and the like. As a commercial product of a bifunctional (fluorenyl) acrylate, for example, ARONIX M-210, ARONIX M-240, ARONIX M-6200 (above, East Asian Synthetic Company), KAYARAD HDDA, KAYARAD HX-220, and R- can be cited. 604, UX-2201, UX-2301, UX-3204, UX-330 1, UX-4101, UX_6101, UX-7101, UX-8101, MU-2100, MU-4001 (above, Nippon Chemical Co., Ltd.), Viscoat260 312, 335HP (above, Osaka Organic Chemical Industry Co., Ltd.). Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane triacrylate, trimethylolpropane trimethyl propyl ester, neopentyl alcohol triacrylate, and neopentyl alcohol. Tridecyl acrylate, neopentyl alcohol tetrapropionic acid S, neopentyl alcohol tetramethyl acrylate, bis-46-201235751 pentaerythritol pentaacrylate, dipentaerythritol pentamethyl Acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propenyl oxiranyl) phosphate, tris(2-mercapto propylene oxyethyl) phosphate Examples of the hexa-functional fluorenyl acrylate include a linear alkylene group and a compound having an alicyclic structure and having two or more isocyanate groups, and one or more molecules in the molecule. A polyurethane acrylate-based compound obtained by reacting a compound having three, four or five acryloxy groups and/or a decyl propylene fluorenyl group. Examples of the commercially available product of a trifunctional or higher (fluorenyl) acrylate include ARONIX M-309, ARONIX-400, ARONIX 402, ARONIX-405, ARONIX-450, ARONIX-1310, ARONIX-1600 'ARONIX-1 960. 'ARONIX -7100 'ARONIX -8030, ARONIX -8060, ARONIX -8100, ARONIX -8530, ARONIX -8560, ARONIX -9050, ARONIX TO-1450 (above, East Asia Synthetic Company), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA- 20 &gt; KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3 5 10 (above, Nippon Kayaku Co., Ltd.), Viscoat 295, Viscoat 300 'Viscoat 360 'Viscoat GPT 'Viscoat 3PA 'Viscoat 400 (The above-mentioned Osaka Organic Chemical Industry Co., Ltd.), as a polyurethane acrylate-based compound, for example, NEW FRONTIER R-11 50 (first industrial pharmaceutical company), KAYARAD DPHA-40H (sakamoto chemical company) as a free The use ratio of the base-reactive monomer is preferably 5 parts by mass to 120 parts by mass, more preferably 10 parts by mass to 80 parts by mass, per 100 parts by mass of the [A] photo-aligned polyorganosiloxane. -47-201235751 When a cationic polymerization-based [B] photocuring catalyst is used, a cationically reactive component may be used in combination, or the epoxy group-containing polymer may be used, or an epoxy-reactive monomer may be added. The epoxy-reactive monomer is preferably a monomer having two or more epoxy groups, and examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and triethylene glycol diglycidyl ether. , polyethylene glycol diglycidyl ether, propylene glycol diglycidyl bond, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxydecyl propane triglycidyl ether, water added bisphenol A diglycidyl ether, bicinch A diglycidyl ether, and the like. Examples of the products sold as a compound having two or more epoxy groups include EPOLIGHT 40E, EPOLIGHT 100E, EPOLIGHT 200E, EPOLIGHT 70P, EPOLIGHT 200P, EPOLIGHT 400P, EPOLIGHT 1 500NP, EPOLIGHT 80MF, EPOLIGHT 100MF, EPOLIGHT 1 600, EPOLIGHT 3002, EPOLIGHT 4000 (above, Kyoeisha Chemical Co., Ltd.), etc. The use ratio of the epoxy group-reactive monomer is preferably 50 parts by mass or less, more preferably 1 part by mass to 30 parts by mass, per 100 parts by mass of the [A] photo-aligned polyorganosiloxane. In addition, the liquid crystal alignment agent may contain a curing agent other than the above [B] photohardening catalyst, a curing catalyst, and the like. &lt;[C] Other Polymers> The liquid crystal alignment agent can contain [C] other polymers as suitable components. Examples of the other polymer of [C] include a group consisting of polyproline, polymethylamine-48-201235751, a vinyl unsaturated compound polymer, and a polyorganosiloxane having no photo-alignment group. At least one polymer selected from the group. By containing the other polymers of these [c], the content of the polyorganosiloxane having a high production cost in the liquid crystal alignment agent can be reduced, and the production cost of the liquid crystal alignment agent can be reduced. [Polyuric acid] Polylysine can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound. Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more. Examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride and the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3. 3&,4,5,91?-six rats-5-(four-rat-2,5-dioxo-3-°phoranyl)-naphtho[l,2-c]furan-1,3- Diketone, 1,3,3&,4,5,91?-hexahydro-8-mercapto-5-(tetrazo-2,5-dioxo-3-.f. 11) [1,2-〇]°fu-1,3-di-, 3-oxabicyclo[3.2.1]octyl-2,4-dione-6-spiro-3'-(tetrahydrofuran-2' , 5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-indolyl-3-cyclohexene-1,2-dicarboxylic anhydride, 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''6]undec-3,5,8,10-tetraketone, and the like. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and tetracarboxylic dianhydride described in Japanese Patent Application No. 20 1 0-97 1888. -49- 201235751 Among these tetracarboxylic dianhydrides, it is preferred that the alicyclic ring is 2,3,5-trimercaptocyclodecyl acetic acid two-needle or sulphuric acid two-needle, more acid dianhydride, particularly preferably 235 — &amp; ,,,4_锿丁烷四carboxy々一·3,5-dicarboxy% pentyl acetic acid _ human • 丨, δ+* 〇 as 2,3,5-trimercaptocyclopentyl acetic acid dianhydride The amount of the tetracarboxylic acid two needles is relatively more than the total of the four, 2, 3, 4 - cyclobutane, more preferably 2 〇 m 〇 1% or more ~ needle, preferably - Μ) &amp; Α τ® Λ &quot; z * It consists of only 2,3,5-dicarboxyl-pentyl acetic acid dianhydride or i, 2 3 4_. The term "tetracarboxylic dianhydride" can be exemplified by, for example, a flavonoid diamine or an alicyclic ring: an organic oxaxanthene or an aromatic diamine. These diamined σ materials may be used alone or in combination of two or more. Examples of the aliphatic diamine include meta-xylene diamine, &quot;--amine, oxime-butane diamine, pentamethylenediamine, 1,6-hexanediamine, and the like. 44, which is an alicyclic diamine, may, for example, be diaminocyclohexanone, methyl group: (cyclohexylamine), U-di(aminomercapto)cyclohexane or the like. I, as a diamine-based organic oxalate, can be exemplified by, for example, 1,3-bis(3-amine:propyl)-tetramethyldiazepine, and the Japanese Patent Publication No. 2009-97188. Diamine. As the aromatic diamine, for example, p-phenylenediamine, 4,4,-diaminodiphenyl, ρ Λ, -, 4 - diaminodiphenyl sulfide, 1,5 - 2 can be cited. Amino-amp; r, 4,4-diaminobiphenyl, .4,4,-diamino-2,2'-di(gas methyl), stupid, 2,7-diamino苐, 4,4,-diaminodiphenyl ether, 筅-[4-(4_;k-phenoxy)phenyl]propane, 9,9-bis(4-aminophenyl) 2'2 — [4-(4_Aminophenyloxy)phenyl]hexafluoropropane, 2,2-di(4-indolyl)hexa-I-propan, 4,4'-(p-phenylene diisopropylidene Base) bis(aniline), -50- 201235751 4,4'-(m-phenylene isopropylidene) bis(aniline), anthracene, 4_bis(4-aminophenoxy)benzene, 4,4' - bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diamine. ratio. D,2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminopurine, N-mercapto-3,6-diaminocarbazole, N-ethyl -3,6-diamino group. Cascade, N-phenyl-3,6-diaminocarbazole, n,N,-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl) _n,n,_Dimethylbenzidine, 1,4-bis(4-aminophenyl)pipera, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diamine Benzobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, eighteen Alkoxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecanedecyl-2,5-diaminobenzene, pentadecyloxy-2 ,5-diaminobenzene,hexadecanyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diamine Benzobenzene, cholestyloxy-3,5-diaminobenzene, cholestyroxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3, 5_diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid choline alkenyl ester, 3,5-January female basic citric acid wool residual vinegar, 3,6-two ( 4-Aminobenzoquinone-based oxy) Cholesterol, 3,6._bis(4-aminophenoxy)cholane, 4-(4,-trifluorodecyloxybenzylideneoxy) Cyclohexyl-3,5-diamine Benzoate, 4-(4,-trifluoromethylbenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, (4-((aminophenyl)methyl)benzene _4_butylcyclohexane, ^-bis(4 ((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, l,l-di(4-((aminobenzene) Oxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl) Cyclohexane, 2,4-diamino-N,N-diallylaniline, aminobenzylamine, 3-aminobenzylamine, and a compound represented by the following formula (A-i), -51 - 201235751

(Formula (Al)t, X1 is an alkyl group having 1 to 3 carbon atoms, *_〇·, COO or -〇c〇_. Among them, a bond having a "*" is bonded to a diaminophenyl group. r is 〇 or i. s is an integer of 〇~2. t is an integer of 丨~2〇). The ratio of use of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polyproline is preferably 〇2 with respect to the amine group contained in the oxime equivalent diamine compound. Equivalent to 2 equivalents, more preferably 0.3 equivalents to 1.2 equivalents. The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably -2 (TC~15〇t, more preferably 〇t~1〇(rc. The reaction time is preferably 0.5 hours to 24 hours, more preferably 2 hours to 12 hours.) as an organic solvent. There is no particular limitation as long as it can dissolve the synthesized polyamic acid, and examples thereof include N_mercapto-2-pyrrolidinone (NMp), N,N-dimercaptoacetamide, and N,N_: An aprotic polar solvent such as methyl decylamine, N,N-dimercaptoimidoxime, dimethyl sulfoxide, γ-butyrolactone, tetradecyl urea, hexamethylenephosphonium diamine; a phenolic solvent such as indophenol, xylenol, phenol, or halogenated phenol. The amount of the organic 'valency agent (a) relative to the total amount of the four tetrahydrous dianhydride and the diamine compound (b) and the amount of the organic solvent The total amount (a + b) is preferably 0.1 mass ° / 〇 ~ 5 〇 mass. / 〇, more preferably 5% by mass to 30 mass. / 〇. The polyglycine solution obtained after the reaction can be directly used for The liquid crystal alignment agent is prepared to be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, and the separated polyamic acid can also be purified -52-201235751, For the preparation of the liquid crystal alignment agent, the method for separating the phthalocyanine, and the method for separating the lysine, for example, a method of injecting a reaction solution into a large amount of a poor solvent and drying the precipitate obtained under reduced pressure; a method of distilling off a reaction solution by an evaporator under reduced pressure, etc. As a method for purifying polylysine, it is exemplified that the separated polylysine is dissolved again. A method of precipitating in a poor solvent in an organic solvent; a method of repeating a step of extracting an organic solvent or the like by vacuum distillation under reduced pressure of 1 - human or multiple times by distillation. [Polyimide] Polymerization Dehydration is the complete water-closed compound before it. The ring closure of the proline acid hydrazide water ring can be called ruthenium imine by ring closure of the proline complex of the poly-proline. It can be produced. Polyimine can be the proline acid structure of the living body, which can be made up of all the dehydrated aminated imides; or it can be only the structure of the proline structure. a part of the amine with an imine ring structure is a polyimine The method of the present invention can be exemplified by the method (hereinafter, sometimes referred to as "method (1)"), (); = dissolved in an organic solvent, and a catalyst is added to the solution, and heating is carried out as needed ( In the following, there is a method of dehydration ring closure of poly-proline by a method of a (11)"), etc. The reaction temperature in the square ~(i) is preferably 5 〇. 匚~2 〇〇 Wt-not. Anti-Caojia production does not # + better response when the fox is less than 50 C, can not adequately close the water ring reaction; such as; 5 廄,, Tian Xujia, α "feeding and fruit removal reaction degree more than 2 〇 For crc, the molecular weight of the obtained imine can be adjusted to M Me ^ C ^ 3 ♦ to defend against this decrease. The reaction time is preferably from 〇 to 48 hours, more preferably from 2 hours to 2 hours. ·5 hours-53- 201235751 The polyimine obtained in the method (1) can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyimine, or can be separated. After the polyimine is refined, or the obtained polyimine is refined, it is used to prepare a liquid crystal alignment agent. The dehydrating agent in the method (ii) may, for example, be an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. As the amount of the dehydrating agent, the guanidine structure relative to 1 mol of polyaminic acid is appropriately selected according to the desired hydrazine imidization ratio, preferably O.Olmol to 20 mol ° as the dehydration ring closure in the method (ii). The catalyst may, for example, be acridine, trimethylpyrene, or dimethyl. Than bite, triethylamine, etc. The amount of the dehydration ring-closure catalyst used is preferably from 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent. Further, the more the amount of the above dehydrating agent and the water-removing ring-closing agent, the higher the yield of quinone. The organic solvent used in the method (ii) may, for example, be the same organic solvent as the organic solvent exemplified as the solvent used for the synthesis of the polyamic acid. The reaction temperature in the method (ii) is preferably 〇~1 8 〇^, more preferably l〇°C~15 (TC. The reaction time is preferably 0 5 , ι ρ j υ hr to 2 〇 hours, More preferably, it is 1 hour to 8 hours. By setting the reaction conditions to the above range, the dehydration ring-closure reaction proceeds sufficiently 'and the molecular weight of the obtained polyimine can be appropriately set. In the method (Π), it can be obtained. A reaction solution of an amine. The reaction solution can be directly used for preparing a liquid crystal alignment agent; 7 / 蜊 can also be used to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and then used for making a liquid crystal with a liquid crystal. 201235751 A reagent, which can be used for preparing a liquid crystal or refining a separated polyimine, and then preparing the liquid crystal for removing a dehydrating agent from the reaction solution and a dehydration ring-closing catalyst, for example, solvent replacement. The method and the purification method can be exemplified by the same method as the polyamine method and the purification method, etc. [Vinyl unsaturated compound polymer] As [c] other polymer The vinyl group is unsaturated and can be obtained by polymerizing a known vinyl group by a known method. For example, (a) an epoxy group-containing ethylenically unsaturated compound (hereinafter, "(a)" may not be used. a saturated compound), (b 1) an ethylenically unsaturated carboxylic acid, and/or a polymerizable unsaturated anhydride (hereinafter, sometimes referred to as a "(bl)" unsaturated compound) (a) an unsaturated compound and (bl) no An unsaturated compound other than a saturated compound (hereinafter sometimes referred to as "(b2)" unsaturated copolymer (hereinafter sometimes referred to as "(A 1) copolymerization") is obtained as (a) an unsaturated compound. For example, (fluorenyl) glycidyl acrylate, α-ethyl acrylate α-n-propyl acrylate glycidyl ester, α·n-butyl propylene oil from hydrazine, (meth)acrylic acid 3, 4 — ring Oxybutyl butyl ester, ethyl propyl oxybutyl acrylate, 6,7 epoxide heptyl acrylate, α _ 6,6 epoxide heptyl ester, etc.; as (b 1) unsaturated compound, it can be enumerated For example: alignment agent, alignment agent. Method of hydrazine, separation of amine: acid isolate polymer! &gt; The compound 'sometimes also called 'polyvalent carboxylic acid, and the polymerizability and compound') &amp; J) Polymerized water glycidyl acid glycidic acid 3,4-based propylene oxime-55- .201235751 (meth)acrylic acid, croton Acid, α-ethylpropionic acid, decenoic acid, α-n-butylacrylic acid, maleic acid, s-n-n-propenyl acetonitrile, citraconic acid, benic acid, itaconic acid, etc. ; an unsaturated polycarboxylic acid anhydride such as maleic anhydride, itaconic anhydride, tococanic anhydride, cis], 2,3 4 phthalic anhydride, etc.; as (b2) unsaturated compound, for example,曱基)propyl benzoic acid 2 - light base 乙 克, (甲其,工^ _ Λ. (methyl) oleic acid 2-hydroxyl 1 δ 曰 special (fluorenyl) propylene benzoic acid super carbyl ester *; · 1,4-tetrahydro rr 丞) propylene | sing ^ 0 曰, (methic acid, n-propyl acrylate, isopropyl (meth) acrylate propylene day (τ 丞) acrylic acid n-butyl (fluorenyl) acrylic acid Isobutyl acrylate, (meth)acrylic acid alkyl ester such as dibutyl acrylate (meth) acrylate, styrene &amp; butyl second ester; (meth)acrylic acid cyclopenta vinegar, (methyl) C Dilute acid cyclohexaacetic acid 2-methylcyclohexane vinegar, (methyl) acrylic acid tricyclo [521 〇 2 methyl ^ I vinegar (to Τ, will be tricyclic [5.2 丄〇 2, 6]癸_8_ group is called "di ==", (meth)acrylic acid 2_dicyclopentyloxyethyl, (methyl) bis, / phorsyl ester (meth) acrylate Cyclic esters;

Phenyl (meth) acrylate, benzyl (meth) acrylate, etc. (aryl methacrylates; &amp; W Malay I-ethyl hydrazine, although diethyl malate, diethyl itaconate, etc. Saturated binary acid-lowic acid diacetate; N-phenyl maleimide, N-membered maleimide, n-cyclohexylmaleimide, N_amber quinone imine-3-mar醯imino benzene f-ester, heart sulphonide imino group _4_maleimide butyrate, N-sodium bromide imine-6-maleimide caproate, N_ Amber quinone imine _3_maleimide propyl-56- 201235751 unsaturated dicarbonyl sulfenic acid ester such as quinone imine, n-(9-acridinyl) horse derivative; Acrylonitrile ethylene compound; cyanated (fluorenyl) acrylonitrile and decylamine compounds such as α-gas acrylonitrile and cyanated vinylene; the present ethylene, α-methylethylene, vinyl fluorene complex; amine, Anthracene, anthracene-dithiol (fluorenyl) acrylamide, etc., such as unsaturated vinyl, m-phenylstyrene, p-methylbenzene, p-methoxystyrene, etc. , 1,3 - butyl dioxin, isohexyl yoke and other olefinic compounds; with 2, 3 - 2 The content ratio of acetylene, vinylidene chloride and vinyl acetate in the (Α1) copolymer is lower than that of all structural units derived from (a) unsaturated compounds. _% by weight, more preferably 20 quality denier, preferably 10% by mass to 70%, and %)~6 (&quot;). / The structural unit of the compound in her - in. , as a content of (b 1) unsaturated, preferably 5 mass% to 4 〇f%, relative to all structural units, more preferably from (b2) unsaturated hydrazine, more preferably 10% by mass to 30% by mass 'all structures The unit has a content ratio of the structural unit of the &lt;° relative to the mass I 1 〜1 〇% by mass to 7% by mass, more preferably 20 in the presence of a polymerization initiator. It is used as a solution for the formation of polyglycolic acid. (Α1) The copolymer can be synthesized in a suitable solvent and, for example, by radical polymerization, and the organic solvent is the same as the organic solvent exemplified as the mixture, for example, -57-201235751. The 2,-azo 2 1 agent can be exemplified by, for example, 2,2'-azobis, (/, nitrile, 2,2-azobis-(2,4-dimethylvaleronitrile); Azo compounds such as gas-based 2,4·dimethylvaleronitrile), benzoic acid, butyl ester, M,-di (first, oxidized laurel, third peroxypivalate; dibutyl Peroxidation of organic peroxides such as cyclohexane; by these peroxidation and the like. Redox initiators formed by these polymeric y spear reducing agents [No photoalignment: 蜊 can be used alone or in combination of two or more. ^ ^ B ^ polyorganosiloxane [5], in addition to the Japanese enzymatic agent, can also be used as a [C] other polymer without the addition of a group other than a polyorganosiloxane. The photo-aligned oxime, preferably a polyorganosiloxane having a first-aligned group, and a water shovel: one selected from the group consisting of structural units represented by the following formula Ο3 . a group-aligning group composed of a condensate of the hydrolyzate thereof: polyorganism: 1 2 which = the alignment agent contains most of the organic light without the organic matter;: 'the two have a directional group The oxygen burning is independently present, and the other 4 [A] photoalignment polyorganisms can be present as a condensate of the [A] photoalignment polyorganosiloxane.

I ~Si—ΟΥ2 -58- (5) 201235751 In the above formula (5), an alkyl group on a silk enthalpy, a halogen atom, an alkyl group of a carbon atom, an alkoxy group having a carbon atom number of 1 to 6 or Carbon atom. The aryl group. Y2 is a hydroxy-, a mountain-based or a slave atomic number of 1 to 10 as an atomic diligent &amp; The alkyl group having a singularity of 1 to 20 can be exemplified by a branched or branched methyl group, a rhenium group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

Base, octyl, decyl, octa-jBL I fluorenyl, undecyl, dodecyl, tetradecyl, pentane, hexadecane, heptadecyl, nonadecyl, two Decylene and the like. Examples of the alkoxy group having a carbon number of A 1 MA t β of 1 to 6 include a ethoxy group, a ruthenium group, and a ruthenium group; The aryl group having 6 to 2 carbon atoms may, for example, be a naphthyl group. The polyorganosiloxane having no photo-alignment group can be at least one decane compound (hereinafter, also referred to as "original") composed of an alkoxyline compound and a dentate compound, preferably A suitable organic solvent, A, is synthesized in water and under hydrolysis, hydrolysis or condensation. The starting decane compound may, for example, be tetradecyloxydecane, tetraethoxydecane, tetra-n-propyltetraisopropyldecyldecane, tetra-n-butoxydecane, tetra- or tetra-butoxybutane. , tetrachlorodecane, etc.; methyltrimethoxydecane, methyltriethoxynonanepropoxydecane, methyltriisopropoxydecane, methyltrimethylene, methyltris-2-butoxydecane, The third sub-number of methyl three is 1~20 F number is 6~20 dry basis. For example, a linear chain, a hexyl group, a heptyl group, a tridecylalkyl group, an octadecyl group such as a methoxy group, an isobutoxy group such as a phenyl group, and an oxygen group derived from, for example, a decane compound catalyst selected from the group, Latex-based calcination, methyl tri-n-n-butane-based decyloxylate, -59- 201235751 methyldiphenoxy oxazide, decyl trioxane, ethyltrimethoxy decane, ethyl three Ethoxy decane, ethyl tri-n-propoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri-n-butoxy decane, ethyl di-t-butoxy Decane, ethyltrichlorodecane, phenyldimethoxydecane, phenyltriethoxydecane, phenyltrichlorodecane, etc.; monodecylmonomethoxynonane, dimercaptodiethoxydecane , dimercaptodichlorodecane, etc.; dimercaptomethoxy decane, tridecyl ethoxy decane, tridecyl chlorodecane, and the like. Such orders are preferably tetradecyloxydecane'tetraethoxydecane, methyldimethoxydecane, mercaptotriethoxydecane, phenyltrimethoxydecane, phenyltriethoxy. Decane, dimercaptodimethoxydecane, dimercaptodiethoxydecane, trimethylmethoxydecane or trimethylethoxydecane. In the case of synthesizing a polyorganosiloxane having no photo-alignment group, examples of the organic solvent which can be used arbitrarily include an alcohol compound, a ruthenium compound, a guanamine compound, an ester compound or other aprotic compound. These may be used alone or in combination of two or more. The amount of the alkoxy group and the tooth atom of the water used in the synthesis of the polyorganosiloxane having no photo-alignment group is preferably 0.001, preferably 0.01 mol to 1 〇〇m〇1, more preferably Ο·1ιηο1 〜30m〇I, particularly preferably from 1 mol to 1.5 mol. The catalyst which can be used in the synthesis of the polyorganosiloxane having no photo-alignment group can be exemplified by, for example, a metal chelate compound, an organic acid, no-60-201235751, an organic base, an alkali metal compound, or an alkaline earth metal compound. Amines can be used singly or in combination of two or more. The raw material decane compound is used as a catalyst: f, preferably 0.001 parts by mass to 10 parts by mass, more preferably & 〇 〇〇1 parts by weight to 1 part by mass. &amp; Adding a polyorganosiloxane which is a fluorene-aligning group is added intermittently or continuously to a solution in which a decane compound as a raw material = or a money compound is dissolved in an organic solvent. The catalyst is added to the water which is dissolved or added to the solution which is formed as a raw material in the raw material (four)-burning compound. The reverse degree of the polyorgano-oxygen burning without the photo-alignment group is synthesized. Cars are good for (rc~10 (rc, better for saying ~ should be time 祛蛊Λ &lt;, + 丨 马 反 反 〜 〜 24 hours, more preferably 1 hour ~ 8 hours. = crystal matching agent in When the [c] other polymer is contained, the ratio of the polymer is preferably 根据 to (10) f parts by weight of the [10] photo-aligned polyorgano 7-oxo, preferably. 10,000 parts by mass or less. Early <other optional components> Contains: The crystal alignment agent can have one or two or more acetal ester structures of [D] carboxylic acid, tannic acid, within a range not impairing the effects of the present invention. (4) The structure, the 丨-alkylcycloalkyl I structure of the carboxylic acid, and the structure of at least one selected from the group consisting of the third carboxylic acid structure of the carboxylic acid are sometimes referred to as "ester-containing structures" a compound of eight compounds with a right 5,1, a knife, and an epoxy group (hereinafter, sometimes It is called "epoxy-61 - .201235751 compound", a functional decane compound, a surfactant, a photosensitizer, etc. The following is described in detail. [[D] The ester-containing compound The liquid crystal alignment agent can cause the acid of the [A] photo-aligned polyorganosiloxane to be cross-linked by the acid generated by the compound containing the [D] ester-containing structure in the heat treatment step, and the result can be further improved. Thermal stability of the phase difference film. The liquid crystal alignment agent can form a liquid crystal alignment film excellent in heat resistance and the like by the compound [D] containing an ester structure. [D] The ester-containing compound has two molecules in the molecule. More than one selected from the group consisting of an acetal structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a third butyl ester structure of a carboxylic acid A compound of a structure] D] The compound having an ester structure may be a compound having a structure of the same kind in two or more of these structures, or may be a combination of two or more of these structures. The group represented by the following formula (D]) and formula (D_2), R13 - 〇-〇-CH^〇_r14 ( D_" Ο (In the formula (D-1), ρΐ314 R and R are each independently an alkyl group having a carbon eyebrow early 1 n, a carbon atom number of 1 to 2, and a double ring of 3 to 10, The aryl or carbon atom of the Shishengdian is an aralkyl group having a 6 to 1 π subnumber of 7 to 10. In the formula (D-2), nl is an integer of 2 to 10.) -62- 201235751 In Rl3 in the above formula (Di), a methyl group is preferably a methyl group; an alkane having a number of 1 to 20 is preferably a cyclohexyl group; and an alicyclic group having a number of 3 to 10 is used as a hydrazine group. The aryl group having an atomic number of 6 to 1 () is further preferably an aryl group having a carbon number of Λ, and preferably a phenyl group of 14 to 10, preferably 芊|R having a carbon number of L. The number of the sub-numbers is two: 3 to 10 alicyclic groups, preferably a carbon ruthenium ruthenium group; as carbon, preferably a phenyl group; and A is 6 to 1 Q aryl hydrazine The anti-atomic number of the stone is 7 to 10, and its λ group or 2_phenylethyl group. As a formula (referred to as U: is a group I: formula = two groups, W group, ... 2 = a few groups, b n-propoxy ethoxy 4 second butanyl, b isobutoxy Ethoxy: a lactyl ethoxy group, a "third butoxy group, a 1-% hexyloxy group, and a p-long-milk base" - "oxy-rebase, Ethoxylate, 1-merylethoxymethyl, (cyclohexyl) (methoxy =, (cyclohexyl) (cyclohexyloxy) methoxyl methoxy group, (ring己美二:: group, (cyclohexyl) (phenoxy) I hexyl) (fluorenyloxy) methoxycarbonyl = formazan (tetra), (phenyl) (cyclohexyloxy) methoxy :, ( ΓΛ 二 L L-oxycarbonyl, (phenyl) (, oxy) methoxyl group, decyl) methoxycarbonyl fluorenyl) (cyclohexyloxy) methoxymethoxy group Oxyl group, (nodal group) (nodal group oxy group) The group represented by the above formula (D-2) includes, for example, 2 furanyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group. Etc. -63- 201235751 Among these, 1-ethoxyethoxycarbonyl, 1-n-propoxyethoxy group is preferred. a 1-cyclohexyloxyethoxy group, a 2 -tetrazirconium-oxycarbonyloxy group, a 2 -tetrahydropyranyloxy group, and a group containing the ketal ester structure of the above carboxylic acid, For example, a group represented by the following formula (D-3) to (D-5), R15

I -C — 0 — C-Ο R&quot; ( D - 3 )

II I o R16 01 cyo R18li, n2 H2 c.

4 ID o 9 R1 ο - cy ο ο -c. η3 Η2 c. D-5 (In the formula (D-3), R15 is an alkyl group having 1 to 12 carbon atoms. R16 and R17 are each independently An alkyl group having 1 to 12 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. In 4), R18 is an alkyl group having 1 to 12 carbon atoms, n2 is an integer of 2 to 8, and in the formula (D-5), R19 is an alkyl group having 1 to 12 carbon atoms. Integer). The alkyl group having 1 to 12 carbon atoms of R15 in the above formula (D-3) is preferably a methyl group; and the alkyl group having 1 to 12 carbon atoms in R16 is preferably -64 to 201235751. It is a methyl group; the number of carbon atoms is 3 to cyclohexyl; and the number of carbon atoms is A 7 group, preferably 7 to 2 carbon atoms. Preferably, it is a phenyl group; the number of carbon atoms is 7~ soil is 卞. The R 丨 7 is an alicyclic group having a carbon number of from 1 to 6 and is preferably an alicyclic group having a carbon number of from 1 to 6 and an alicyclic group of b 6 to 10 as a carbon source. The number of atoms in the group is phenyl. The aryl group having a carbon number of 7 to 2 〇: 6 to 20 is preferably a 2-phenylethyl group. The base of the formula (D-4) is preferred. Preferably, it is a subunit, and as a n2, the number of carbon atoms of Rl9 in which the number of carbon atoms is from 1 to 12 is 丨~^, or 4 is obtained as the formula (D-5). N3 is preferably 3 or 4. Alumina, preferably a methyl group. As a group represented by the above formula (D-3), a small methoxyethoxy group, a hydrazine methyl group Example (6) 1-methyl 1-methyl-1-n-butoxyethoxycarbonylpropyl: ethoxycarbonyl, benzyl, "methyl second butoxy-di-anthracene-isobutoxy ethoxylate Tributoxyethoxy group, i-methylmethyl-1-yl, methyl-methyl-decyloxyethoxyethoxy ethoxylated ethoxy group, κmethyl Ethyl ethylene diryl]-phenoxyethoxyethane group, K cyclohexyl small group;:::1 methyl]-benzenecyclohexyl Cyclohexyloxyethoxy group", benzyl, i-yl, 1-phenyl methoxyethoxy ethoxyoxyethoxyethoxy, 1-phenyl]-benzene Oxyethylene bis-diyl ethoxy ethoxy ethoxy group, benzyl methoxy group, 丨 phenyl phenylcyclohexyloxy ethoxy group, i-pyringyl group,基 ethoxy ethoxy ethoxy ethoxy group, etc. * oxy ethoxy 'carbon group, -65- 201235751 As the group represented by the above formula (D-4), for example, 2_(2_甲甲A tetrahydrofuranyloxycarbonyl group, a 2-(2-hydrazinotetrapyranyl)oxycarbonyl group, etc. 1 As a group represented by the above formula (D-5), for example, an anthracene-methoxy group can be exemplified. Cyclopentyloxycarbonyl, 1-methoxycyclohexyloxycarbonyl, etc. Among these, preferably 丨-mercaptomethoxyethoxycarbonyl, i methyl-1-cyclohexyloxy B The group represented by the following formula (D-6), R20, as the group containing the quinone-alkylcycloalkyl ester structure of the carboxylic acid.

(D-6) Meal... The alkyl group having a carbon number of W2 is an integer of 1 to 8). \ The alkyl group having R of the above H(D_6)t and the number of carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms. The group ' represented by the earth ring propylene 2 ΐΓΓ 6) can be exemplified by, for example, fluorenyl-methyl fluorenyl group, 1-methylcyclobutoxycarbonyl group, 1 _formam ps WT group % decyloxyethylcyclobutoxide Base: "base ring methoxyl group, 〗 - oxycarbonyl ' 丨 - ethane octagonal: ethyl pentyl carbonyl, ethyl cyclohexyl, (4) propylene oxygen = carbon bis (iso) propyl基 丙 ) ) ) 其 其 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 癸 癸 癸 A 、 、 a benzyl group, a hexyl hexyloxy group, a 1,4-(4) butylcycloheptyl yl-66 - 201235751 iso-butylcyclodecyloxycarbonyl group, a fluorenylcyclooctyloxy group, a w-iso; Hexyl-based, W-hexylcyclobutoxy-based, w-iso; hexamethyleneamino, _(4), #己气美,其土, oxycarbonyl, 】-(iso-j hexyl hexyl acrylate Rebellion, __(iso) hexyl 壬璟癸 狰 狰 ^ ^ ^ 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳Oxyl group, L(iso)octylcyclopentyloxy group; octyloxy group, W iso)octylcycloheptyloxy group, i_( Iso)) = hexyl ruthenyl, 1-(iso)octylcyclodecyloxycarbonyl, etc. The above-mentioned oxo group-containing oxo group described by octyloxy octoxide. As a compound represented by the formula (4) in the present invention, "D1 is a compound of the formula (4).

TnR· · (6) (In the formula (6), 'T疋 the above formula (4)-”~(7), the middle-group or the third butoxy group, ..., the base of the pound: 2 to: _〇... L: is an n-valent group or a carbonogen obtained by deuterium, and a y-valent hydrocarbon group having a number of 1 to 18) η is preferably 2 or 3. When R' in (6) is a chain-burning 1 in which the number of carbon atoms is i~12, a bond which cites a single bond ^t is a base, a stupid base, an i 1拙~, a phenyl group, 2, &quot;Naphthyl, 5 Liu Ji-Μ, 笨美申: tetrabutyl sulfonyl-1,3-phenylene, etc..

When η is 3, it is the above R group, benzene-1,3,5-triyl or the like. As shown in the release -67- 201235751 ο c2h4. Ν

Ν C2H4- 〇人人〇

I c2h4 - It is preferably linear as the above-mentioned bond dimer. The compound of the [D]-containing (tetra) structure represented by the formula (6) can be synthesized by a ten-step method of an organic group or an appropriate combination. For example, T in the above formula (6) is synthesized by the above two-two method. a compound (wherein R is a stupid base; (= shows: in the presence of a group of agents] by making the compound MC〇〇H)n (i, R: reminder: and in the above formula (6) ❺ Definition, (', and: knife r14-〇-ch=r13, (wherein 丨4 and compound R13' are added and synthesized from the group defined by the above formula (D-&quot;). The atom obtains the tauyanide in the above formula (6), preferably in the compound τ of the group represented by f 1 /, formula (D·2). (C〇〇H)n (wherein, the straw is made by the chemical contract) and the compound of the following formula and η are respectively combined with the definition of the above formula (6), (form t , II] and Bu.+. ^ _ .. The definition in the far type (D-2) is the same as the 3H liquid crystal gfi A) The amount of the sword to the sword is so cool as to consider the requirements of the # &amp; J 3 buckle (7) The structure of the compound contains the heat resistance of the water, etc., and the six 疋 / / has a special limit ~ 68 ~ .201235751 'relative to 1 〇 0 temporary county eight ^ Μ ^ ^ volume injury [Α] light alignment Polyorganosiloxane, [D] Compound 4 with a oxime structure LJ 3 1 part by mass to 50 parts by mass, more preferably the mass part is 20 parts by mass, and the amount is 1 贞 5 wounds, particularly preferably 2 parts by mass to 1 part by mass.

[裱Oxygen compound J based on further description of ancients, My·a

It is known that the liquid formed on the surface of the film is bonded to the surface of the substrate on the surface of the substrate, so that J J contains an epoxy compound in the liquid crystal alignment agent. Examples of the epoxy compound include, for example, ethylene glycol di-distillate, polyethylene glycol dimerization _ _ _ 'from glycidyl ether, propanol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol. Diglycidyl ether glycol dimethyl condensate (IV), U•hex: alcohol diglycidyl (tetra), glycerol t glyceryl ether, 2,2-dibromopentyl glycol diglycidyl ether, condensed tetraglycidyl group 2,4_hexanediol, N,N,N,,N,_tetra, glycidyl diphenylbenzene January, 1,3_bis (N,N-diglycidylamino) Ring, N, N, N', N'.·tetraglycidyl_4,4,-diaminodiphenylmethane n,n-diglycidyl-nodal amine, N,N diglycidyl Base _:, Cyclohexane, and the like. The content ratio of the methyl group as the epoxidation catalyst is preferably 40 parts by mass or less, more preferably 40 parts by mass or less, relative to the [A] photopolymerized organic siloxane and the arbitrarily contained [c] other polymer. In principle, the liquid crystal alignment agent can effectively produce a cross-linking reaction when an epoxy compound is contained, and can be used together with a catalyst such as 丨-benzyl-2 in 0; h ^ Α κ. [Functional decane compound] The above functional decane compound can be used for the purpose of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. -69-201235751 As the functional decane compound, for example, a 3-amino group can be exemplified. Propyl methoxy decane, 3-aminopropyl triethoxy decane, 2-aminopropyl dimethoxy decane, 2-aminopropyl triethoxy decane, N_(2 amine B 3-aminopropyltrimethoxydecane, N-(2aminoethyl)aminopropylmercaptodimethoxydecane, 3·valurylpropyltrimethoxydecane, Hongyu Urea Triethoxy decane, N•ethoxycarbonyl_3_aminopropyltrimethoxy decane, N-ethoxycarbonyl _3_ Propyl triethoxy decane, triethoxymethoxymethyl propyl triethylamine, trimethoxy decyl propyl triethylamine, 10 tricate - Hi triazazapine, 10 -diethoxy gangue oxime 丨, 4,7 triazaindene, 9-trimethoxy decyl _3,6-diazepine Acetate, 9-triethoxydecyl- 3,6-diazadecyl acetate, N-benzyl-3-I-propyltrimethoxydecane, N-.benzyl _3_Aminopropyltriethoxydecane, N_phenyl_3_aminopropyltrimethoxydecane, ΝPhenyl-3-I-propylpropyltriethoxy oxime, Ν-二( Oxidized ethyl)_3_aminopropyltrimethoxy decane, bismuth (oxyethyl)-3-aminopropyltriethoxydecane, 3 _glycidoxypropyl decyloxy a reaction product of decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy oxime, tetrazoic acid dianhydride, and a decane compound having an amine group, and the like, 6 3 _ 2 9 1 9 2 No. 2, the reaction product of the tetrazoic acid di-hepatic acid and the amine group-containing decane compound, etc. The content ratio of the decane compound is preferably 50 parts by mass or less, more preferably 20 parts by mass, based on [A] the photo-aligned polyorganosiloxane and the arbitrarily contained [C] other polymer. The following -70-201235751 [Surfactant] As the surfactant, for example, a non-separating agent, an anionic surfactant, a cationic interfacial surfactant, an organic ceramsite surfactant, a polyphosphorus, a fluorine-containing interface can be cited. The active agent, etc. The use ratio of the surfactant is preferably 10 parts by mass or less based on 100 parts by mass of the whole. [Photosensitizer] A photosensitizer group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is an alkyl group having a number of 1 to 6) which can be contained in the liquid crystal alignment agent, -CH = At least one group selected by CH2 and S02C1 and a photo-sensitizing structure reacting the above-mentioned polyorganosiloxane having an epoxy group with a mixture of a specific and a photosensitizer, which is a photo-aligned polyorganosiloxane The alkane has both a photosynthetic structure derived from a specific cassia (cinnamic acid structure) and a photosensitizer. The light sensitizing structure has a function of being excited by light irradiation to provide a photosensitive structure close to the excitation energy. This may be single or triple, but based on long energy movements, it is preferably triple. The above light sensitizing light is preferably light having a wavelength in the range of 150 nm to 600 nm. Since light having a wavelength shorter than the above lower limit cannot be operated in the system, it is not suitable for use in the photo-alignment method, and the light energy having a wavelength longer than the upper limit is small, and the excited state of the inductive structure is difficult. Sub-Interfacial Activity Active Agent, Amphoteric Oxygen Interacting Agent The liquid crystal alignment agent, more preferably one type, is a compound having a group consisting of a carboxy hydrogen atom or a carbonogen. The sensitizing sensitizing structure of the [A] acid derivative contained in the cinnamic acid derivative in the enamel can be excited in the polymer state and the ultraviolet ray absorbed by the effective structure or visible in ordinary optics. On the other hand, the light-increasing-71 - 201235751 is induced, and examples of the photosensitizing structure include an acetophenone structure, a benzophenone structure, a fluorene structure, a biphenyl structure, a carbazole structure, and a nitroaryl structure. The oxime structure, the naphthalene structure, the fluorene structure, the acridine structure, the fluorene structure, and the like can be used alone or in combination of two or more. These photosensitizing structures are derived from acetophenone, benzophenone, hydrazine, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, anthracene, anthracene, acridine or hydrazine, respectively. A structure formed by a group of 1 to 4 hydrogen atoms. Here, the various structures of the acetophenone structure, the carbazole structure and the fluorene structure are preferably those obtained by removing 1 to 4 of hydrogen atoms from a benzene ring of acetophenone, carbazole or anthracene. The structure formed. Among these photosensitizing structures, preferred are selected from the group consisting of an acetophenone structure, a benzophenone structure, a fluorene structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure. At least one, particularly preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, and a nitroaryl structure. As a light sensitizer, a compound having a reductive group and a photo-sensitizing structure is preferable, and a compound represented by the following formulas (H-1) to (H-10), etc., may be mentioned as a more preferable compound, - 72- 201235751

〇-(CH2)-COOH

COOH CH3 (H-1 (H-2)

(where 'q is an integer from 1 to 6). What is the aperture used in the present invention? A w , a tropism polyorganosiloxane compound, in addition to the above-mentioned epoxy group-polymerized polyoxon gas and a specific cinnamic acid derivative, it is also possible to The reaction is synthesized in an organic solvent. In this case, as the amount of the AW 丄 疋 cinnamic acid derivative, for the 1 mol of the epoxide atom of the poly right-hand A erionite ♦ organic oxirane having an epoxy group, compared with O. OOlmol ~ lOmol, more Wei Yan Λ two for O.Olmol ~ 5mol, especially good five 0.05mol ~ 2mol. As a light sensation #丨 马 u曰斌 engraved with 罝, relative to lm〇1昱

The epoxy group of polyorganophosphonium O O.O00lmol~0.5mol, more preferably π horse and mad two 0.0005mol~〇.2mol, especially good hair 0.00 1 mol~0 · 1 mol. MA•73- 201235751 &lt;Modulation of Liquid Crystal Aligning Agent&gt; The liquid crystal alignment sword such as ^^ Γ contains [Α] photo-alignment f right-learning gas and [B] photo-curing catalyst gate polymerization The organic stimulating component is preferably prepared as a solution in which a squeegee can be dissolved in an organic solvent as a solvent, and is preferably a six-burning, (8) photohardenable catalyst, and is prepared as a long-lasting compound. The organic solvent to be reacted with the oxime-organic polyorganisms: two; the other components used, and the organic solvent not used for it, may be the same in any of the liquid crystal alignment agents. The type of other polymers [C] contained in Kang Renyong does not contain [B] photohardenable catalyst and [] pre-aligned polyorganosiloxane and solvent in the liquid crystal alignment agent, and can be cited as Good organic organic solvent. This is exemplified by the solvent used in the case of the polyamic acid. The two organic solvents can be used singly or in combination of two or more kinds of liquid crystal alignment agents, and the preferred solvent used for the preparation of i π s, _ #种戈两录物 and its kind, combining the above organic" is a species Or two or more kinds of solvent-based solvent concentrations, precipitation, night-like solvent does not have the surface tension of the preferred solid-liquid crystal alignment agent: the components contained in the agent, and The liquid crystal of the invention is in the range of m〜4~m〇mN. The concentration of the solvent rr solid component in the crystal alignment agent, that is, the mass of all the components of the liquid agent, occupies 1% by mass of the liquid crystal alignment to 1% by mass. Preferably, the liquid crystal alignment agent is raised by two: the solid content concentration is 3% by mass, and the film is obtained by a good method; and the film thickness of the liquid crystal alignment film is too small, which may be advantageous for the alignment film. On the other hand, if the solid content is -74 - .201235751 degrees exceeds ίο% by mass, the film thickness of the coating film is too large, and a good liquid crystal alignment film may not be obtained. In addition, the liquid crystal alignment agent may have a large coating property. Insufficient feelings The preferred range of the solid content concentration is in accordance with the method used for coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is used, the solid content concentration is preferably in the range of 15 mass. When it is carried out by the printing method, the solid content of the solid component is preferably in the range of 3% by mass to 9% by mass, whereby the solution viscosity is in the range of 12 mPa and s to 50 mPa·s. When the inkjet method is used, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, and the viscosity of the solution is in the range of 3 mPa·s to 15 mPa·s as the liquid crystal alignment agent of the present invention. The temperature is preferably 〇200 ° C, more preferably 〇 ° C 〜 4 (TC. '[Embodiment] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not subject to these embodiments. In addition, the roots are synthesized by repeating the synthesis route shown in the following synthesis example: a compound and a polymer, thereby ensuring the necessary amounts of the compound and the polymer used in the following examples. Synthesis of epoxy-based polyorganosiloxanes &gt; Synthesis Example 1] In the reaction with a stirrer, a thermometer, a commercial liquid temperature τ shoulder, a night/genus and a reflux condenser, the reaction of the glutinous rice is added to the 〇〇 〇 的 2 Π 4 for the S 1 1 oxycyclohexyl methoxy Baseline (ECETS), 500g of meringidine ia δ 呉 butyl ketone and l〇.〇g diethylamine' are mixed at room temperature. Then, you., high: deposit, 'e, 丨 have a shoulder funnel After adding 100 g of deionized water dropwise for 30 minutes, it was mixed under reflux, and it should be 6 hours under 8 Torr. After the reaction was completed, the organic layer was taken out and washed with an aqueous solution of ammonium nitrate of 2 mass -75-201235751. After the washed water is neutral, the solvent and water are distilled off under reduced conditions to obtain a polyorganosiloxane having an epoxy group as a viscous transparent liquid. The 1H-NMR analysis of the polyorganosiloxane having an epoxy group gave a theoretically based epoxy group-based peak at a chemical shift (δ) = 3.2 ppm, confirming that the epoxy group did not produce a side reaction in the reaction. . The obtained polyorganosiloxane having an epoxy group has a Mw of 2,200 and an epoxy equivalent of 1 8 6 g/m ο 1 ° &lt;Synthesis of a specific cinnamic acid derivative&gt; Synthesis of a specific cinnamic acid derivative The reaction is all carried out in an inert atmosphere. [Synthesis Example 2] In a flask, 20 g of palladium tetraphosphate, 0.98 g of tris(2-quinophenyl)phosphine, and mercaptoacetamide were mixed. Then, by note, with a syringe

,Time. Adding 7 g of acrylic acid to TLC (thin-layer chromatography) in a 500 mL three-port bromodiphenyl ether with a condenser tube, 0.18 g palladium acetate, (32.4 g triethylamine, 135 rnL dimercaptoethyl II) Add at I20°c,

After confirming the reaction in 1N, a 1:1 (mass ratio) solution of precipitated hexane was recovered from the aqueous hydrochloric acid solution, and the filtrate was injected into 300 rnL of 1N salt. These sediments were recrystallized from ethyl acetate to give 8.4 g of the formula (K-1) (K-1).

-76-201235751 &lt;[A] Synthesis of photo-aligned polyorganosiloxane] Synthesis Example 3 Into a 100 mL three-necked flask, 9 3 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 was added. Alkane, 26 g of methyl isobutyl ketone, 3 g of the quinone cinnamic acid derivative (κ _ 1) and 〇. 1 〇g quaternary salt (SAN-APRO, UCAT 18X) of Synthesis Example 2, at 8 (Stirring at TC for 12 hours. After the reaction was completed, 'precipitate with decyl alcohol, the precipitate was dissolved in acetic acid to obtain a solution, and the solution was washed 3 times, and then the solvent was distilled off to obtain 6 3 g of [A] photoalignment. Polyorganosiloxane (A_丨) is a white powder. The weight average molecular weight M w of the photo-aligned polyorganosiloxane compound (A_丨) is 3,500 = &lt;[C] Synthesis of other polymers&gt; [Synthesis Example 4] In a flask having a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 2 parts by mass of diethylene glycol oxime were added. Base ethyl ether (DEGME). Next, 40 parts by mass of glycidyl thioglycolate as (a) unsaturated compound and 3 parts by mass of unsaturated compound are added. Acetic acid, 10 parts by mass of styrene which is (b2) non-saturated compound and 20 parts by mass of cyclohexylmaleimine were replaced by nitrogen, and slow stirring was started. The temperature of the solution was raised to 7 〇t, The temperature was maintained for 5 hours to obtain a polymer solution of a copolymer (c-1) containing poly(indenyl 彳 1λλ) acrylate. The obtained polymer was subjected to a ^ &amp; 3 · 1% by mass. The number of the obtained copolymer was &lt;, hexamethylene soft average molecular weight was 7,000 Å &lt;Preparation of liquid crystal alignment agent&gt; [Example 1] -77-201235751 The conversion was obtained in Synthesis Example 3. [A] Photo-aligned polyorgano-oxygen (A-1) is added in an amount of 5 parts by mass to the bismuth salt of the [B] photohardening catalyst (San-APRO Co., Ltd.). , CPI-200K) 'then mixed ethylene glycol monobutyl ether (Egmb) and diethylene glycol methyl ether (DEGME) 'solvent combination into eGMB: DEGME = 90:10 (mass ratio), solid concentration of 4. 〇% by mass solution. The solution was filtered by a sieve size of 1 μm to prepare a liquid crystal alignment agent (s_丨β [Example 2] A solution containing the copolymer (C-1) obtained in Synthesis Example 4 as another polymer of [C] was selected, and converted into a copolymer of poly(meth)acrylate contained therein (C- 1) an amount corresponding to 1, 〇〇〇 by mass, to which 5 parts by mass of the [Α] photo-aligned polyorganosiloxane (A_i) obtained in Synthesis Example 3 was added, and 75 parts by mass was added thereto. The sulfonium salt of the photohardening catalyst (SAN-APRO, CPI-200K), and then the EGMB and DEGME' are mixed to form a solvent grade of EGMB: DEGME = 90:10 (mass ratio), and the solid content concentration is 4 · 0 mass% Solution. The solution was filtered by a sieve of pore size ’ μη to modulate the liquid crystal alignment agent (s_2). [Synthesis Example 5] 13.1 g of poly(2-hydroxyethyl methacrylate) was dissolved by heating in 5 mL of NMP, and after cooling to room temperature, 丨〇mL pyridine was added. Thereto was added 17.0 g of cinnabar xenon, and the mixture was stirred for 8 hours. After the reaction mixture was released with nmp, sterol was added, and the precipitate was sufficiently washed with water and dried to obtain 25 g of a polymer. Mixing 3 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 2-methyl [4_(sulfonium thio)phenyl]_2_ pyridin-1-propane, EGMB with respect to 1 part by weight of the polymer In combination with DEGME, the solvent is formed into a solution of •78-201235751 EGMB:DEGME=90:10 (mass ratio), and the solid content is 4% by mass. This solution was subjected to tearing using a sieve 1 μιη screening procedure to prepare a composition (c S -1 ;). &lt;Production of Liquid Crystal Alignment Film&gt; [Example 3] As a coating film forming step, a liquid crystal alignment agent (") was prepared by using a spin = cloth on the side of the TAC and the ^ ^ ^ ^ / film. Nitrogen gas was placed in a box and heat treated for 2 minutes under the crucible to form a film thickness. Then, as a coating film hardening step, a non-biased #8, 8' & coating film containing a 365 nm glow was irradiated on the #m „ ν lamp. The 蜉 的 非 紫外线 紫外线 紫外线 , , , , , , , , , , , , , , , , , , , , 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予Shooting right w, cousin 仗 substrate method, producing 3 polarized ultraviolet light with 313 nm glow line, line 丽 / m2 coating liquid crystal alignment film 0 [Case 4 and 5] as liquid crystal alignment agent, in addition to implementation and implementation Example 3: F = l-like iL 〇, (CS-1), and the same operation was carried out to produce a liquid crystal alignment film. [Comparative Example 1] J m was used as a coating film forming step, and a liquid crystal alignment agent (S·1) prepared by spin-exchanged twist rt I was used on the side of the TAC film coating application & , in the box of nitrogen coating film 1 〇 ^ heat treatment for 2 minutes 'formation of film plant drought, so S 2, liquid crystal alignment ability step, on the surface of the coating · &quot; and Gran-Taylor prism, from the substrate normal Vertically, -79-.201235751, a polarized ultraviolet light of 300 J/m2 containing a 133 Å phosphor line was produced to produce a liquid crystal alignment film. &lt;Evaluation of Liquid Crystal Alignment Film&gt; The following evaluation was performed on each of the produced phase # &amp; β μ difference ruthenium films. The results are shown in Table 1. <<[Adhesiveness] The liquid crystal alignment film obtained in the examples and the comparative example 1 was used as a 〇 〇 〇 使用 使用 使用 使用 p p p p p p p p p p p p 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶Morning Court An Ming (4) Next, set the scotch tape on the plaid pattern, and the cow is firmly attached to the 梅* connected cold plum. 揭 Uncover the scotch tape. Observing to reveal transparency

After the glue can be applied to the film, Qiuqiu W ^ f Μ % 4.1 11 knives. 'The line that is removed along the main film or the one that is in the middle of the intersection. 〇1 S 〇/ D* , , can be judged when the number of all the patterns of the ^ sub-pattern is less than 15% The symmetry is "B" is "B". ". In the above case, [membrane hardness] was judged to be the use of a smectic alignment film on the TAC film. The liquid of the liquid crystal distribution example 1 was measured. "Hardness measurement knot = in = wrong pen scratch tester Hardness is "one hardness measurement fruit = the film hardness is "B". Each judgment is

-80-.201235751 &lt;Production of retardation film&gt; [Examples 6 to 8 and Comparative Example 2] On the faces formed by the liquid crystal alignment films produced in Examples 3 to 5 and Comparative Example 1, by the aperture 〇 The _2 μιη screening program filtered the polymerizable liquid crystal (Merck, RMS 03_013c), and then coated with a spin coater, baked on a hot plate at 60 ° C for 1 minute, and then used H g - on the polymerizable liquid crystal coated surface. The X e lamp was irradiated with a non-polarizing ultraviolet ray of 3 5 5 nm and a 相位J/m 2 to produce a retardation film. &lt;Evaluation of retardation film&gt; The following evaluation was performed for each of the produced retardation films. The results are shown in Table 2. ° [Liquid alignment property] For the retardation films produced in Examples 6 to 8 and Comparative Example 2, the presence or absence of an abnormal region was observed by a % microscope, and no abnormality was observed, and φ was i or 1 The moon shape 'evaluation of the liquid crystal alignment is "A"'. When the abnormal region is observed, the valence liquid crystal alignment property is "B". [Heat Stability] In addition to the production of the south and the blown crystal β祺 under the irradiation conditions of the liquid crystal alignment (A), 'before applying the polymerizable liquid crystal, the crucible is added at 150 ° C. The retardation film of Example k of Example 2 was produced in the same manner as in Example 3 except that ', ' and 1 hour. Then, the case where the abnormality region was not observed as the sf price of the liquid crystal alignment was regarded as the thermal stability "the case where the abnormal region was observed was taken as the thermal stability "B". 81 - 201235751 [Table 2]

&lt;including liquid crystal alignment energy, the phase difference of the region where the direction of the knife is different is thin

Manufacturing S

[Example 9] In the same manner as in Example 3, after the cured coating film was formed on the substrate, the polarizing direction of the polarized ultraviolet ray which was irradiated from the first step of imparting the liquid crystal illuminating energy was 90, and the transmission portion and the light shielding were performed. The masks formed in a long strip pattern were arranged in parallel with each other, and a second polarized ultraviolet ray (polarized ultraviolet ray 300 J/m 2 containing a bright line of 31 claws obtained by using a Hg-Xe lamp and a Glan Taylor prism) was irradiated. Next, the polymerizable liquid crystal (Merck's 'RMS03-013C)' was applied to the surface on which the liquid crystal alignment film was formed by using a spin coater after being subjected to a screening procedure of a pore size of 2 μm, at 6 Å &gt; After baking for 1 minute on a hot plate, the polymerizable liquid crystal coated surface was irradiated with 30,000 J/m 2 of non-polarized ultraviolet light having a 365 nm wavelength, and a phase of a region including a liquid crystal alignment ability was produced using a Hg-Xe lamp. Poor film. -82-.201235751 [Examples] In the same manner as in the case of the solid addition 3, the liquid crystal alignment agent was applied onto the substrate, and the first half of the step of imparting the liquid crystal directional energy was irradiated while blocking the light of the substrate - half. Polarized ultraviolet light (polarized ultraviolet ray _/m containing a 313 nm (quad) line obtained using a Hg_xe lamp and a Taylor prism). Then '% in rotation from the initial polarized UV. The direction of polarization: the light that is exposed to the exposed portion of the first exposure, in order to illuminate the unexposed part with polarized ultraviolet light, the second partial phoenix 妒 green γ is used as the first ultraviolet light (using Hg-Xe lamp and each ^ Taylor) The prism obtained a polarized ultraviolet bribe &amp; Included in the 313 nm (four) line. Next, the polymerizable liquid crystal (MM company, R deleted 3_〇13C) 'by the hole 〇 〇. 2 μ m screening borrowed; net, gold &amp; 榭 榭 private filter, using spin coater Coating: The surface on which the liquid crystal alignment film is formed is baked on the hot plate of (10) for 1 minute, and then the Hg-Xe lamp is used, and the polymerizability 'Han Riji coated surface is made. · 30,000 J/m contains wavelength 365n... The difference between the non-polarized ultraviolet rays of the person's illusion and the non-polarized ultraviolet ray of the person, the phase difference film of the region in which the direction of the liquid crystal alignment ability is different [the evaluation of the direction of the liquid crystal alignment ability is different], the phase difference 溥 film is obtained in the ninth embodiment The phase difference film is disposed between the polarizing plates disposed under the y 下 Λ έ έ υ _ _ prism strips, so that the light is observed from the opposite direction of the observation side, Directional flat rod $ When the polarized light of the external line is placed in the mouth or vertically, it is irrelevant to the pattern of the Hitachi. Day. On the other hand, if the phase difference is thinned at the 45. The retardation film is independent of the pattern: 疋 has birefringence. Jade 4 is exempted, indicating that there is a partial aspect of the observation of polarized ultraviolet irradiation with 201235751. Regardless of the film, it is shown that the phase arrangement of liquid crystal containing Example 6 is included, and the case and darkening are the same as in the case of irradiation and irradiation. Whether it is dark or not. In the other 4 5 ° ', the phase difference is all brighter. In addition, the retardation film obtained by 9 or 10 is overlapped and confirmed by the angle. Example 1 Polarization of the line of the 〇: The polarization of the ultraviolet ray is obtained by the bipolar refracting of the phase difference illuminating polarized violet. The parallel or light direction film is arranged vertically in the film of the outer line and the side difference film which is observed under different light direction members, and the plane of the plane rotating polarization direction is parallel or straight as the phase of the above-mentioned embodiment According to the present invention, it is possible to provide a method for producing a liquid crystal alignment film having high productivity, a method for producing a retardation film excellent in liquid crystal alignment property and thermal stability, and the above-described productivity. In the method for producing a high liquid crystal alignment film, light alignment can be performed even when a small amount of radiation is irradiated, and a liquid crystal alignment film excellent in film hardness and adhesion can be efficiently produced under lower temperature and short-time heat treatment conditions. Further, the liquid crystal agent can also be applied to a roll-to-roll method which is excellent in mass productivity. Further, the liquid crystal alignment agent is also suitable for a liquid crystal alignment film in a region containing different directions of liquid crystal alignment, such as 3D image use. [Simple description of the diagram] None. [Main component symbol description] None. -84-

Claims (1)

.201235751 VII. Patent application scope: A method for manufacturing a liquid crystal alignment film, which has the following steps: (1) coating a liquid crystal alignment agent on a transparent film; forming a step of forming a film; and 2) A step of irradiating the coating film with radiation, curing the coating film, and (3) irradiating the coating film after the curing with radiation. The liquid crystal alignment, the liquid crystal alignment, the center, the L, x, and the J ^ method are as follows: / The liquid crystal alignment film is used for the retardation film. 3. The method for producing a liquid crystal alignment film according to the invention of claim 2 or 2, wherein the radiation in the above step (2) is non-polarized; the outer line is opened, and the radiation in the above step (3) is caused. Polarized ultraviolet light. A method for producing a retardation film, comprising the steps of: (1) applying a liquid crystal alignment agent to a transparent film to form a coating film; and (2) irradiating the coating film with radiation to cure the coating film. (3) a step of irradiating the coating film after the curing with radiation and imparting a liquid crystal alignment ability; (4) a step of applying a polymerizable liquid crystal to at least a part of the liquid crystal alignment crucible; and (5) making the polymerizable liquid crystal The step of hardening. 5) The method for producing a retardation film according to claim 4, wherein the above step (3) has the following steps: (3-1) irradiating a part or all of the cured coating film first a step of emitting radiation; and '-85-.201235751 (3-2) a step of irradiating a portion of the cured coating film with a second radiation having an incident direction or a polarization direction different from the first radiation. 6. The method for producing a retardation film according to claim 5, wherein the step (3-2) is (3-2,) at least a portion of the coating film after curing which is not irradiated with the first radiation. The step of illuminating the second radiation described above. 7. The method for producing a retardation film according to the fourth aspect, wherein the radiation in the step (2) is non-polarized ultraviolet light, and the radiation is polarized in the step (3). UV rays. A liquid crystal alignment agent for use in a production method according to any one of claims 1 to 7, which comprises [A] a polyorganosiloxane having a photo-alignment group and [B] Photohardening catalyst. The liquid crystal alignment agent according to claim 8, wherein the photo-alignment group is a group having a cinnamic acid structure. 10. The liquid crystal alignment agent according to claim 9, wherein the group having the above cinnamic acid structure is a group derived from a compound represented by the following formula (1) and from the formula (2) At least one selected from the group consisting of a group of compounds, H^(-R4—R5 COOH (2) -86- .201235751 Inhibition (1) R is a stretching phenyl group, a stretching phenyl group, a stretching terphenyl group or a stretching hexyl group, a phenyl group, a stretching phenyl group, a stretching terphenyl group or a stretching group. A part or all of the hydrogen atom of the cyclohexyl group may be substituted by an alkyl group having a carbon number of 1 Å, an alkoxy group having a fluorine atom of "1 〇, a fluorine atom or a cyano group; and r 2 is a single bond. , an alkanediyl group having a carbon number of 3, an oxygen atom, a sulfur atom, _CH=CH_, _nh_, 丨〇〇_ or -OCO-, a is an integer of 〇~3, wherein, in f: Ri, R , the same 'may be different; r3 is a fluorine atom or a chaotic base 'b疋〇~4 integer; - has mR4 is a stupid base or a stretched hexyl group, the stretch phenyl or stretch two = two t sub-parts or all... It is substituted by a chain or a smectite pit, a fluorine atom or a cyano group of a chain or a ring-shaped alkyl group having a carbon number of 1 to 10 and a ring of carbon atoms. ; R5 β η 子意 i: helmet 1 1 ΑΑ 疋 early bond, alkanediyl group with a carbon number of 1 to 3, an oxygen atom, sulfur is an integer of 1 to 3, glycine, or -ΝΗ- 'c, , medium, when c is 2 or more, More or the same, can be different, ... is a gas atom or two solids... can be an integer, ^ is an oxygen atom, d is a 0~4 t group, a bivalent alicyclic group, a divalent heterocyclic ring (a) aromatic The nucleobase ^ is a single bond, CH2)f_* or; base: a connection key with "*" and (4) connection, f 2) 〆, where integer, e is an integer from 0 to 3, where It is M0 and R8, each of which may be the same or different. - Above, on R7, 1), such as the application of the patent Fanguang ^ ^ 苐 苐 8 of the liquid crystal alignment of the first alignment of the polyorganophthalocene 其中 ', [burning, its hydrolyzate and its oxy-organic stone In the group consisting of the condensate of the oxygen solution, the group of the above formula is formed by the combination of the compound represented by the above formula (1) and the compound represented by the formula (7). The anti-12 of the J~ species is as claimed in any one of the claims 8th to 7th, wherein the further human τ ws nocturnal alignment step contains [C] from poly-proline, and the decyl non-alkenyl group is not The saturated compound polymer and at least - 锸s % selected from the group consisting of the imine groups of the imine group and the ethyl oxoxane are as described in the patent range 8 to the polymer. A liquid crystal alignment film formed by the agent. The liquid crystal alignment according to the above-mentioned item is as shown in the patent specification θ, the liquid crystal alignment crystallization alignment threshold described in the Uth item, and the έΐΑ έΐΑ b knife direction different regions. Further, a liquid phase alignment film 骐 is provided, which is provided with a liquid crystal alignment film as described in claim r.丨粍 帛 13 or 14 A liquid crystal display element for phase 叩 image according to item 15 of the patent application. Differential binding film, which is applicable to -88- 201235751 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: