TW201219934A - Method for producing cholesteric liquid crystal display, cholesteric liquid crystal display, and liquid crystal alignment agent - Google Patents

Abstract

The purpose of present invention provides a cholesteric liquid crystal display, a method for producing the cholesteric liquid crystal display, and a liquid crystal alignment agent for forming such liquid crystal alignment film. The present invention is a cholesteric liquid crystal display, which has a pair of substrates positioned in the direction of opposition; cholesteric liquid crystal, positioned separately in multiple zones of the substrate divided in vertical direction to the substrate; and liquid crystal alignment films, laminated respectively between aforementioned each substrate and cholesteric liquid crystal. The cholesteric liquid crystal display is characterized in that the aforementioned liquid crystal alignment film on at least one side is formed by a radiation-sensitive liquid crystal alignment agent.

Description

201219934 VI. Description of the Invention: [Technical Field] The present invention relates to a cholesteric liquid crystal display method, a cholesteric liquid crystal display, and a liquid crystal alignment agent. [Prior Art] A cholesteric liquid crystal display liquid crystal to which a prescribed chiral liquid crystal (chiral nematic liquid crystal) is added with respect to a base liquid crystal is used to selectively reflect light of a color corresponding to a chiral pitch without using a color; a light sheet or A clear color outside of the polarizing plate. The cholesteric liquid crystal display can maintain writing (memory) even when the electric field is cut off by applying a voltage. Therefore, good quality can be achieved without using a main manufacturing cost. Display. Further, according to the biliary display, by using the memory, the electric field for driving the liquid crystal can be cut off first in the display signal, thereby suppressing the electric power. The application of the cholesteric liquid crystal display to electronic paper or the like is being studied. In the cholesteric liquid crystal display, the rotted color component ' usually has a three-layer structure in which three original layers corresponding to blue, green and red are laminated. However, since such a three-layer liquid crystal layer liquid crystal display has a complicated structure, it is difficult to manufacture, and has a thickness of three layers, so that the thickness is limited. Thus, a cholesteric liquid crystal display having a structure in which the respective liquid crystals corresponding to the two primary colors are separated and arranged (the cholesteric device of the manufacturer of JP-A-2000-267142, JP-A No. 2-772419, Because of this, it is possible to display in color. This is a function of the state of the moving element, and the sterol type liquid crystal is not changed. Therefore, the color of the liquid crystal displayed in the color of the flexible display is cholesteric and Proposed in a plane L曰本特号号 bulletin). 201219934 However, in such a cholesterol split liquid crystal display, since a partition wall or the like for separating the respective liquid crystals is present, there is a case where a liquid crystal alignment film for imparting alignment to the liquid crystal beer is formed in a flat method. Next, the wave crystal alignment film is formed in a shape of a cladding shape and is formed by partitioning the partition walls. It is generally difficult to carry out the above-described polishing treatment in such a crystal alignment film, and the polishing can be performed in a desired direction while uniformly exhibiting liquidity. Therefore, the 'liquid crystal alignment ability of such a liquid crystal is poorly present' and the uniformity of the liquid crystal connected to the liquid crystal alignment film cannot be said to be sufficient. Therefore, there is still room for improvement in display performance such as the resolution of the cholesterol type liquid a. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PRIOR ART The purpose of the present invention is to provide a sterol type liquid crystal display, the cholesteric liquid crystal and the non-state method, and a liquid helium liquid crystal display for forming such a liquid crystal alignment film. The liquid a absorbs the dichroic alignment film, so the alignment uniformity of the liquid crystal is high. In order to solve the above problems, a 胆__π-based cholesteric display includes a pair of opposed substrates, and the cholesteric type is provided on the surface. Also, the concave liquid chemistry of the wall is a kind of biliary manufacturing side in the crystal alignment direction, and the liquid alcohol type liquid liquid liquid of the bile force '-5-201219934, the liquid crystal is placed on the high solid cutting wall And a liquid crystal alignment film laminated between each of the substrates and the cholesteric crystal, respectively, wherein the liquid alignment is performed on at least one side of the substrate The film is formed of a radiation sensitive liquid crystal alignment agent. The liquid crystal alignment film on at least one side of the smectic cholesteric liquid crystal display is formed of a radiation-sensitive liquid crystal alignment agent. Therefore, even if the liquid crystal alignment film is not formed on a plane, the liquid crystal alignment ability of the uniform sentence can be obtained in the desired direction by irradiating the radiation. In view of the above, the cholesteric liquid crystal display can exhibit excellent display uniformity of liquid crystal alignment and excellent display performance. The above plurality of regions may pass through the shape. By dividing the cholesteric liquid crystal display, it is possible to prevent each region' and further improve the performance of the cholesteric liquid crystal which is displayed in a grid-like partition wall. Separation and transfer; 2^ The liquid of the organic decane in the film to the film. The above-mentioned group of liquid crystal sensitizing liquid crystal alignment agents may contain [A] and polyorganisms (hereinafter also referred to as Is "[A]i oxane"). The irradiation of the coating film formed of the above-mentioned [A] photo-alignment polycrystal alignment agent can improve the alignment of the molecules forming the alignment enthalpy. In the liquid crystal display W, the alignment uniformity of the liquid crystal is improved. The photo-alignment group is preferably a photo-alignment group having a cinnamic acid structure and a cinnamic acid or a derivative thereof as a basic skeleton, and is easily introduced. The liquid BJ formed by the agent has a higher liquid crystal with a matching optical organic enthalpy, then a group of 0. The cinnamic acid is formed by the light alignment -6-201219934. Therefore, the alignment of the liquid crystal can be achieved. Uniformity--Improving the above-mentioned cinnamic acid in the cholesteric liquid crystal display, the character represented by the formula (1), the earth mass 'may be composed of a group derived from the following compound, and from the formula (2) At least one selected from the group consisting of the clusters represented. H-(-R1 - R2 H-{-R4 - R5

COOH (2) (1) (In the formula (1), R1 is a benzene-extension ring group. The (4) group, a stretched terphenyl group or a part or all of a hydrogen atom is bonded to a ring or a cyclohexyl group. An alkane group having a fluorine number of 1 to 10, an alkoxy group having a cesium atom number of 1 to 10, a sulfhydryl group, an early bond of the stomach, and a carbon atom number of 1 to 3 , q Q alkane 2 ~ 'claw atom, _CH = CH-, -ΝϋΚΘΓ» 3 integer. > (denier a., $ 00...a is 〇 (5),, —疋 although a is 2 In the above, each R丨 and r2 may also be X m η 3 1 R. The ruler is a fluorine atom or a cyano group. b is an integer of 〇~ (2, Φ, 4). R is a phenyl group or Extend the ring hexyl. The extension of the G | the base of the G + 8 into the base or the ring or the 戸, knife or king hydrogen atoms can be 1 to 1 碳 carbon atoms. Oxygen long-shaped alkane The bond of a chain, a carbon atom number A 1 to 10, a chain oxy group, a ϋ/sv ^ bond or a cyclic fluorene bond is substituted by a cyano group. R5 is a single bond and has two carbon atoms. However, d, milk atom, sulfur atom or ·, is an integer of 1 to 3. When c is 2 or more, both r4 and r5 may be used. 201219934 同. R6 is a fluorine atom or a cyano group. d is an integer of 〇~4. R7 is an oxygen atom, -C00-* or -0C0-*, wherein a linkage with * is linked to R8. r8 is a divalent An aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. R9 is a single bond, _〇CO_(CH2)f_* or -〇( CH2)g·*, wherein 'the linkage with * is linked to the carboxyl group. f and lyse are each an integer of 1 to 1 。. 6 is an integer of 〇~3. But when e is 2 or more, 'R7 and R8 are each By using the group derived from the above specific cinnamic acid derivative as the above group having a cinnamic acid structure, the optical alignment property of the obtained liquid crystal alignment film can be further improved, so that the film can be further improved. The alignment uniformity of the liquid crystal in the cholesteric liquid crystal display. ^ [A] The polyorgano oxoxane is preferably a reaction product which is composed of a polyorganosiloxane having a nucleus group and the above formula ( 1) In the group of the compound represented by the compound and the compound represented by the above formula (2), In the [A] polyorganosiloxane which has a linear liquid crystal alignment, it is possible to use a reactivity between an organic oxoane having an epoxy group and a specific cinnamic acid derivative. It is also easy to introduce a side bond group derived from a specific cinnamic acid derivative having a light-generating group into a polyorganosiloxane which is a main chain. The above liquid crystal alignment agent preferably further contains [B] At least a compound selected from the group consisting of polyamidones, polyamidiamines, ethylenically unsaturated compound polymers, and polyorganosiloxanes having no-orthogonal groups (hereinafter referred to as 'the same' "[B] Other polymers,,). In the liquid crystal alignment film formed by the upper side to the J, it is clear that the polyorganism_burning is unevenly distributed in the vicinity of the surface layer. Therefore, by containing [the 201219934 other polymer, even if the content of the polyorganosiloxane in the liquid crystal alignment agent is reduced, the polyorganosiloxane can be unevenly distributed on the surface of the liquid crystal alignment layer, and the alignment of the liquid crystal can be improved. Light alignment performance, therefore, can maintain the uniformity of liquid crystal alignment. Therefore, it is possible to reduce the content of the high-organism polyorganism in the liquid crystal alignment agent, thereby reducing the manufacturing cost of the cholesteric liquid crystal display. The above liquid crystal alignment agent preferably further comprises [c]. having two or more polychlorinated structures, a ruthenium-based structure, and (b) a b-based base-based vinegar structure and A compound of at least one structure selected from the group consisting of a tertiary Tg structure (hereinafter, also referred to as "[c] a compound containing a vinegar structure, wherein the above liquid crystal alignment agent contains a compound containing [c] a p-form, The liquid crystal alignment agent forms an acid at the time of coating and promotes (4) polyorganisms by the generated acid; the father's 'the result' can further increase the obtained liquid crystal alignment film and the cholesteric liquid crystal display The heat-resistant method of manufacturing a cholesteric liquid crystal display according to the present invention is a method for manufacturing a cholesteric liquid crystal display, which has a counter-tilt plate; in a vertical direction with respect to each of the substrates, a plurality of cholesteric liquid crystals arranged in a wide area between the substrates of A; and a liquid crystal alignment film which is provided between each substrate and the cholesteric type a and having a nighttime, and the manufacturing method (1) At least one The step of coating the substrate with the radiation-sensitive liquid crystal alignment agent and the step of forming the coating film (2) The step of irradiating the coating film and the formation of the liquid crystal alignment film -9 - 201219934 (1) A step of filling a cholesteric liquid crystal in each divided region. 'The crystal display can be efficiently produced, and can promote low growth. The coating of the linear liquid crystal alignment agent can be coated by an inkjet method. In the cholesteric liquid crystal display, the cholesteric liquid crystal display has a sense of radiation linearity in a liquid between a cholesteric liquid substrate and a cholesteric liquid crystal disposed in a direction perpendicular to the respective substrates. Further, the liquid crystal alignment film included in the display is used to improve the alignment uniformity of the liquid crystal. Since the liquid crystal display has a film having a film, the display performance of the liquid crystal is uniform. Therefore, the flexible display such as the adhesive electronic paper is used. The improvement of the yield of the cholesterol type liquid which is excellent in uniformity and the production method according to the present invention is mainly The manufacturing cost is reduced by the inkjet method. The liquid crystal alignment agent of the present invention which is efficiently used in the plurality of regions to be cut out is a liquid crystal alignment for the liquid crystal alignment film: a pair of substrates; a plurality of region crystals between the divided substrates; and a layer of the respective crystal alignment films respectively, wherein the liquid crystal alignment ability is imparted to the cholesteric liquid crystal in a direction in which the liquid crystal alignment direction according to the present invention is Therefore, the liquid crystal compatibility of the cholesteric type excellent liquid crystal alignment ability according to the present invention is high, and various liquid crystal display devices to which the resolution alcohol type liquid crystal display can be applied can be improved.

-10-201219934 [Embodiment] The cholesteric liquid crystal display of the present invention, an alignment agent thereof, and a method for producing a cholesteric liquid crystal display will be described with reference to the accompanying drawings. - The appropriate <cholesterol type liquid crystal display> The cholesteric liquid crystal display i of Fig. 1 is provided with the opposing substrates 2 (2a and 2b); the substrate which is divided in the direction perpendicular to the respective substrates 2a and 2b. The cholesteric liquid crystal 3 is disposed in each of the two regions, and the liquid crystal alignment film (four) 4b is laminated between the respective substrates n 4 zb and cholesterol H 3 . The plurality of diol-type liquid crystals 3) are partitioned by the partition walls 5. Further, the cholesteric liquid crystal display 1 is provided with transparent electrodes 6a and 6b which are laminated on the respective substrates 2& and the opposite surfaces. In addition, in the first figure, the side is emitted. That is, the first side light is incident and reflected from the upper side, and in the upper side of Fig. 1, the pair of substrates 2a and 2b which are visually recognized on the upper side are transparent. Examples of the respective substrates 2a and a few include a glass substrate such as float glass or nano-glass, triethylene glycol (TAC), polyethylene terephthalate, and polybutylene terephthalate. a diol ester, a polyether sulfone, a polyamine, a polyimine, a polymethyl methacrylate, a polycarbonate, a ring-opening polymer of a cyclic olefin, a compound thereof, an addition polymer of a cyclic olefin, and a fragrance A transparent substrate such as a plastic substrate such as a family (four). When the substrate 2a temple 2b is a plastic substrate, the cholesteric liquid crystal can be used for a flexible display including electronic paper. 201219934 The transparent electrode 6a is laminated on the opposite surface side of the substrate 2 at the lower side A, and the transparent electrode 0b is laminated on the surface of the opposite surface side of the substrate 2b Β0 φ ^ and θ han b. The transparent electrodes 6a and 6b are strip-shaped films, 4- n, ^ , m 〇, and we can set them as follows: The transparent electrodes are orthogonal when viewed from the upper side in Fig. 1. Further, the portions where the respective intersections are the substantially central portions of the respective pixels and the respective pixels correspond to the plurality of divided regions. Examples of the transparent conductive electrode (thin m _ U film) include a NESA film formed by tin oxide curry 2) (registered indium oxide-tin oxide (In2〇3_Sn〇2) by ppG Corporation, USA). ι 〇 〇 ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” 'When viewed from the upper side of _ τ in Fig. 1, it is divided into a plurality of regions corresponding to the respective pixels. According to the cholesteric liquid crystal display, the upper partition is passed along the partition walls 5 along the two substrates. In the vertical direction, that is, the opposing direction of the two substrates is separated, it is possible to prevent the movement of the cholesteric liquid crystal 3 disposed in each domain, and to further improve the display performance. The material of the partition wall 5 is not particularly limited, and for example, it is known to use. The photo-resistance material, the protective film material of the acrylic acid or the polyimine, etc. The liquid crystal alignment film 4a is laminated on the opposite side of the substrate 2a by a transparent electrode 6a. | Volume · $ ^, ⑴ Wang surface. Further, the liquid crystal alignment portion M 4b through the transparent electrode 6 b + insects and the sound is not erected to sigh layer on the surface side of the substrate 2b is provided on the portion of the partition wall 5.

The β-ray liquid crystal alignment films 4a and 4h, rt>~r~., , t. .A T *b, are formed by the radiation-sensitive liquid crystal alignment agent described in detail below. Therefore, the pile a ^ is specially spliced and laminated in the partition wall 5 of the 201219934 like the liquid crystal alignment film 4 b, and it is difficult to perform the sanding treatment (not in the plane, the reporter, the hope, the ancient A, ), can also have a uniform liquid crystal alignment capability at '° by irradiating radiation. Cholesterol-type Pan a 1 wide* ^ and Μ 3 are disposed in a plurality of A partitioned by the partition wall 5, and the upper surface thereof is connected to the liquid crystal alignment film 4a, and the lower surface is connected to the liquid crystal film 4b. Each of the cholesteric night owls ‘ disposed in each of the regions is excellent in the alignment property by sandwiching the film (b) formed of the radiation sensitive liquid crystal. Selectively reflect red, green, or δ 玄胆固 83⁄4 Φ〗, 'Jie Θ in each of the divided regions. > U private ^ LCD 3 in order to adjust the chiral spacing of the 3 sterol type LCD repeating order # & 3 kg configuration. According to the cholesteric liquid crystal I, the three kinds of cholesteric liquid crystals corresponding to the three primary colors are arranged in a mosaic shape, whereby the liquid crystal layer of the substantially - layer can be displayed in color. Further, in the case of a monochrome liquid crystal display, a cholesteric liquid crystal may be used, and in addition, two or more cholesteric liquid crystals may be used. The cholesterol-type liquid crystal 3 can be estimated to be used as a material for eight y, and can be obtained, for example, by using a chiral agent in a ratio of tens of 詈 Η / 〇 in the base liquid crystal. Further, the wavelength of the selectively reflected light may be adjusted by the type or amount of the chiral Μ. As the current A c column. Six 曰 1 F hook 5 基础 basic liquid crystal, nitrogen, fluorine, ester or the like nematic liquid a can be used. 0 main ^ soil day. Further, the chiral agent can be appropriately selected in consideration of solubility, twisting force, temperature dependency of the pitch, and the like. : In addition, you can also use the cholesteryl ester of the cholesteryl ester from the * > Further, in the case of the cholesteric type, it is also possible to contain and use a polymer in the day of the gypsum type liquid crystal. In this case, photopolymerizable such as acryl vinegar-13-201219934 or methacrylate can be previously blended in the cholesteric liquid crystal. A thermosetting polymer precursor such as a polymer precursor or an epoxy compound, and a reaction initiator is added and used as needed. In the cholesteric liquid crystal display 1, by controlling the alignment state of the cholesteric liquid crystal 3 by application between the transparent electrodes 6a and 6b, it is possible to control the transmission or reflection of incident light. Therefore, the cholesteric liquid crystal display 1 can perform color display without using a polarizing plate and a color filter by arranging three kinds of cholesteric liquid crystals in a mosaic form. At this time, the liquid crystal alignment film provided in the cholesteric liquid crystal display 1 can have a uniform liquid crystal alignment ability in a desired direction by irradiating radiation, although it is not formed on the above-described one plane. Therefore, according to the cholesteric liquid crystal display device 1, it is possible to exhibit excellent display performance such as excellent uniformity of alignment of the liquid crystal, high resolution, and the like. The cholesteric liquid crystal display can be used for television or personal electric

The alignment uniformity of the liquid crystal alignment film to be paid. Brain monitor device, mobile phone, game console, and other liquid crystal display devices

<Radiation-sensitive linear liquid crystal alignment agent>

The liquid crystal of the polyorganismite of the group preferably contains [A] a photoalignment type alignment agent. The above liquid crystal alignment agent is composed of

Since S-14-201219934 contains [A] photo-aligned polyorganosiloxane, it is possible to reduce the amount of light irradiation necessary for alignment by high-sensitivity optical alignment. Further, since the liquid crystal alignment agent does not require a heating step during radiation irradiation and after irradiation, the liquid crystal alignment film can be efficiently produced. Further, the liquid crystal alignment film obtained from the above liquid crystal alignment agent is excellent in liquid crystal alignment property and thermal stability. Further, the liquid crystal alignment agent preferably contains a compound of [B] other polymer and [C] ester-containing structure, and may further contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, [A] photo-aligned polyorganosiloxane, [B] other polymer, [C] vinegar-containing compound, and optional components will be described in detail. <[A] Photoalignment Polyorganooxane> [A] Photoalignment polyorganosiloxane, which is a light-aligning group on at least a part of the following group, which is a group The group is composed of polyorganic money as a primary bond, a hydrolyzate thereof, and a condensate of the hydrolyzate. By the light, the directional group can make the sensitivity of light alignment good, achieve low light, and ray, and the liquid crystal alignment film is excellent in liquid crystal alignment. In addition, 歜 organic 矽 作为 is used as the main chain. Therefore, the liquid crystal alignment film formed of the liquid crystal alignment agent described above has excellent chemical stability and stability. " As a photo-alignment group, a group derived from a light-aligning property: various compounds can be used, for example. A group having a cinnamic acid structure containing azobenzene or an organism thereof as a basic skeleton, a cinnamic acid group containing cinnamic acid or a living organism thereof as a basic skeleton, and a substance containing a cinnamic acid or a derivative thereof may be cited as a basic a coumarin containing group containing a chalcone group, a dibenzophenone group containing dioxime or a derivative thereof as a basic skeleton, and a cinnamole or a derivative thereof as a basic skeleton A structure or the like containing a polyimine or a derivative thereof as a basic skeleton. Among these photo-alignment groups, if the ease of introduction and the ease of introduction are preferable, it is preferable that the group has a cinnamic acid structure containing cinnamic acid as a basic skeleton. The structure of a group having a cinnamic acid structure, and the bamboo organism as a basic skeleton, is particularly limited in terms of today's ancient wood;;: a group of the above specific cinnamic acid derivative. Stretching biphenyl, #二磁婪A bucket, & Shen-Linken base or stretch ring has S. The benzene: a part or all of hydrogen of the ancient biphenyl or exocyclohexyl group, the number of 2, the atomic number of 1 to 1 〇, and the alkane rolling of a sheet having a gas original of 1 to 1 〇 Substituted by a fluorine atom or a cyano group. R rabbit atomic number odor, ,, ~3 alkanediyl group, oxygen atom, sulfurogen, ·,.'·(:00_.a is an integer of ◦~3. When 乂, each Rl and R2 may be the same Further, it may be a different atom or a cyano group. b is an integer of 〇~4. It is a compound represented by the above formula (1), for example, a compound represented by the formula: 'The orientation of the quinone and the quinone imine is derived. The cinnamic acid or preferably the phenyl group, the extended phenyl group can be a single bond of a carbon atom, '-CH = when a is 2. R3 is fluorine to enumerate

S -16- 201219934

(1-19) (1-20) wherein 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 a single bond, an oxygen atom or - 〇Η2 = (3Η2-.!) is preferably 0~1. When a is 1 to 3, b is particularly preferably 0. -17- 201219934 In the above formula (2), r4 is # lean I + , 丄 , .? . AA is a stretching base or a cyclohexyl group. Some or all of the soils of the phenylene-extension hexanyl group can be broken by the chain number of the atomic number A 1 10 or the ring-shaped courtyard base, and the carbon source "the number of the two is 1~ The chain- or cyclic alkoxy group of ～10, the alkane R having an atom or a cyano-coating of 1 to 3 is an integer of the number of the early bond and the number of slave atoms. When C is 2 or more, R4 "go...C For 1~3 + can not be F1 亍R and R5 can each be the same, but also different. RU fluorine atom or cyano group. j is an integer of hydrogen®, two υ4. R7 horse rolling millennium - coo-* or -oco-*. Among them, choose the ancient ^ R8 connection. R8 is > μ — , with a linkage bond and a 2 valet aromatic group, a 2 valence heterocyclic group or a 2 valence two: valence group, 2 〇C〇(cu , ^ is a fine σ Niang group. R9 is a single bond, -〇C〇-(CH2)fO(c _* early bond-based linkage. f and ▼ have * linkages and carboxyrg valleys are 1~ In the case of 1〇, the number is +, and e is an integer of 0 to 3. When the field 6 is 2 or more, it may be different. The ruler and the ruler may be the same, and the formula (2) is also expressed as the formula (2). -1) ~ (2_u D, for example, may be exemplified by ^ 2).

'COOH : 2-1) q_hC3^c. -ch==ch~<(^-< ch-Q_ (Form 10: The number of carbon atoms is ! base, the number of carbon atoms A 1 1Λ 1 〇 chain or ring number of alkane is 1~1 The chain or cyano group of fluorene. f is synonymous with the alkane group and the fluorine atom-specific cinnamic acid derivative in the formula (2). The conventionally known formula, the order, and the like are particularly limited, and can be synthesized by a combination of methods. For the representative synthesis of shun-18-201219934, for example, it can be exemplified that (1) under the conditions of the test, the ring having the halogen atom is substituted.

The ruthenium compound is reacted with acrylic acid in the presence of a transition metal catalyst to obtain a ruthenium | 4 main AJ method of ruthenium cinnamic acid derivative, (π) under a basic strip of 4 cows "J 4 吏 ^ ^ iS stained fs, A method in which a cinnamic acid in which an oxygen atom is substituted by a halogen atom and a compound having a benzene ring skeleton substituted with a functional atom are reacted in the presence of a transition metal catalyst to form a specific cinnamic acid derivative. ^As a part of the [A] photo-aligned polyorganosiloxane, which is contained in the main chain as the main chain, the hydrolyzate and the condensate of the hydrolyzate, as long as it has the following part, &quot And particularly limited, the portion is derived from a structure in which the above-mentioned = group can be introduced] A] photo-aligned polyorganophosphorus oxide, a hydrolyzate, and a mixture of the water: a portion of at least one of; a group derived from a compound that does not emit light. The above-mentioned light alignment can be introduced as the above-mentioned light alignment, for example, a radical, a ring @H, and the like. " mercapto, fluorenyl, yl, aryl λ oxy. Γ is preferably ring U] photo-aligned polyorgano oxy- oxy, preferably well-defined and expressed by the above formula (1) and / or (7) In the above liquid crystal alignment agent, the reaction by: and the reaction between the machine and the specific oleic acid derivative is as follows: the gas base is easily used as the main chain. The polyorganoquinone may be derived from a specific cinnamyl having a photo-alignment:: birth: group ' -19- 201219934 匕 ^ , the claws are simply introduced into the polyorganosiloxane to form an epoxy group as a side chain, washed 'There is also a special limitation. The polyisocyanate having an epoxy group as described above can be a hydrolyzate of a polyorganooxane having an epoxy group, or can be hydrolyzed by the county a condensate of matter. The polyorganofluorene-based emulsion having the epoxy group is preferably a polyorganoquinone having a structural unit represented by the following formula (3), a hydrolyzate of the emulsion and a condensate of the hydrolyzate. At least one of the selected groups. Solution X1 (3)

SiΟΥ1 (Formula (3", Χΐ is a radical having an epoxy group, a carbon number is ΚΗ) (tetra)oxy group, a carbon atom-based alkyl group or an aryl group having 6 to 20 carbon atoms). The hydrolyzed condensate of polyorgano-oxyxane having the above-mentioned type of door _ « _ no structural unit ^ 7 includes not only the hydrolysis condensate of the polyorganosiloxane, but also the oxygen amp The hydrolysis of the structural unit shown in the above formula (3), in the table of the above formula (3), the process of the formation of polyorganooxane by the main filament of the genus, and the above " branching or cross-linking, etc. The obtained polyorganismite oxidized product - the hydrolysis condensate in the case of the structural unit of the above formula (3). The enthalpy of the above formula (3), σ circle, is not particularly limited, and the monovalent organic group which may have a ring gas group shrinks. The glycerol oxyhydroxide U is, for example, a group containing a glycidyl group or a ketoxycyclohexyl group, etc., and Χι ^ „ is represented by the following (10)·Μβ·2). (4) As X, better -20- 201219934

(In the formula (X1-]:), A is an oxygen atom or a single bond. h is an integer from 1 to i of 0 to 6. wherein, when i is 0, A is a single form (X^2), j An integer of 1 to 6. In the formulas (X1-;!) and (X^2), * each represents a connection key). Further, in the above formula (X^1) or (XL2), an integer of 3 represented by the following formula or (X1-〗-!) is preferable. key. Epoxy group.

(In the formula (X^11) or (X, 2-l), * represents a linkage bond.) In the Y1 of the above formula (3), the alkoxy group having 1 to 10 carbon atoms may be 歹I. An oxy group, an ethoxy group or the like; an alkyl group having 1 to 20 carbon atoms, which may be an alkyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl n-octyl group, a n-decyl group or a positive group.癸基,正十二统基,正十正十四烧基,正十五烧基,正六烧烧基,正十正十八烧基,正九烧基,正二十烧基, etc.; For example, hydrazine such as hydrazine, n-heptyl group, tris-alkyl group, heptadecyl group, and -2 1-201219934 are aryl groups having a number of slave atoms of 6 to 2 Å, and examples thereof include benzoin and the like. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation color 1 (GPC) of the epoxy group-containing polyorganosiloxane is more than 500 to 100, _, more preferably 1, just ~1〇, 〇〇〇, and especially good for i _ ~ 5,000. Further, Mw in the present specification is a polystyrene-converted value measured by Gpc in the following manner. Branch: manufactured by Tosoh (stock), TSKgelGRCXLII Solvent: tetrahydro-β-flane temperature: 40 ° C Pressure: 6.8 MPa Considering the polyorganosiloxane having an epoxy group, it is preferred to pass! Proper organic solvent, water The mixture is synthesized by hydrolyzing or hydrolyzing and condensing in the presence of a catalyst, and the mixture is preferably a mixture of a decane compound having an epoxy group or a decane compound having an epoxy group and another decane compound. & As the above decane compound having a %oxy group, for example, glycidoxypropyltrimethoxy^, 3-glycidoxypropyldiethoxydecane, and 3g-glycidoxypropylmethyl group can be mentioned. Dimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, diglycidoxypropyl dimethyl methoxy decane, 3-glycidoxypropyl dimethyl ethoxylate Basearane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4.epoxycyclohexyl)ethyltriethoxydecane, and the like. -22-201219934 Examples of the other ceramsite-containing compound include, for example, four gas smelting, tetramethoxy smoldering, tetraethoxy sulphur, tetra-n-propoxy sulphide, tetraisopropoxy sho , tetra-n-butoxy-Xi Xing, tetra- or two-butoxybutanthine, trichlorodecane, trimethoxydecane, triethoxydecane, tri-n-propoxylate, triisopropoxydecane, three-positive Butoxy decane, tri- or two-butoxybutane, fluorotrichlorodecane, fluorotrimethoxydecane, fluorotriethoxy fluorene, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorine Tri-n-butoxy-oxan, fluorotri-n-butoxy decane, methyl trioxane, decyl tridecyloxydecane, methyltriethoxydecane, methyltri-n-propoxy oxime, hydrazine Triisopropoxy decane, decyl tri-n-butoxy decane, decyl tri-n-butyl decyl decane, 2 (trifluoromethyl)ethyl trioxane, tri-sodium methyl) ethyl trimethyl decyl decane , 2_(Trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2(trifluoromethyl)ethyltri Propoxy decane, 2·(trifluoromethyl)ethyltri-n-butoxydecane 2-(difluoromethyl)ethyltri-n-butoxypropane, 2-(perfluoro-n-hexyl)ethyl Chlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyl bis-propoxy oxane, 2-(Perfluoro-n-hexyl)ethyltriisopropoxydecane, 2 U-fluoro-n-hexyl)ethyltri-n-butoxyoxane, 2-(perfluoro-n-hexyl)ethyl-butoxybutane, 2-(perfluoro N-octyl)ethyltrioxane, 2__(Wangfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)棊 棊 tri-n-propoxy decane, 2 · (perfluoro-n-octyl) ethyl triisopropoxy oxa sulphate, 2 _ (perfluoro-n-octyl syringyl di-n-butoxy decane, 2- (perfluoro N-octyl)ethyl tri- or two-butoxybutyrene, residue methyltrichloro- 79, trans-f-group tri-f-oxyl, thiophene-23-201219934 ethyltrimethoxydecane, hydroxy decyl N-propoxy decane, hydroxymethyl triisopropoxy phenol, transmethylmethyl tri-n-butyl Oxyquinone, transmethylmethyltri-n-butoxydecane, 3-(methyl)propenyloxypropyltrioxane 3 (meth)acryloxypropyltrimethoxy decane, 3_(A Acryloxypropyl I ethoxy decane, 3-(methyl) propyl # methoxy propyl tri-n-propoxy decane, 3-(methyl) propylene methoxy propyl triisopropoxy Basear, 3-(indenyl)propenyloxypropyltri-n-butoxydecane, 3-(indenyl)propenyloxypropyltri-n-butoxypropane, 3·mercaptopropyltrioxane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane, 3-mercaptopropane Tri-n-butoxy decane, 3-mercaptopropyl tri-n-butoxy decane, decylmethyltrimethoxy decane, decylmethyltriethoxy decane, vinyl trioxane, vinyl trimethoxy Decane vinyl triethoxy decane, vinyl tri-n-propoxy decyl ethylene triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri- or 2-butoxy decane, allyl tri Gas decane, Propyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl diisopropoxy zephyr, propyl propyl tri-n-butoxy oxylate, rare Propyl tri- or two-butoxy decane, phenyl trioxane 'phenyl trimethoxy decane, phenyl diethoxy sulphur, phenyl tri-n-propoxy sulphur, phenyl triisopropoxy Decane, phenyl tri-n-butoxydecane, phenyl tri-n-butoxy decane, methyl dichlorodecane, decyl dimethoxy decane, decyl diethoxy decane, decyl di-n-propoxy矽, methyl diisopropoxy decane, decyl di-n-butoxy decane 'mercapto di- or two-butoxy decane, dimethyl dioxane, dimethyl dimethoxy decane, dimercapto Ethoxy decane, dimercapto

S -24- 201219934 n-propoxy decane, dimercaptodiisopropoxy decane, dimethyl di-n-butoxy oxysphate, dimethyl di- or di-butoxy alcohol, (methyl) [Μ Gas n-octyl)ethyl]dichlorohydrin, (methyl)[2·(all-gas n-octyl)ethyl]dimethoxycarbazide, (methyl)[2_(perfluoro-n-octyl) Diethoxylate, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl] Diisopropoxydecane, (fluorenyl)(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2_(perfluoro-n-octyl)ethyl]di-n-butoxy Decane, (fluorenyl) (3-mercaptopropyl) dioxane, (methyl) (3-mercaptopropyl) dimethoxy decane, (methyl) (3-mercaptopropyl) diethoxy decane, (indenyl)(3-mercaptopropyl)di-n-propoxydecane, (methyl)(3-mercaptopropyl)diisopropoxydecane, (methyl)(3-mercaptopropyl)di-n-butyl Butoxy decane, (mercapto) (3_mercaptopropyl) di- or two-butoxy sylvestre, (methyl) (ethene) a gas-fired, (meth)(ethinyl)dimethoxy oxime, (meth)(vinyl)-ethoxylated, (meth)(vinyl)di-n-propoxy decane, (fluorenyl) (vinyl) diisopropoxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (vinyl) di- or 2-butoxy decane, divinyl bis Gas decane, divinyl decyl decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl-isopropoxy oxa sulphate, monoethylene di-n-butoxy Base stone kiln, diethylene dibasic butadiene oxime, diphenyl dioxane, diphenyl dimethoxy oxane, diphenyl diethoxy decane, diphenyl di-n-propoxy Base smoldering, diphenyl diisopropoxy oxime, dipyridyl di-n-butoxy oxylate, a stupid one- or two-stage butadiene zephyr, gas dimethyl sulphur, methoxy Methyl oxime, ethoxy dinonyl decane, gas tridecyl decane, m-trimethyl sulfonium, trimethyl decane, decyl tridecyl decane, ethoxy triterpene-25- 20 1219934 Benzane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, secondary butoxy trimethyl decane, tertiary butoxy trimethyl ru Burned, (gas) (vinyl) dimethyl I, (methoxy) (vinyl) decyl decane, (ethoxy) (vinyl) dimethyl decane, (gas) (methyl) two A decane compound having one ruthenium atom such as phenyl decane, (methoxy) (methyl) diphenyl decane or (ethoxy) (methyl) diphenyl decane. The trade name may, for example, be KC_89, KC 89S, X-21-3153, X-21-5841, X_21_5842, χ_21·5843, X-21-5844, X-21-5845, χ_21_5846, χ_21_5847, X-21- 5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-1 70DX, X-22-176B, X-22-176D, X-22-176DX , X-22-176F, X-40-2308, X-40-265 1, 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-41-1 805, X -41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A 'KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR92 1 8, KR9706 (above, Shin-Etsu Chemical Industry Co., Ltd.);

Glass Resin; SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning); FZ3711, FZ3722 (above, Unicar, Japan) ; s -26- 201219934 DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S4 5 , DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-993 1, XMS-5025 (above, Chisso); methyl decanoate MS51, decyl phthalate MS56 (above, Mitsubishi Chemical Corporation) ; Ethyl citrate 28, ethyl decanoate 40, ethyl decanoate 48 (above, Colcoat); GR100, GR650, GR90 8, GR950 (above, Showa Denko Co., Ltd.) special partial condensate. Among these other decane compounds, from the viewpoints of the alignment property and chemical stability of the obtained liquid crystal alignment film, tetradecyloxan, tetraethoxydecane, methyltrimethoxydecane, and decyl are preferable. Ethoxy decane, 3-(meth) propylene methoxy propyl trimethoxy decane, % (methyl) propylene methoxy propyl triethoxy decane, vinyl trimethoxy oxime >, ethylene Triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy fluorene II: 3-mercaptopropyl trimethoxy decane , 3 - mercaptopropyl triethoxy decane, sulfhydryl trimethoxy hydrazine, sulfhydryl methyl triethoxy valence, dimethyl dimethoxy decane or dimethyl diethoxy decane. = Polyorgano having an epoxy group used in the Ming, for the amount of the photo-aligned side chain 'and at the same time suppressing the undesired side-reactor due to the introduction of excess epoxy groups, 铋A·· 1 苟 Its bad oxygen field 乂 good for i〇〇g / Moer ~ I0,000g / Moh, and better Mo ~ ooog / Moer. Therefore, in the synthesis of polyorgano-27-201219934 decane which is 150 g/wt and has a % oxy group, it is preferred to adjust the use ratio of the decane compound having an epoxy group and other oxalate compounds to the obtained ratio. The epoxy equivalent of the polyorganosiloxane is in the above range. Specifically, the total amount of such a decane compound is preferably from 0% by mass to 50% by mass, and more preferably 5%, based on the total of the polyorganococcal oxynitride having an epoxy group and other cerium compounds. Mass%~3〇% by mass. The organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group is, for example, a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, an alcohol compound or the like. Examples of the hydrocarbon compound include indene benzene and xylene; and examples of the ketone include acetophenone, decyl isobutyl ketone, decyl ketone ketone, and ethyl ketone; and as the above ester, For example, the above-mentioned ethers may be exemplified as, for example, n-butyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl acetoacetate, oxime acetate, ethyl lactate, and ethyl lactate; Ethylene glycol dimethyl ether, ethylene glycol: diethyl ether, tetrahydrocyan B, decane, etc.; as the above alcohol, for example, hexanol, decyl-2-pentanol, ethylene glycol monoterpene ether, H is preferably a non-aqueous substance such as ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl, ethylene glycol mono-top, propylene glycol mono-methyl, propylene glycol mono-ethyl, and 2-alcohol mono- (4). These four agents may be used singly or in combination of two or more. The amount of the organic agent used is less than 1 GG parts by mass; the second is preferably 10 parts by mass to 10,000 parts by mass, and more preferably 5 (Shixi oxygen 1, GGG f $ part. Further, the manufacturing has The water usage amount of the polyorgano 0= of the epoxy group is preferably relative to all the money compounds. The ear is ~100 times moles' and more preferably i times moles to 3 moles.

S -28- 201219934 Organic hydroxymorphine, amine, dinitrogen, etc. have such a pyridine, the like, etc., or alkane, the gold test is well-known, the annual ladder is used as the above catalyst, &quot;SJ* For example, an acid, a metal compound, a base, a titanium compound, a wrong compound, and the like are listed. Examples of the alkali metal compound include sodium hydroxide, potassium carbonate, sodium methoxide, potassium decoxide, sodium ethoxide, and potassium ethoxide. The above-mentioned organic base is exemplified by, for example, ethylamine, diethylamine or piperazine. An organic primary amine or a secondary amine such as pyrrolidine or pyrrole; an organic tertiary amine such as triethylenedi-n-propylamine, tri-n-butylamine, pyridine, 4-didecylaminopyridine or heterobicycloundecene; Methyl ammonium hydroxide machine quaternary ammonium salt and the like. Among these organic bases, organic tribasic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridinium di-n-butylamine, and pyridinium are preferred in view of the fact that the reaction is stabilized. Organic quaternary ammonium salt of hydrogen hydroxide. As a catalyst for producing a polyorganosiloxane having an epoxy group, it is a metal compound or an organic base. By using an alkali metal compound as a catalyst, it is preferable that the ring-opening or the like of the epoxy group is not generated and the target polyorganophosphorus can be obtained at a high hydrolysis rate and condensation rate, and thus the production stability is excellent. Further, the present inventor semiconductor alignment composition containing a reaction product of an epoxy group-containing oxalic acid oxide and a specific cinnamic acid derivative synthesized using a compound or an organic base as a catalyst has excellent storage stability. Very beneficial. The reason is as follows, Chemical Reviews, Vol. 95, p. 1409 (1995), which states that it is presumed that a random structure, a structure or a cage structure is formed when an alkali metal or an organic base is used as a catalyst in hydrolysis or condensation reaction, and It is possible to obtain a polyorganooxane having a sterol group content of -29-201219934. And it is less, so it can be suppressed, and it is speculated that the thiol group contains a ratio of ... condensed groups of the thiol groups, and in addition, the organic semiconductor alignment of S. In addition, the other polythene temples described later can also suppress the condensation reaction between the sterol group and the gamma ^ / and his polymer of the sputum sputum, so that the storage stability is excellent. Machine test: Tincture is especially good for organic testing. The amount of organic test is 1 L ^ ^ .. ^ 1 j depending on the type of organic base, temperature, etc. and it can be appropriately = 1 specific use amount of the test, for example, relative to all::; Momo ~ 3 times Mo, and more preferably 0.05 times its ear ~ 1 times Mo. = Hydrolysis of polyorgano-oxo-oxide with epoxy group, the reaction is preferably passed through Other decane compounds required for the oxidization of the oxane are dissolved in an organic solvent / mixed with an organic test and water, and heated by, for example, an oil bath: when the liquid is hydrolyzed or condensed, it is desired to make an oil bath. Heating the warm sound shell is 130. The following, and better "4〇t: ~1〇 (rc, and better:: good 0.5 hours ~ 12 hours, better for heating i hours ~ 8 hours. Plus" ', The mixture may be stirred or the mixture may be refluxed. In the heat, after the reaction is completed, the organic solvent layer which is separated from the reaction liquid is preferably washed with water. When the washing is carried out, the column containing the small amount is used. The ammonium nitrate aqueous solution or the like is washed as in about 0.2% by mass, and the polyester operation becomes It is preferred that this aspect is preferred. The washing is carried out, and the aqueous layer after the washing is made neutral. Then, the organic solvent layer is dried by using an appropriate desiccant such as anhydrous sulfuric acid to a sieve to remove the solvent. The polyorganosiloxane having an epoxy group can be obtained as a target. Thus, -30-201219934 In the present invention, a commercially available product can be used as a polyorganosiloxane having an epoxy group. The product 'for example, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, chisso company), etc. [A] photo-aligned polyorgano-oxygenated compound ' may also contain an epoxy group a part of the hydrolyzate formed by the hydrolysis of the polyorganosiloxane itself, or a part of the hydrolyzed condensate which is hydrolyzed and condensed with each other by the polyorganooxime having an epoxy group. These are the constituent materials of the above-mentioned part. The hydrolyzate or the hydrolyzed condensate ' can be prepared in the same manner as the hydrolysis or condensation conditions of the polyorganosiloxane having an epoxy group. <A] Synthesis of Photoalignment Polyorganooxane> Used in the present invention [A] optical alignment The polyorganooxymethane can be synthesized, for example, by reacting the above polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, preferably in the presence of a catalyst. The amount of the derivative used is relative to the poly 1 Mohr, preferably 〇001 moles ~ 5 moles, and particularly preferably 〇〇5 where 'as a specific cinnamic acid organic decane has an epoxy group of ~10 moles, more preferably 〇〇 In the above-mentioned catalyst, a so-called curing accelerator which reacts with an anion compound and an acid anhydride can be used as the above-mentioned catalyst, and the organic phase test is, for example, the same as the above-mentioned phase S. The cedar\ is the above-mentioned curing accelerator, and examples thereof include a cyclohexyl group: a second amine: a 2,4,6-tris(didecylaminofluorenyl)phenol, a tertiary amine such as diethanolamine; -31 - 201219934 , 2,4-diamino _6_(2'-n-undecylimidazolyl)ethyl_s trimethylimidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylene Kimi sitting, 2-phenyl_4-methylimidazole, 丨_benzyl-2-methylimidazole, phenoxy-2-phenylimidazole, U2-dimethylimidine Saliva, 2 ethyl·enylmethyl, oxazole, di(2-cyanoethyl)_2•nonyl imidazole, 丨_(2-cyanoethyl)_2-n-decyl-alkyl hydrazine 1-(2- Cyanoethyl)-2-phenylimidazole, "(, cyanoethyl) 2 - ethyl-4-mercaptoimidazole, 2 - phenyl _4_ fluorenyl _5_ thiomethyl sulphate, ^ Phenyl-4,5-bis(hydroxymethyl)imidazole, 1(2 cyanoethyl)^•styl 5_bis[(2,-cyanoethoxy)indolyl]imidazole, helium cyanide Base ethyl)·2·^ 十'一炫基味唾录苯苯酯,W2_cyanoethyl)_2_phenylimidazolium stupidate, ^(2-cyanoethyl) _2_Ethyl_4_decyl imidazolium trimellitate, 2,4-diamino _6_[2,-methylimidazolyl-(1,)]ethyl 2,4-diamino _6-[2,-Ethyl-4,-mercaptoimidazolyl-indole,]]ethyl-s•triazine, isocyanurate oxime of 2-methylimidazole, 2-phenylimidazole Isocyanuric brewing adducts 2,4-diamino _6_[2,·methylimidazolyl (1,)]ethyl _s·opened isocyanuric acid adducts and other sodium salicyl compounds; ; organic phosphorus compounds such as phenylphosphine, triphenylphosphine, triphenyl phosphite; f-diphenyl gasification town, four Butyl bromide, methyltriphenyl bromide, ethyl diphenyl bromide, n-butyltriphenyl bromide, tetradamine, scaly, ethyltriphenyl iodide , ethyl triphenyl squaternary acetate, tetrasyl sulphate, hydrazine, hydrazine-diethyl dithiophosphate, tetra-n-butyl phenyl benzoate, tetraphenyl phenyl tetraphenyl borate, Four-grade salt of tetra-n-butyl quaternary tetrafluoroborate, tetra-n-butyl butyl tetraphenyl borate;

S -32- 201219934 l8·—Azabicyclo[5.4,〇]-|-carbene-7, its organic acid salt, etc., diazabicycloalkenyl; zinc octoate, tin octoate, aluminum acetamidine acetate Organometallic compounds such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium tetrachloride, tetra-n-butylammonium chloride, etc.; boron difluoride, triamyl borate a boron compound; a metal halide such as zinc sulfide or vaporized tin; a high melting point dispersion type latent curing accelerator such as an amine monoamine or an amine and an epoxy resin addition product; a microcapsule-type latent curing accelerator coating the surface of the imidazole compound, the organophosphorus compound, the quaternary phosphonium salt, etc.; an amine salt type latent curing accelerator; a Lewis acid salt A latent curing accelerator such as a pyrolysis type thermal cationic polymerization latent curing accelerator. Among these catalysts, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred. The amount of the catalyst to be used is preferably 1 part by mass or less, more preferably 1 part by mass to 100 parts by mass, and particularly preferably 0, based on 100 parts by weight of the polyoxyxanthene having an epoxy group. "Parts by mass to 20 parts by mass. . The reaction temperature is preferably 〇°c to 20CTC, and more preferably 5〇 °C to 15Gt. The reaction time is preferably from G. 1 hour to 5 hours, and more alumina is from 0, 5 hours to 20 hours. -33- 201219934 [A] Photoalignment polyorganic sand oxy-combustion, which can be synthesized in the presence of an organic solvent as needed. The organic solvent may, for example, be a hydrocarbon compound, a test compound, an anthraquinone compound, a ketone compound, a guanamine compound or an alcohol compound. The Φ scale compound, the ester compound, and the ruthenium compound are preferable from the viewpoints of the respective properties of the raw material and the product, the six h, - -η T quinone, and the ease of purification of the product. The solvent is preferably 4, and the concentration of the solid component (the ratio of the mass of the component other than ^ in the reaction solution to the total mass of the solution) is 0% by mass or more and 70% by mass or less and more preferably 5% by mass. The amount of the above amount of % or less is used. The Mw of the [A] photo-aligned polyorgano-oxygenated gas obtained in this manner is not particularly limited, but is preferably 1 〇〇〇 2 υ,000, and more preferably 3,000 2 5, _. When it is in this molecular weight range, good alignment and stability of the liquid crystal alignment film can be ensured. When the Mw is less than the lower limit, there is a case where the electrical characteristics such as the voltage holding ratio of the formed liquid crystal alignment film are lowered. In other respects, when Mw exceeds the above upper limit, it is easy to store the alignment agent at the following temperature. The agglomeration of the edge-forming polymer '^ and the clogging of the ink jet head, the ink ejection amount is unstable, resulting in poor coating. [A] photo-aligned polyorganophospho-oxygen, introduced from a specific cinnamic acid derivative by a slow-acting group of a specific cinnamic acid derivative and a ring-opening gas with an epoxy group-polymerized "oxy(tetra) epoxy group) In the present invention, it is also an extremely suitable method in terms of the introduction rate of the structure derived from the specific cinnamic acid derivative. In the present invention, within the range not impairing the effects of the present invention, It is also possible to use a compound represented by the following formula (4) in place of a part of the above specific cinnamic acid derivative-34-201219934 organism. At this time, the synthesis of the [A] photoalignment polyorganosiloxane compound can be carried out by having an epoxy group. The polyorganosiloxane is reacted with a mixture of a specific cinnamic acid derivative and a compound represented by the following formula (4): R1 R R11_R12 (4) is preferably R1Q in the above formula (4). An alkyl group or alkoxy group having 8 to 2 carbon atoms, or a fluoroalkyl group or a fluoroalkoxy group having 4 to 21 carbon atoms. As R11, a single bond, a hydrazine, a 4-cyclohexylene group or a fluorene group, and a 4-phenyl group are preferable. R12 is preferably a carboxyl group. The compound represented by the above formula (4), for example, a compound represented by the following formula (4-1) to formula (4-3).

(4-3) The compound ' represented by the above formula (4) can contribute to the deactivation of the active site of the photoalignment polyorganosiloxane, thereby improving the stability of the above liquid crystal alignment agent. In the present invention, when the compound represented by the above formula (4) is used together with a specific cinnamic acid derivative, the ratio of use as a total of the specific cinnamic acid street organism and the compound represented by the above formula (4) is relative to The polyorganooxyalkylene has an epoxy group, preferably from 0.001 mol to 1.5 mol, more preferably 〇〇1 mol to i mol, and -35-201219934 is preferably 0.05 mol. The amount of the compound used in the above formula (4) is preferably 50 mol% as a result of the above formula (4), and is represented by the above formula (4). More preferably, it is 25 mol% or less. If %, it may produce a defect that the liquid crystal s exceeds 50 m &lt; [B] other polymer &gt; The above liquid crystal alignment agent can be used as a component. As [B] other poly-l[B] other polymers as suitable imines, ethylenic unsaturation:: Listed by poly-branched acid, poly-branched poly(4) oxygen-fired composition 2: light-aligned When there are other polymers in these groups, the species in each of the clearings are removed from the liquid formed by the upper liquid in the daytime alignment agent, and it is clear that the main a ^ & organic stone eve The oxane is unevenly distributed near its surface layer. Therefore, 诵 & & ^ ^ ^ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The knives are placed on the surface of the alignment film, so that sufficient liquid crystal alignment can be obtained. Therefore, the present invention can reduce the content of the polyorganosiloxane having a high production cost in the above liquid crystal alignment agent, so that the production cost of the above liquid crystal alignment agent can be lowered.

[Polyacrylic acid; I polyglycine can be obtained by reacting a tetrabasic acid dianhydride with a diamine compound to obtain β as a tetracarboxylic dianhydride, and examples thereof include aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic acid. Acid dianhydride, aromatic tetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides may be used singly or in combination of two or more.

S-36-201219934 Examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic acid, dihepatic acid and the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&amp;;,4,5,913-hexanitro-5-(tetrazo-2,5-di-oxy-3-carboyl)-na[1,2-(;]0-pentan-1,3-dioxin Same, 1,3,3&amp;,4,5,91)-hexa-6-indenyl-5-(tetrazol-2,5-di-oxy-3-fluorolanyl)-na[1] , 2-〇]°furan-1,3-dioxin, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5' -di-copper), 5-(2,5-di-branched tetra-mole-3 -0-f-butyl)-3 -mercapto-3 - sulphur-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-two-pin, 4,9-dioxatricyclo[5.3.1.02,6]undec-3,5,8,10-four remuneration, etc. The aromatic tetracarboxylic dianhydride may, for example, be pyromellitic dianhydride, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2010-97 1888. Among these tetracarboxylic dianhydrides, preferred are alicyclic tetracarboxylic dianhydrides, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane. The tetracarboxylic dianhydride is particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The amount of use of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferably 10% based on the total tetracarboxylic dianhydride. Mole% or more, more preferably 20 mol% or more, and particularly preferably only 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane tetracarboxylic acid Anhydride composition. 37-201219934 Examples of the diamine compound include an aliphatic diamine, an alicyclic diamine, a diaminoorganosiloxane, an aromatic diamine, and the like. These diamines may be used singly or in combination of two or more. The aliphatic diamine ' may, for example, be m-xylylenediamine, 1,3-propanediamine, tetradecyldiamine, pentamethylenediamine or hexamethylenediamine. Examples of the alicyclic diamine' include, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 1,3-bis(aminomethyl)cyclohexane. Wait. Examples of the diamine-based organomethoxyalkane include hydrazine, 3 bis(3-aminopropyl)-tetramethylbicyclohexane, and the like, and in addition to this, exemplified by 曰本特愿2009-97188 The diamine described in the number. Examples of the aromatic diamine include p-phenylenediamine, 4,4,-diaminomonophenyl decane, 4,4'-diaminodiphenyl thioether, and I% diaminone, 2 , 2 -dimercapto-4,4'-diaminobiphenyl, 4,4,diamino 2,2,_bis(-fluoroindolyl)biphenyl, 2,7-diaminopurine , 4,4'-diaminodiphenyl ether, 2,2_[4 (4 aminophenyloxy) phenyl] propyl, 9,9 bis (4-aminophenyl) fluorene, 2^2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2•bis(4aminophenyl)hexafluoropropane, 4,4,_(p-stupylene) ) bis(stupylamine), (m-phenyl-isopropylidene) bis(aniline i, bis (heart amine phenoxy) Ben '4,4'-bis(4-aminophenoxy) Benzene, 2,6-diaminol group, 3 diamine group, 2,4-diamine group, 3,6-diamino group, 丫, 3,6_' Amino-based, N-methyl- 3,6-diamine-based saliva, N_ethyl_3,6-diamine-based, N-local _3,6-diamine-based miso, n,n,bis(4.aminophenyl)-linked HH bis(4.aminophenyl)-N,N'dimethylbenzidine, n

S-38- 201219934 bis(4-aminophenyl)piperidin, 35-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4_ Diaminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, Dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy -2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteneoxy_3,5_ Diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid choline alkenyl ester, 3,5-monoaminobenzoic acid lanolinide, 3,6-bis(4-aminophenoxy)cholane, 3,6-bis(4-aminophenoxy)cholane, 4(4,trifluoromethoxybenzyloxy)cyclohexyl-3,5-diaminobenzoate, three Fluoromethylbenzylideneoxy)cyclohexyl-3,5-diaminobenzoic acid vinegar, U1•bis(4-((aminophenyl)indenyl)phenyl)_4_butylcyclohexane , hydrazine, decylaminophenyl)methyl)phenyl)-4-heptylcyclohexene, 1,1-bis(4-((amino)oxy)methyl hydrazine-heptyl Cyclohexene, (aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane,-diamino _ν,ν-dipropylpropylaniline, 4·amine A quinone-amine, a 3-amino-based amine, and a diamine compound represented by the following formula (6)).

It is a linking group of 1 to 3, a bond of *-〇_, : and a diamine group (in the formula (Α-1), 'χΐ is a carbon number-COO- or *-〇c〇_. With a connection. Γ is 〇 or 1. 8 is 〇~2 201219934 The ratio of use of the tetracarboxylic dianhydride and the diamine compound provided for the polyamine synthesis reaction is relative to the amine group contained in the diamine compound. The acid anhydride group of the tetracarboxylic dianhydride is preferably 0.2 equivalent to 2 equivalents, and 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 -20 °. C~150 ° C, and more preferably ~100 t ^ as the reaction time, preferably 0.5 hours to 24 hours, and more preferably 2 hours to 2 hours. As an organic solvent 'as long as it can dissolve the synthesized polylysine There is no particular limitation, and examples thereof include N-fluorenyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, n,n-dimethyldecylamine, n,N-difluorene. Aprotic polar solvents such as imidazolidinone, dimercaptosulfoxide, γ-butyrolactone, tetradecylurea' /, methyl oxime diamine; interstitial, diterpene, phenol, halogenated A phenolic solvent such as a phenol, etc. The amount (a) of the organic solvent used is a total (a + b) of the total amount (b) of the tetrazoic acid and the diamine compound and the amount (a) of the organic solvent used. Preferably, it is 0.1% by mass to 5% by mass, and more preferably 5% by mass to 30% by mass. The polyamido acid solution obtained after the reaction may be directly supplied to the liquid crystal alignment agent, or may be prepared. The poly-proline contained in the reaction solution is separated and supplied to the liquid crystal alignment agent, or the separated poly-aracine can be purified and then supplied to the liquid crystal alignment agent. As a method for separating the poly-branched acid For example, a method of injecting a reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator may be mentioned.

S-40-201219934 A method for purifying poly-aramidic acid, for example, a method in which the separated polyamine is further dissolved in an organic solvent, and then precipitated with a poor solvent, or A method of a step of distilling off an organic solvent or the like under reduced pressure using an evaporator a plurality of times. [Polyimide] The polyienimine ' can be produced by subjecting the proline structure of the polyamic acid to dehydration and ring imidization. The polyimine may be a 70-bulk imine obtained by dehydrating and ring-closing all of the proline structures of the bulk polyamic acid. Alternatively, it may be a part of the structure of the proline which is dehydrated and closed. A partial quinone imide that has an acid structure and a quinone imine structure. Examples of the method for synthesizing the polyimine include (1) a method of heating poly-proline (hereinafter sometimes referred to as "method (i)"), or (Η) dissolving poly-proline in an organic solvent. A dehydrating agent and a dehydration ring-closure catalyst are added to the solution, and a method of dehydration ring-closure reaction using polyglycolic acid, such as a method of heating (hereinafter sometimes referred to as method (U)), as required, is used as the method (1). The reaction temperature is preferably 5 (r (: 〜2 〇〇. 死, and more preferably 60 C to 170 ° C. When the reaction temperature is less than 5 (rc, the dehydration ring closure reaction cannot be sufficiently carried out, and when the reaction temperature When the amount exceeds 2 Torr:, the molecular weight of the obtained polyimine will decrease. The reaction time is preferably from 0.5 to 48 hours, and more preferably from 2 to 2 hours. The polyfluorene obtained in the method (1) The imine can be directly supplied to the preparation of the liquid crystal agent, or the preparation of the liquid preparation can be carried out after separating the polyimine, or the separated polyimine can be refined to the preparation of the liquid crystal alignment agent. 201219934 C as a dehydrating agent in method (ii) For example, an acid needle such as acetic anhydride, an acid anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used can be appropriately selected according to the desired ruthenium imidization ratio, but the proline structure 1 with respect to polyglycine Mohr, preferably 0_01 mol to 20 mol. As the dehydration ring-closing catalyst in the method (ii), for example, pyridine, fluorenyl η-pyridine, dimercaptopyridine, triethylamine, etc. may be mentioned. The amount of the dehydrating agent to be used is preferably 〇·〇1 mol to 10 mol. Further, the more the content of the above dehydrating agent and the dehydration ring-closing agent, the more the imine can be increased. The organic solvent used in the method (ii) may, for example, be an organic solvent similar to the organic solvent exemplified as the solvent used in the synthesis of the polyamic acid. The reaction temperature in the method (Π), It is preferably 〇υ~180&lt;t, and more preferably 1 0 C~1 50 °c. As the reaction time, it is preferably 〇5 hours to 20 hours' and more preferably 丨 hours to 8 hours. The reaction conditions are in the above range and can be sufficiently The dehydration ring-closure reaction is carried out, and the molecular weight of the obtained polyimine can be appropriately determined. In the method (II), a reaction solution containing a polyimine can be obtained. The α-reaction/gluten solution can be directly supplied to the preparation of the liquid crystal alignment agent. Alternatively, after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, the preparation of the liquid helium-aligning agent may be supplied, and the poly-imine may be separated and then: the liquid crystal alignment agent may be adjusted t' or The purified polyimine is purified and then supplied to a liquid crystal alignment agent. As a method for removing the X 钊 and dehydration ring-closing catalyst from the reaction solution, for example, dissolution is exemplified.

S '42- 201219934 Method of agent replacement, etc. The separation method and the purification method of the polyimine are, for example, the same as those exemplified as the separation method and the purification method of the polyaminic acid. [Ethylene Unsaturated Compound Polymer] The ethylenically unsaturated compound polymer of [B] other polymer can be obtained by polymerizing a known ethylenically unsaturated compound by a known method. For example, (a) an epoxy group-containing ethylenically unsaturated compound (hereinafter, sometimes referred to as "(a) unsaturated compound"), (bl) an ethylenically unsaturated carboxylic acid and/or a polymerizable property may be used. A saturated polybasic acid anhydride (hereinafter sometimes referred to as "(bl) unsaturated compound") and a polymerizable unsaturated compound other than the (a) unsaturated compound and the (b 1) unsaturated compound (hereinafter sometimes referred to as " The copolymer of (b2) unsaturated compound ") (hereinafter referred to as "(A 1) copolymer) may be obtained by copolymerization). Examples of the (a) unsaturated compound can be exemplified. For example, glycidyl (mercapto) acrylate, glycidyl a-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate , (mercapto) 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl (meth)acrylate, α- 6,7-epoxyheptyl ethacrylate, and the like. Examples of the (b 1) unsaturated compound include, for example, (meth)propionic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, and fumaric acid. , unsaturated carboxylic acids such as citraconic acid, mesaconic acid, itaconic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, Chuanyou-1,2,3,4-tetrahydrophthalic anhydride, etc. Unsaturated polycarboxylic anhydrides such as shellfish. -43- 201219934 The (b2) unsaturated compound may, for example, be a Z-acid alkyl vinegar such as (meth) propyl 2-ethyl acetoacetate or (meth) acrylic acid 2 _ propyl propyl vinegar. ·) Methyl vinegar (meth) methacrylate, ethyl (meth) acrylate, propyl propyl acrylate, isopropyl sulfonate, propyl acrylate Wife (methyl) propionate isobutyl, (methyl) propyl benzoic acid secondary vinegar, (methodyl, butyl methacrylate, etc. alkyl (meth) acrylate; two (〒 Base) acrylic acid pentane vinegar, (meth)acrylic acid cyclohexaacetic acid 2 _ $ base ring, cool, [Tianhe, soil) hexamethylene (meth) acrylate tricyclo [5.2.1.02 61 eight burning |, base vinegar (the following 'tricyclic ring [5·2·102, ^-8 base is called "bicyclo ring: dilute base", (methyl) propyl (tetra) 2 - dicyclopentanyloxy acetoacetate, (a, Acrylic acid isopropyl vinegar, etc. (?) acrylic acid alicyclic vinegar; &quot; (meth)acrylic acid, (meth)acrylic acid hydrazine, etc. (aryl aryl esters; diethyl primate, The people lacking a horse, Ma Yiyi - Ethyl, Yikang Unsaturated dicarboxylic acid diethyl ester buffer;

Phenylmaleimide, Ν_benzylmaleimide, Ν·cyclohexamidine, N-1/t Τώ ΤΓ I ...-imino3·maleimine Formic acid gt, N-breaking white imine, g ^ 醯 imidate butyrate, N- succinimide, -6 - maleic imine hexanoate, - amber quinone imine-3- Malay yttrium

Acidic acid, N- (9-吖σ定定, 艮A soil,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, a gasified vinyl compound such as cyanated ethylene;

S-44- 201219934 Unsaturated guanamine compounds such as (meth)acrylamide and N,N-dimethyl(meth)acrylamide; styrene, α-methylstyrene, m-methylstyrene, An aromatic vinyl compound such as p-methylstyrene, vinyl toluene or p-methoxystyrene; an anthracene derivative such as hydrazine or 1-methylhydrazine; 1,3-butadiene, isoprene, 2 a conjugated diene compound such as 3-dimercapto-1,3-butadiene, and ethylene, vinylidene chloride, vinyl acetate, and the like. In the (A 1) copolymer, 'the content ratio from the (a) unsaturated structural unit is preferably 10% by mass/〇 to 70% by mass based on the total structural unit. /. More preferably, it is 2% by mass to 6% by mass, and the total content of the structural unit derived from the (b 1) unsaturated compound is preferably 5% by mass to 4% by mass based on the total structural unit. And more preferably 1 〇 mass ° / 〇 ~ 3 〇 mass % ' as a content ratio of the structure derived from the (b2) unsaturated compound, preferably 10 质 / 〇 相对 relative to all structural units 70 mass 0/g, and more preferably 20 mass. /〇~50% by mass. The (A 1 ) copolymer ' can be synthesized by, for example, radical polymerization in the presence of a suitable solvent and a polymerization initiator, and can be exemplified as, for example, and as a poly-proline. The solvent used is the same organic solvent as the organic solvent exemplified. Examples of the polymerization initiator include, for example, 2,2'/azobisisobutyronitrile, 2,2,-azobis-(2,4-di-f-pentylfluorenyl-(4-decyloxy). Oxide such as _2,4_dimethylvaleronitrile; -45- 201219934 Benzene f-based peroxide peroxidized pivalate, 〗 〖, j, _ machine peroxide; laurel-based peroxidation Hydrogen peroxide, such as (secondary butyl peroxidation), cyclobutyl butyl hexane, etc.; oxidation of the agent by these peroxides and reducing agents, and the formation of these collective initiators, π s use. Used alone or in combination with two or more [polyorganosiloxanes without photo-alignment groups]: liquid crystal alignment agent, in addition to (eight) photo-aligned polyorganic ~ ' [B] Polyorganosiloxanes of other polymer w groups. As A n , , , with a prioritizing group ^, as a polyanthracene having no photo-alignment group, it is preferable to have the following formula: The organic hydrazine, the hydrolyzate thereof, and the at least one type of condensate selected from the group consisting of::=: I I 氺 A § § § The above liquid crystal alignment agent contains the right π Directional group @ polyorganooxane Nippon &quot; Polyorgano-oxygen oxygenation pits with non-tropic groups, if there is no photo-dispensing oxirane independently, - 卩,, and [Α The condensate of the photo-aligned poly-converging polyorganisms - and ^ can also be used as (4) light-matching ( 2 (5) &quot;Si-〇-V2 over the formula (5), Χ2 is Μ λα a * Atomic atom, a carbon atom, a 2 〇 alkyl group, an alkoxy group having a carbon number of 1 to β 〜 or a carbon atom number of 20. γ2 is a hydroxyl group or a carbon The alkoxy group having a number of 1 to 10 in the range of 1 to 10 0 - 201219934 The alkyl group having 1 to 20 carbon atoms may, for example, be a linear or branched methyl group such as a linear heptyl group or an octyl' fluorene group. Butyl, pentyl, hexyl, .+, fluorenyl, lauryl, dodecyl, decyl, tetradecyl, pot, butyl hexadecyl, hexadecyl, seventeen An alkyl group, a pyridyl group, a decyl group, a decyl group, etc. 10. The alkoxy group having a carbon number of 6 may, for example, be methoxyisopropoxy, n-butoxy or isobutoxy. Ethoxy, n-propoxy, etc. 2 Examples of the aryl group of hydrazine include benzene as a 6-membered carbon group, a naphthyl group, etc. Polyorganosiloxane having no photo-alignment group, preferably in a suitable organic solvent, in water and a catalyst The storage group 2 is selected from the group consisting of pitoxy money compounds and chemylated m compounds, and at least one decane compound (hereinafter sometimes referred to as "raw material decane compound") is hydrolyzed or hydrolyzed and condensed to synthesize. The starting decane compound may, for example, be tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, dipropoxy decane, tetra-n-butoxy decane, tetra- or 2-butoxy decane, and four or more. Butoxy decane, tetrachloro decane, etc.; methyl dimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy Base decane, methyl di-2-butoxy decane, methyl tris-butoxy decane, methyl phenoxy decane, methyl trichloro decane, ethyl trimethoxy decane, ethyl diethyl hydrazino Decane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyl n-Butoxydecane, ethyl tri- or 2-butoxybutane-47- 201219934 alkane, ethyl tri-tert-butoxy decane, ethyl tri-s-decane, phenyl tri-methoxy decane, phenyl triethoxy Base decane, phenyltrichloromethane, etc.; monomethyldimethoxy decane, dimethyldiethoxy decane, dichlorodichlorodecane, etc.; trimethyl methoxy decane, trimethyl ethoxy decane , trimethoprim &amp; decane and so on. Rustic among them, preferably tetramethoxy decane, tetraethoxy decane, methyl methacrylate: methoxy decane, methyl triethoxy decane, phenyl trioxy decane: phenyl triethoxy decane, Dimethyldimethoxydecane, didecyldiethoxypropane, trimethylmethoxydecane or trimethylethoxydecane. Examples of the organic solvent which can be used arbitrarily when the synthesis does not have the "orthogonal group" polyorganic compound include, for example, an alcohol diketone compound, a brewing amine compound, a human &amp; upper sputum or other aprotic servant. Things. They may be used singly or in combination of two or more. As a hydrazine used in the synthesis of a polyorganooxy oxyalkylene which does not have 弁w % with an u曰4 prior-aligning group, the total amount of atoms is 1 mole relative to the raw material, Μ # &amp; Λ #卤,斗Preferably, 0. 01 moles to 100 moles, 0.1 moles to 30 moles, more preferably soar and especially good for 1 mole to 1.5 moles. As a catalyst for synthesizing polyorganooxazane-p which does not have a light g? nine-orthogonal group, it can be used as a catalyst, an inorganic acid, an organic base, an alkali organic ruthenium metal compound, Earth-care metal servant, 氦 4. They can be used separately as the amount of catalyst used. The mass part is preferably 〇·_quality t 胄 in the raw material of our compound just in parts by mass. Know ~1〇 part by mass, and better (10)i

S -48- 201219934 In addition to the addition of a photo-alignment group, the addition of 121 971 organic decane may be intermittently or continuously added as a substance ###杜The decane compound of the starting material may be dissolved in a solution of the organic solvent in advance. The catalyst is dissolved in a solution of an organic solvent, and is also added to the water. ^ Solution or dispersion in the reaction to be added as a synthetic temple without a photo-alignment group, the value of the dish is better than 10t: ~10 (rc, and more Preferably, the reaction time is preferably 〇. 5 hours to 2 4 t ndt hours to 8 hours. 24 hours 'and more preferably when the above liquid crystal alignment agent contains [Β] other polymers, other polymers The content ratio 'based on [Β] other polymers is: same, but relative to [Α] photo-aligned polyorganosiloxane, 1〇〇 is less than 10,000 parts by mass. The substance 'more than <[c] Compound of the ester structure&gt; The liquid crystal alignment agent contains a combination of [c] ester-containing structure to form a liquid crystal alignment enthalpy excellent in heat resistance and the like. [C] A compound having a structure of i, is in a molecule, and two are in L. a compound having at least one structure consisting of an acetal structure of a carboxylic acid, a ketal structure of a carboxylic acid, a tertiary alkyl vinegar structure, and a tertiary carboxylic acid. [C] The character 4 is two or more of the same type of structure in two or more of these structures, and may have two or more Φ 丁 仏 仏 — 构 构 构 构 。 。 。 。 。 。 。 。 。 。 。 。 。 。 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为LIST -49- 201219934 R13 I c〇- II I —CH— •0—R14 (C-1) 0 C — 〇—II ΛΗ1 &gt;CH2)n1 (C-2) 0 0 ～20 alkane The carbon or the carbon is independently an alicyclic group having a number of carbon atoms of ό~10, a cyclone group of a carbon atom, a carbon group, or a carbon® precursor, Ύ' ^ (C-2) In the middle, the rabbit is an aralkyl group of 10. Nl is an integer of 2 to 1 )). In the R&quot; of the above formula (C-1), an alkyl group, preferably A, is used as A 1 "a group having an atomic number of 1 to 20, preferably a ring having a ring of 3 10 months. The ring type is preferably... The aromatic fluorene having a carbon number of 6 to 10 is preferably a base group. As the aryl group of π: , it is preferred that the carbon number of R is H. The burning: the number of scorpions is 1~6 alkyl, for the smashing of the original 丨f苟 slave atomic number is 3~1 俾 俾 group, preferably carbon; 1 曰衣式厌原An alicyclic group of 6 to 10 千, an aryl group having a number of 6 to 10, preferably an aryl group of ~1 Å, preferably ... 2 is an inverse atomic number of 7

ΛΛ 冯 , von benzyl or 2-phenylethyl. Nl, preferably 3 or 4 in the formula (C). (C-2) As a group represented by the above formula (C-1), 1), for example, methoxyethoxy Alkyl, h ethoxyethoxymethyl, b = yl, i-n-butoxyethoxy group, b isobutoxy B: =, bis-butoxy ethoxy Base group... three-stage butoxide

Carbonyl, 1-cyclohexyloxy, 7 ϋ II ethoxycarbonyl, 1 -norbornyloxyethoxycarbonyl, 1-phenoxyethoxycarbonyl, (cyclohexyl)(methoxy)methyl Alkyl, (cyclohexyl) (cyclohexyloxy)methoxy", (cyclohexyl) (Benzene 50 201219934 rolling) methoxycarbonyl, (cyclohexyl) (benzyloxy) anthracene Mesquite K methoxy)methoxymethyl, (phenyl) (cyclohexyl, (phenyl), (phenylphenylphenoxy)oxyl group, (phenyl group, (group base armor) Oxy) methoxy group, (nodal group) (cyclo = methoxy methoxycarbonyl, (benzyl) (phenoxy) methoxy;:) methoxycarbonyl, etc. (decyloxy) tetrahydrogen = represents a group, and examples thereof include a 2-oxyl group, a 2-tetramethylpyranyloxycarbonyl group, etc. an oxy group:=diethoxyethoxy group , n-propoxyethyloxy group, 2-tetrachloro-folyloxytetramine 1^pyranyloxycarbonyl. The following group has the group represented by the formula (C-5). -C —〇—〇_li O R16 —Ο—R17 (0-3) -c—0 II o (C-4) R18 -C^CH. 0 R19 I o

• C — 〇 ~~— II 0 CH (C-5) and Rl7&quot; Each R is a burnt group having 1 to 12 carbon atoms. The site having a ruthine number of 3 to 20 is an alkyl group having 1 to U carbon atoms, a carbon atom having a carbon atom group, and an alicyclic group having 2 carbon atoms. The aryl group is an aralkyl group of 7 to 2 Å. -5 1- 201219934 In the formula (C-4), r18 is an integer of Shishan 28. An alkyl group having a number of 1 to 12 is used. N2 is a 12-base base. N3 is 2 (C-5), and Rl9 is an integer of carbon §). In the above formula (c-3), 1 is preferably a methyl group, and as the RU RI5, the alkane having 1 to 12 carbon atoms is preferably a methyl group, and the carbon atom as a carbon atom is 1~. The alkyl group of 12, preferably a cyclohexyl group, is an alicyclic group having A ^ κ and a number of 3 to 2 Å, and is an aryl group having a carbon number of 4 and a number of 6 to 20, preferably stupid. R" has a carbon number of 7 to 22 Å, preferably a benzyl group, and is an alkyl group of ό. The alkyl group as Α, preferably has a carbon number of 1 and is preferably an atomic number. 6 to 丨.: 〜 alicyclic group, 6 to 20 aryl, preferably awkward. As the number of carbon atoms is aralkyl, preferably the beauty or ^ as the number of slave atoms is The number of carbon atoms of ruthenium of 7 to 20 is two: a base ethyl group. Preferably, it is 3 or 4 in the formula (c-4), and is a m &amp; base, preferably a methyl group. As a core, it is a formula (C). The alkyl group of ρ丨^ mountain in 5) is preferably a methyl group and has a reverse atomic number of 1 to 12 as a group represented by the above formula (C3::n3, preferably 3 or 4. 3). Methyl-1-methoxyethoxy^ is exemplified by, for example, 1-yl, 1-methyl+n-butyldi-W methyl-1_n-propoxy B Oxidyloxy group, "methyloxymethyl", methyl + isobutoxy tertiary butoxyethoxyoxy, benzyl, methylcarbonyl, 1-methyl-1 - Tablet: f-based-1*hexyloxyethoxyoxyethoxymethyl, a... phenylethoxy ethoxydiyl wide oxyethoxy group, &quot; Soil 1-% hexyl-1_methoxyethoxycarbonyl

S-52- 201219934 yl, i-cyclohexyl-fluorenylcyclohexyloxyethoxycarbonyl, indolecyclohexyl-indole-phenoxyethoxycarbonyl, hydrazine-phenyl-hydrazine-methoxyethoxy Carbonyl, 丨-phenyl-1-ethoxyethoxycarbonyl, fluorenyl-phenylphenoxyethoxycarbonyl, phenyl-1-butoxyethoxycarbonyl, benzyl hydrazine Ethyloxycarbonyl, 1-pyryl-1-cyclohexyloxyethoxycarbonyl, benzyl-nonyloxyethoxycarbonyl, fluorenyl-benzyl-1-ethoxyethoxycarbonyl, etc. . The group represented by the above formula (C-4) may, for example, be a 2-(2-methyltetrahydrofuranyl)oxycarbonyl group or a 2-(2-methyltetrahydroindenyl)oxycarbonyl group. The group represented by the above formula (C·5) may, for example, be a 1-methoxyl-pentyloxycarbonyl group or a methoxycyclohexyloxycarbonyl group. Among them, preferred are 1-indenyl-indole-methoxyoxycarbonyl group and methyl-1-cyclohexyloxyethoxycarbonyl group. The group represented by the following formula (c-6) is exemplified as the group having the 丨-alkylcycloalkyl ester structure of the above carboxylic acid. R2〇

(C-6) (an integer of 1 to 8 in the formula (C-6)). R is an alkyl group having 1 to 12 carbon atoms. N4 is 1 : 乍 is an alkylene having 1 to 12 carbon atoms of R 2 ° in the above formula (C·6), and is preferably an alkyl group having 1 to 10 carbon atoms. Examples of the group represented by the above-mentioned '(6) include, for example, 1-methylphosphonoxycarbonyl, 丨@.1methyl-tert-butyloxycarbonyl, 1-methylcyclopentane* , Keqilu 3 - oxycarbonyl, 1-methylcyclodecyloxycarbonyl, -53- 201219934 1-ethylcyclobutoxycarbonyl, 1-ethylcyclopentyloxycarbonyl, 1- Ethylcyclohexyloxycarbonyl, 1-ethylcyclodecyloxycarbonyl, 1-(iso)propylcyclopropoxycarbonyl, 1-(iso)propylcyclobutoxycarbonyl, 1-(iso)propyl Base oxime oxycarbonyl, 1-(iso)butylcyclobutoxycarbonyl, 1-(iso)butylcyclopentyloxycarbonyl, 1-(iso)butylcyclohexyloxycarbonyl, 1- (iso) Butylcycloheptyloxycarbonyl, 1-(iso)butylcyclodecyloxycarbonyl, 1-(iso)pentylcycloheptyloxycarbonyl, 1-(iso)pentylcyclooctyloxycarbonyl, 1- (iso)hexylcyclopropoxycarbonyl, 1-(iso)hexylcyclobutoxycarbonyl, 1-(iso)hexylcyclopentyloxycarbonyl, 1-(iso)hexylcyclohexyloxycarbonyl, 1-(iso) Hexylcyclodecyloxycarbonyl, 1-(iso)hexylcyclodecyloxycarbonyl, 1-(iso)octylcyclopropoxycarbonyl, 1- ( Isooctylcyclobutoxycarbonyl, 1-(iso)octylcyclopentyloxycarbonyl, 1-(iso)octylcyclohexyloxycarbonyl, 1-(iso)octylcycloheptyloxycarbonyl, 1 -(iso)octylcyclooctyloxycarbonyl, 1-(iso)octylcyclodecyloxycarbonyl, and the like. The group containing the tertiary butyl ester structure of the above carboxylic acid is a tertiary butoxycarbonyl group. The compound of the [C] ester-containing structure in the present invention is preferably a compound represented by the following formula (C).

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

S-54-201219934 The R in the above formula (c), when 11 is 2, the alkanediyl group having 1 to 12 carbon atoms, 丨2_ to exemplify a single bond, M-phenylene group, 2, 6-Cai Ji, 5_Sodium Thio-... Shen ^ ^ Stupid base, scale thio-1,3-phenylene and so on. Soil 5·tetrabutyl When η is 3, examples of the above R include a group, a benzene_1, a 3,5-triyl group and the like. Indicated 0 'c2h4. 0 input

The human 〆c2h4-Nc2h4- is preferably a linear chain as the above-mentioned alkanediyl group. The conventional method of [c] chlorinated structure represented by the above formula (C), which has been subjected to organic chemistry, can be synthesized by a conventional method or can be synthesized by appropriately combining the specifications. For example, the compound of the above formula (c) (except that Rl3 is a group represented by the stupid j), except for the case of the base group, can be passed through the phosphoric acid catalyst. In the presence of ό, 加, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R The above formula ((,, (c-1) is synonymous. R13. is a group obtained by removing a deuterium atom of a gas from a carbon of R丨3 in the above formula (CM)). The compound of the formula (C) wherein τ β ., 1 and Τ are a group represented by the above formula (C-2) can be added to the compound R in the presence of a light y* soil # f phenylene pico-acid catalyst. -(C〇〇H) u is added to i &lt;, +-i 九 (which makes R and η each synonymous with the above formula (C)) and is synthesized by a compound represented by the following formula. 55- 201219934 ο- ~(CH2) η1-1 (wherein η 1 and μ ^ ' are synonymous with the formula (C-2)). As the above-mentioned liquid crystal .θ electric charge agent, [C] contains a 鲳 of 1 ’ as long as it is a test tiger. The heat resistance and the like required for the ~f of the compound are not particularly limited, but the amount of θ and the amount of the ruthenium is ~ gas phase for [A] photoalignment 100 parts by mass '[C] age-old organic oxane &amp; The compound of the structure is estimated to be &amp; 5 parts by mass, more preferably, R is preferably 〇·ι mass parts to 1 part by mass to 20 parts by mass ^ parts by weight to 10 parts by mass. 'Best quality is 2 quality &lt;other optional components&gt; The liquid crystal alignment is also 丨1 ~ 'In addition to the above components, γ γ which impairs the effect of the present invention can also be contained in the ? A curing agent, a solid curing accelerator, a molecular curing catalyst, at least one epoxy group in ten, sometimes referred to as a "ring gas compound", and a functional stone gas burning material Surfactant, photo-sensitization, etc. Hereinafter, the other: ^: table will be described in detail. Components [curing agent, curing catalyst and curing accelerator] In order to make [Α] photo-aligned polyorganosiloxane The cross-linking reaction is strong, and the liquid crystal alignment agent t may contain a curing agent and a **ti /* agent. In addition, in order to promote the curing reaction controlled by the curing agent, the core may contain the above-mentioned curing in the liquid crystal alignment agent. Promoter. 1 As the curing agent, a solid servant which is used for curing and which is generally used as κβ, and a curable composition which is usually used for a curable compound having an epoxy group or a compound containing a G epoxy group, may be used. It can be cited as a female ~ An amine 'polycarboxylic acid anhydride, a polycarboxylic acid, etc.>> U.S. Patent No. 201219934, as a polycarboxylic acid anhydride, may, for example, cyclohexane tricarboxylic anhydride and other polycarboxylic acid anhydrides. Examples of the cyclohexane tricarboxylic anhydride include cyclohexane. Alkane-1,2,4-tricarboxylic acid, cyclohexane-indole, 3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4- Tricarboxylic acid _3,4-anhydride, cyclohexane_1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane_1,2,3-tricarboxylic acid _2,3·anhydride, etc. Examples of the other polycarboxylic acid anhydrides include, for example, 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecenylsuccinic acid needle, acid station needle, maleic acid needle, and adjacent The mono-anhydride, the bismuth trimellitate, the compound represented by the following formula (6), and the tetracarboxylic dianhydride which is generally used in the synthesis of poly-proline are also listed as α_品品Early reaction products of alicyclic compounds having a common roll double bond, such as alkene and belleth, and Diels Alder of a maleic acid needle, and their hydrides and the like.

(In the formula (6), ρ is an integer of 1 to 20). The curing catalyst may, for example, be a diazonium salt, an iodonium salt, a salty salt, an aluminum alkoxide or an aluminum chelate compound. Commercially available products include AMERICURE (BF4) (adiabatic rust salt from ACC), ULTRASET (BF4, PF6) (diazo rust salt from Asahi Kasei Kogyo Co., Ltd.), and UVE 糸 column (filled iron salt from GE). , Photoinitiator 2074 ((C6F6)4B) (Rhone Poulenc company's moth salt), CYRACURE UVI-6974, CYRACURE UVI-6990 (above is UCC company's strontium salt), UVI-508, UVI-509 (above GE)铳 salt), OPTOMER SP-150, OPTOMER SP-170 (Asahi-57-201219934 industrial company's strontium salt), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (above It is a salt of Sanxin Chemical Industry Co., Ltd., IRUGACURE 261 (a metallocene compound of Ciba Geigy Co., Ltd.), Alumichelate A (W) (Chaiyan Fine Chemical Co., Ltd.), and the like. These curing catalysts may be used alone or in a mixture of two or more. The use ratio of the curing catalyst is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the [A] photo-aligned polyorganosiloxane. When the liquid crystal alignment agent contains a curing catalyst, the content ratio thereof is preferably 30% based on the total of the above [A] photo-aligned polyorganosiloxane and any other polymer used [B]. It is below the mass part, and more preferably 20 parts by mass or less. Among these curing catalysts, a phosphonium salt and a ruthenium chelate compound are preferable, and among the phosphonium salts, a compound containing an antimony hexafluoride or a phosphorus hexafluoride or the like as an anion species is more preferable. Examples of the onium salt include a ruthenium hexafluoride salt of methyl studyl fluorenyl hydrazine, a ruthenium hexafluoride salt of ethyl phenyl fluorenyl fluorene, and a hexafluorophosphoric acid of methyl phenyl dimethyl hydrazine. Salt and so on. These onium salts may be used alone or in a mixture of two or more. As a commercial product of these onium salts, San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (above, Sanshin Chemical Industry Co., Ltd.), UVI-6990, UVI-6992, UVI can be cited. -6974 (above is Union Carbide), ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170, ADEKAOPTON CP-66, ADEKA OPTON CP-77 (above is Solectron Chemical Industries, Inc.), IRGACURE 261 (Ciba Geigy). S-58-201219934 Examples of the curing accelerator include imidazole compounds; quaternary compound; quaternary amine compound; diazabicyclo[5.4.0]undecene-7 or its organic acid salt Heterobicycloalkenes; organometallic compounds such as zinc octoate, tin octoate, and aluminum acetonitrile acetate complex; boron compounds such as boron trifluoride and tris-borate; metals such as zinc chloride and vaporized tin a high-melting-point-dispersion latent curing accelerator such as a diamine diamine, an amine-forming accelerator such as an amine and an epoxy resin; and a microcapsule coated with a polymer such as a quaternary salt or the like Plastic latent curing accelerator; pyrolysis type thermal cationic polymerization type latent curing accelerator such as B-lubric acid salt or blister acid. The ratio of use as the si promoter is relative to [a] photoalignment organic: oxygen burnt. . The parts by mass are preferably 10 parts by mass or less. When the above liquid crystal alignment agent contains a curing agent 4 Α ^ ^ curing catalyst, it is said that Z and 3 are proportional, and R1J is optional for use in the above [A] photoalignment, and Yang et al. The total amount of the other polymers of "[B] is 1 〇〇 or less by mass, and more preferably 1 part by mass or less. 10 - 59 - 201219934 [Epoxy compound] In order to further improve the adhesion of the formed liquid crystal alignment film to the surface of the substrate, an epoxy compound may be contained in the upper iiR liquid a: 4B daily alignment agent. Examples of the epoxidized human &amp; b etiquette include, for example, ethylene glycol diglycolate, polyethylene glycol dioxime, a refractory glyceryl ether, propylene glycol diglycidyl scale, triol monoglycidyl ether, Polypropylene glycol diglycidyl ether, neopentyl glycol hydrazine, from ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2 2 -β A, — 1 &gt; Neopentyl glycol diglycidyl ether, 1,3 5 6 _ diglycidyl-2 4 p - hexane diol, n, n, n, n, -tetraglycidyl _ _ - A * Month*| » —,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Methane, glycidyl-benzylamine, N,N-diglycidyl

Base cyclohexane and the like. The content ratio of 丞T as the % oxygen compound is preferably 40 皙 in the 丨, 丁 2, relative to the total amount of the photo-aligned oxoxane and the optionally used [Β] other polymer. The following is more than 0.1 mass parts of ~30 ^ Ύ1. In addition, when the above liquid crystal alignment agent contains an epoxy compound, the horse cross-links anti-accumulation k ^ and can also be used together. A base catalyst such as 1-benzyl-2-methylthiazolidine. T-based taste [functional decane compound] For the adhesion of the liquid crystal alignment film formed by k, the above-mentioned functional decane compound is used for the adhesion of the surface. As a compound of g 匕 匕 石 石 , ,, 可以 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 , , , 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例 举例Money, 2 r...Acrylaminopropyl 2-7-propylpropyltriethoxy-Xi Xing,Ν·(2-Amino B

S-60- 201219934 yl)-3-aminopropyltrimethoxydecane, ^(2-aminoethyl)_3-aminopropylmethyldimethoxydecane, 3- ureidopropane Tris-methoxyxanthine, 3-bromopropylpropyltriethoxydecane, N-ethoxycarbonyl-3-ylaminopropyltrimethoxysulfate, N-ethoxycarbonyl-3-amino Propyltriethoxy oxalate, N-triethoxycarbamidopropyltriethylenetriamine, &amp;trimethoxy sulfonylpropyldiethylenetriamine, 1 〇trioxane Basic school base - I〆,? · Triazadecane, 1〇-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxymethoxymethylalkyl-3,6-diazaindole Acid ester, 9-triethoxycarbamido_3,6-diazaindolyl acetate, N_benzyl-3-I-propylpropylmethoxy oxime, N_group _3_ Aminopropyltriethoxysulfonium, phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxylate (oxyethylene)- 3-aminopropyltrimethoxyoxime, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, 3-glycidyl, from oxypropyltrimethoxydecane, 2_(3,4 epoxycyclohexyl)ethyltri:oxydecane, tetradecanoic acid, and decane compound having an amine group can also be exemplified by 曰本特开昭03-29 The ratio of the reactants of the four or more _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The total amount of [Β] other polymers used for decane and hydrazine is preferably 〇0 parts, preferably 5 parts or less. The following is known, and more preferably 20 mass [surfactant] as a surface additive, 7 t agent, anionic oxime, and W, for example, nonionic surface activity* 'tongue agent, cationic surface activity Agent, amphoteric surface -6 1- 201219934 Active agent, polyoxetane surfactant, polyoxyalkylene surfactant, fluorosurfactant, and the like. The use ratio of the surfactant is preferably i 〇 by mass or less, and more preferably 1 part by mass or less, based on 100 parts by mass of the total of the liquid crystal alignment agent. [Photosensitizer] The photosensitizer which may be contained in the liquid crystal alignment agent contains a carboxyl group, a hydroxyl group, -SH, _NC0, and _NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) And at least one group selected from the group consisting of _CH = CHh〇s〇2Cl and a compound of a photosensitizing structure. By reacting the polyorganosiloxane having an epoxy group with a mixture of a specific cinnamic acid derivative and a photosensitizer, the [A] photoalignable polyorganosiloxane contained in the liquid crystal alignment agent can be used. It has a photosensitive structure (cinnamic acid structure) derived from a specific cinnamic acid derivative and a photosensitizing structure derived from a photosensitizer. The light sensitizing structure has a function of being excited by light irradiation and imparting the excitation energy to the photosensitive agency in the polymer. The excitation state can be a single weight to the center of gravity or a triplet state. However, in view of long life and effective energy transfer, the surface weight is preferably a triplet state. Preferably, the light absorbed by the light sensitizing structure is ultraviolet or visible light having a π length of 150 nm to 600 nm. Wavelengths 铕 The light at the lower limit of the above is not available in the usual optical system, so this does not apply to the optical alignment method. On the other hand, 夯At θ '&quot; having a wavelength longer than the above upper limit is small, and it is difficult to induce the excitation state of the above-described photosensitizing structure. As such a light sensitizing structure, it is possible to introduce, for example, a phenelzine structure, a benzophenone structure, a fluorene structure, and a kinky structure. Fu, ° card sal structure,

-62- 201219934 A nitroaryl structure, a first structure, a naphthalene structure, an anthracene structure, an acridine structure, an anthracene structure, etc., which may be used singly or in combination of two or more. These photosensitizing structures refer to acetophenone, benzophenone, brewing, biphenyl, and leaf, respectively. A structure formed by a group obtained by removing 1, 4 or more hydrogen atoms from a benzene or a dibasic benzene, naphthalene, anthracene, an anthracene, a quinone or a hydrazine. Here, the acetophenone structure, the carbazole structure and the fluorene structure are each preferably formed by removing 1 to 4 of the hydrogen atoms of the benzene ring of acetophenone, carbazole or anthracene. structure. Among these photosensitizing structures, at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthracene structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure is selected. One, and particularly preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, and a nitroaryl structure. The light sensitizer is preferably a compound having a carboxyl group and a photosensitizing structure. Examples of the compound which is more preferably a compound represented by the following formulas (H-1) to (H-10). -6 3- 201219934

I 八τ , q The photo-aligned polyorganosiloxane used in the present invention is passed through a TU which is preferably stored in the catalyst, which can be used in the following, and preferably in addition to the above-mentioned epoxy "poly organic 11" In the case of the special agent, the compound is synthesized by reacting with a photo-sensitizer. When the acid is derivatized, the polyorganosiloxane having an epoxy group is used as a specific cinnamic acid derivative. J i Wudou, more Wei Moe ~ 10 Moar, better for 〇01 (10) 〇·〇〇ι ^. Bucket, and Tejia Mo Er ~ 2 Mo. As the amount of light sensitizer, relative The oxime atom of the polyorganooxy oxane having an oxy group is preferably a &quot;cafe: ear ~ '5 mo, more preferably 〇〇〇〇 5 moor ~ 〇 2 mo and especially good It is 0_001 mol to 01 mol. -64- 201219934 &lt;Preparation of liquid crystal alignment agent 5 The above liquid crystal alignment agent, polyorganosiloxane, as described above, for example, contains [A] photoalignment optional component, ^ It is preferable that it can contain a suitable component and other liquid composition as needed, and can be prepared as a solution in which the components are dissolved in an organic solvent. As the organic solvent, the alkane and the arbitrarily used compound are dissolved [Α] photo-aligned polyorganosiloxanes. As the above-mentioned liquid θ邴a, one of the "reactive liquid hydrazine alignment agents" is preferred. The organic solvent to be used is different depending on the type of other polymer which is contained in any of the available organic extracts. 3. The above liquid crystal alignment agent contains ^ TR1 # ^ ] pre-aligned polyorganoindole The preferred organic solvent in the case of oxygen is exemplified as an organic solvent which is used as a solvent in the synthesis of polylysine and which is a bovine organic solvent. These organic/gluten can be used alone or in combination. The above group 8 can be used for preparing the above liquid crystal alignment agent. ^ m 1 main is a gluten agent, and one or more of the above organic solvents can be combined according to the presence or absence of other polymers and the J-class of the polymer. The use of these _ 'chore. These solvents in the following preferred solid concentration, do not + I pray out the components contained in the liquid crystal alignment agent, and can make the main ancestor of the liquid crystal alignment agent ... Surface tension is The range of 25 mN/m to 40 mN/m. The solid content concentration of the above liquid crystal alignment agent is also a ratio of the total mass of the liquid crystal alignment agent in the mass of all the components other than the solvent in the liquid crystal alignment agent, and the viscosity is considered. And volatility, etc. are still buried # &gt; from U 崎, and #父佳 is 1% by mass to 10% by mass. When the solid content concentration is less than i% by mass, there is a liquid crystal formed by the above liquid crystal alignment agent The film thickness of the alignment film is too small to obtain a good 液晶, σ ν J 4 of the liquid crystal alignment film. The other side is -65-201219934, when the solid content concentration exceeds 10% by mass, the coating film thickness is too large. It is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased to cause insufficient coating properties. The preferred range of solid content concentration 'is different depending on the method used to coat the liquid crystal alignment agent on the substrate. For example, the range of the solid content concentration when the spin coating method is used is preferably 1.5% by mass to 4.5% by mass. When the printing method is employed, the solid content concentration is preferably in the range of 3% by mass to 9% by mass, and thus the solution viscosity is in the range of 12 mPa. &lt; 5 to a s 50 mPa_s. When the ink jet method is employed, the solid content concentration is preferably 1 mass%. /. The range, and more preferably the range of 3 mass% to 4 mass%, and thus the viscosity of the solution is Μ&quot;~15 must·3 range 'better than 4mPa.s~10mPa_s' circumference' and especially good The range of 5mPa.s to 9mPa*s. It is preferably a cholesteric liquid crystal display having a temperature of 2 〇〇 ° C, and more preferably 〜4 (rc. &lt; cholesteric liquid crystal display manufacturing method > month), which can be manufactured, for example, as a liquid crystal alignment agent The present invention relates to a method for manufacturing a cholesteric liquid crystal display having a monthly (1) coating on at least one of the plurality of regions in which the substrate is divided by a radiation sensitive linear s ^ ^ • 埤Night day alignment agent, step of forming a coating film,

(Z) A step of forming a liquid crystal alignment film by irradiating a coating film with L and a coating film. (3) a step of filling aa in each divided region of the liquid crystal alignment film of the bovine-shaped liquid crystal alignment film. In the following, the cholesterol type and the $7F stealing 1 system in Fig. 1 are ^ ^

The Ik method is described in detail as an example. -66- 201219934 Prior to the step (1), patterned transparent electrodes 6a and 6b are formed on the surfaces (opposing faces) of the two substrates 2a and 2b. The method of forming the transparent electrode is, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film having no pattern, a method of using a photomask having a desired pattern when forming a transparent conductive film, or the like. Then, a partition wall 5 is formed on the opposite surface side of the substrate 2b as a method of forming the partition wall 5, and a method using a photo-resistance agent, for example, may be mentioned. That is, after the photoresist material is applied on the entire surface of the opposite surface side of the substrate 2b (with a portion of the transparent electrode 6b interposed therebetween), the photoresist material is exposed and developed using a regular mask. Thereby, the partition wall 5 can be formed. - The ray-sensitive liquid crystal alignment agent is applied to a plurality of regions divided by the partition wall 5 on the ZD9V clothing (opposite surface). Examples of the coating method include a spray coating method, a slit coating method, a roll coating method, a spin coating method, a printing method, an inkjet method, and a vapor deposition method, but the inkjet method is used by the father. The alignment agent is applied to the plurality of divided regions by coating using an inkjet method. It is noted that the coating method using the ink jet method can be carried out as shown in Fig. 2, in which the liquid crystal alignment agent 4 is discharged from the surface of the substrate 2b by the partition wall 5. The 嗔 2 7 ejecting liquid: the nozzle that is used to match the J 乂. Further, it is preferable that the liquid 1/2 liquid crystal alignment agent 4 which is ejected from the head is preferably low in viscosity. The viscosity of the liquid crystal alignment agent 4 at the time of the congratulation, preferably 15 is called .s' further more..._&quot; Diguo is one ~ 5 mail a.s ~ 9mPa.s. Further, it is preferable that the viscosity of the agent 4 is such that the liquid crystal of the shower head 7 is so as to have a heating means. -67-201219934 6 The radiation-sensitive liquid crystal alignment agent is applied to the entire surface (opposite surface) of the substrate 2a by any of the above methods. The person 'preheats (pre-bakes) the coated surface and then forms a coating film. As a pre-feeding condition, for example, at 40t to 120; 0.1 minute to 5 minutes, post-baking

~3峨, more preferably 13 (TC~22(rc,=piece is preferably 12〇°C 八## I and Kaijia is 5 minutes~2 knives, more preferably 10 minutes~1〇〇 Minutes,,,,.Λ ΛΛ1 After the knife red is baked, the film thickness of the coating film is ο. (Η) 1μιη~1μηι, and more preferably Q is called m~〇5 barrier. Applying the above liquid crystal alignment agent In order to further improve the adhesion of each of the sheets forming the coating film to the coating film, a sulfonium compound, titanate or the like may be applied to the substrate in advance. Next, as step (2), The coating film is irradiated with linearly polarized or glare radiation or unpolarized radiation to impart alignment to the liquid crystal: as the radiation, for example, ultraviolet light and visible light containing wavelength light, and preferably 3 〇〇 nm, may be used. The ultraviolet I of ~4〇〇nm wavelength light can be irradiated from a direction perpendicular to the substrate surface when the radiation used is linearly polarized or partially polarized, and can be moved from the oblique direction in order to impart a pretilt angle. Irradiation, in addition, they can also be combined. In the irradiation of non-polarized radiation In the present specification, the 'pretilt angle' refers to the inclination angle of the liquid crystal molecules in a direction parallel to the substrate surface. Examples of the light source used may include a low pressure mercury lamp, a high pressure mercury lamp, Xenon lamp, metal_chemical lamp, argon resonance lamp, xenon lamp, excimer laser, mercury-xenon lamp (Hg-Xe lamp), etc. The above-mentioned ultraviolet-ray grating of the wavelength -68-201219934 area is preferably used as a The 10,000 J/m2 over-optical alignment method gives the liquid crystal radiation amount, and under the irradiation of radiation, the alcohol-type liquid crystal can be followed by the alcohol-based liquid crystal of each divided region. The liquid and the liquid are filled by using three kinds of liquids, followed by a line. In addition, the gas is inactively filled with a transparent electrode, and the transparent electrode is laminated. The transparent electrode is divided by the partition 5, which can be obtained by a method such as a light source, a filter, or the like. The irradiation amount ' is preferably 1 j/m 2 or more and less, and more preferably 10. i/m 2 to 3,000 J/m 2 . Further, the coating film formed by a conventionally known liquid crystal alignment agent is used. When the force is required to be 10, 〇〇〇j/m2 or more, when the liquid crystal alignment agent is used, the amount of the liquid alignment method is 3,000 J/m 2 or less, and further the loooj/v is used to impart a good liquid crystal alignment. Capability and contribute to the reduction of the manufacturing cost of the biliary display. In the step (3), 'in the blunt domain of the above-mentioned liquid crystal alignment film is formed', three kinds of biliary solids are repeatedly filled in a mosaic form as a filling of the cholesteric liquid crystal. The method of using the ink jet method without a special crystal alignment agent is preferable. The ink method can effectively and accurately crystallize in each divided region. By heating and/or irradiating non-biased radiosteroids as needed The solvent contained in the liquid crystal 3 is dried and allowed to be solidified in the air, or may be carried out under a nitrogen atmosphere. After the sterol liquid crystal 3 is cured, the two substrates (the electrode 6a and the liquid crystal alignment film 4a on the substrate 2a) are bonded to each other by facing the surface such as the laminate. The 6b and the liquid crystal alignment film 4b are laminated on the substrate 2b. And the cholesteric liquid crystal 3 is filled in) "A cholesteric liquid crystal display can be obtained - 69-201219934 In the cholesteric liquid crystal display thus obtained, the ray can be uniformly applied and the liquid crystal alignment ability is imparted in a desired direction. Therefore, the cholesteric liquid "liquid crystal has a high alignment" and can exhibit excellent weather. The cholesteric liquid crystal display of the present invention, the above embodiment. For example, in the cholesterol of FIG. 1, it is also possible to have a cholesteric liquid crystal display having an absorbing layer such as an absorbing layer on the back side of the liquid crystal alignment m4b in the first embodiment of the liquid crystal. Contrast at the time of high display. In addition, the substrate on the back side of the liquid crystal (corresponding to the cholesteric liquid crystal display substrate UP may not be permeable). Further, in the solid solution type liquid crystal display 1, a liquid is formed in a planar shape. Instead of using a radiation-sensitive liquid crystal alignment agent, a general liquid crystal alignment agent is formed. Further, a plurality of i may be coated by the liquid crystal alignment film, and the divided plurality of layers are not separated by the partition walls. Any of the structures, as a crystal display, can be used to perform excellently. 1. The following examples, the specific embodiments of the invention are not limited to these embodiments. The necessary amount of the starting compound and the polymer is ensured by the synthesis of the starting material in the synthetic route diagram shown in the following synthesis example. &quot; 'Looking through the liquid crystal alignment film; the display, its The display performance is not limited to the scoop structure provided on the lower side of the liquid crystal display. The electrode and the electrode 6b according to the further preparation and the bile animal alignment film 4a of Fig. 1 are the partition walls using other regions. ·Can be invented as a cholesterol type liquid, but it is used in this example to require repeated compounds and polymerization.

S-70-201219934 &lt;Synthesis of polyorganosiloxane having a cyclodecyl group&gt; [Synthesis Example 1] In a mixer, a thermometer, a dropping funnel, and a reaction bar, l〇〇.〇g was added. 2-(3,4-epoxyj tridecyloxydecane (ECETS), 500 g decyl isobutylamine, and mixed at room temperature. Next, 10 〇g of deionized water was removed from the dropping funnel, then After mixing under reflux, and after the reaction at the end of I, the organic layer was taken out, washed with a 〇.2 ammonium aqueous solution until the washed water was neutral, and the solvent and water were removed to obtain a polyorganismite as a viscous transparent liquid. Oxygen (. The octylation of the polyorganosiloxane having an epoxy group) results in the same epoxy-based peak at a chemical shift (δ) = 3.2 ppm, thereby confirming the epoxy group The side reaction of the obtained epoxy group was 2,200, and the epoxy equivalent was 186 g/mole. &lt;Synthesis of a specific cinnamic acid derivative&gt; The synthesis reaction of a specific cinnamic acid derivative was carried out. [Synthesis Example 2] 4-fluorophenylboronic acid, 10 g of 4-bromo in a 30 〇mL three-necked flask having a condenser酸酸, 2.7g in bar, 4g sodium carbonate, 80mL tetrahydrofuran and 39mL 8 ° C heated the reaction solution for 8 hours, and through the reflux tube of the I cyclohexyl) ethyl and lO.Og triethyl I 30 minutes of dropwise addition of 8 % by mass of tribasic acid at 8 ° C and then Γ W-NMR fraction with epoxy group under reduced pressure and theoretically strong in the reaction, the polyorganosiloxane was produced in an inert atmosphere. Mix 6.5 g of tetrakis (three stupid base) pure water. Continue to confirm the reaction at TLC 201219934. After cooling the reaction solution to room temperature, inject it into (10)

1... A solid that has been decanted in an aqueous solution. The obtained solid was dissolved in acetic acid, and subjected to liquid separation washing in the order of 1 GGmL of (8) aqueous hydrochloric acid solution, 100 mL of pure water, and 1 GGmL of saturated saline. The organic layer was then dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained @body was vacuum dried to obtain 9 g of a compound represented by the following formula (K·1) (specific cinnamic acid derivative (K-1)).

(K-1) [Synthesis Example 3] In a 20 〇mL three-necked flask equipped with a condenser, 9 5 g of 4-vinylbiphenyl, 1 g of bromocinnamic acid, 〇〇99 g of palladium acetate, and hydrazine were mixed. One (2 phenyl) phosphine, I8 g of diethylamine and 8 〇 mL of dimethyl acetamide. The solution was heated and stirred at 1 20 C for 3 hours, and the end of the reaction was confirmed by TlC, and then the reaction solution was cooled to room temperature. After the precipitate was filtered, the filtrate and the solution were poured into 500 mL of a 1N aqueous acid solution to recover a precipitate. These precipitates were recrystallized using a solution of decyl acetamide and ethanol as hydrazine: hydrazine, whereby llg of a compound represented by the following formula (κ_2) (specific cinnamic acid derivative (Κ-2)) was obtained.

S 201219934 合成] Synthesis of photo-aligned polyorganosiloxane [Chemical Example 4] 9.3 g of a polyorganophosphorus oxide having an epoxy group obtained in Synthesis Example 1 and 26 g were placed in a 100 mL three-necked flask. Methyl isobutyl ketone, 3 g of the specific cinnamic acid derivative (K_1} obtained in Synthesis Example 2 and 〇1〇g quaternary ammonium salt (San-Apro Co., Ltd., UCAT 18X), and stirred at 80° for 12 hours. After the reaction, 're-sinking with decyl alcohol, and dissolving the sulphate in ethyl acetate to obtain a solution. After the solution was washed three times with water, the solvent was distilled off to obtain 6 _ 3 g as a white powder. The light-aligned polyorganosiloxane (S-1). The light-aligned polyorganosiloxane (n) had a weight average molecular weight Mw of 3,500. [Synthesis Example 5] Except that 3 g of the specific cinnamic acid obtained in Synthesis Example 2 was used. A white powder of 7 〇g [A] photo-aligned polyorganosiloxane (S-2) was obtained in the same manner as in Synthesis Example 4 except for the derivative (K-2). Photo-aligned polyorgano-oxygen (S) -2) The weight average molecular weight Mw is 4,900. <[B] Synthesis of other polymers&gt; [Synthesis Example 6] 22.4 g (〇.l Μ ears) 2,3,5_3 ridylcyclopentyl group Acetate dioxon and molar) cyclohexane bis(methylamine) is dissolved in 9.3ρ of 329.3 §, and reacted at 60 ° for 6 hours. After receiving $, the reaction mixture is injected into a very large amount of f alcohol to make the reaction The product H was washed with methanol, and dried under reduced pressure at 4 ° C for 15 hours to obtain 32H proline (PA-2). &quot; '73* 201219934 17.5 g of this (PA-2) ' Add 232 5 g of NMp, 38 g of pyridine and 4.9 g of acetic anhydride' and react at 12 (rc for 4 hours) to carry out the reaction. Then, the reaction mixture was injected into a very large amount of methanol to make The reaction product precipitated β, and the precipitate was washed with methanol, and dried under reduced pressure for 15 hours to obtain i5 g of polyimine (ρι_1). [Synthesis Example 7] 5 parts by mass were added to a flask having a condenser and a stirrer 2,2-azobis-(2,4-dimethylvaleronitrile) and 2 parts by mass of diethylene glycol methyl ethyl ether (DEGME), followed by addition of 4 () parts by weight of glycidyl methacrylate Ester, 10 parts by mass of styrene, 3 parts by mass of methacrylic acid and 2 parts by mass of cyclohexylmaleimide, and after nitrogen replacement, start to slow down Stirring. The temperature of the solution was raised to 7 (rc, and the temperature was maintained for 5 hours to obtain a polymer solution of a poly(fluorenyl) acrylate-containing copolymer (MA_丨). The solid concentration of the obtained polymer solution was 3 3 1% by mass. The number average molecular weight of the polymer to be paid is 7, 〇〇〇. &lt;[C] Synthesis of compound containing ester structure &gt; Synthesis of ester-containing compound (c_) according to the following scheme 1 _ 1).

S -74- 201219934

Ch2=ch—o—c4h9 h3p〇4 CH, C4H9 — 0 —CH—ooc CH3 CH- 〇—C4H9

CH, (c -1.1) COO—CH—0—C4H9 [Synthesis Example 8] In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 21 g of trimesic acid and 6 g of n-butylvinyl group were added. Ether and hydrazine. 9 g of squaric acid, and stirred at 5 (TC for 3 hrs, the reaction was carried out. After the end of the reaction, '5 〇〇 mL of hexanol was added to the reaction mixture to obtain an organic layer, for which the organic layer was followed 2 The liquid was washed with a second aqueous solution of sodium hydroxide and three times of water, and the solvent was distilled off from the organic layer to obtain 5 g of an ester-containing compound (c_丨_丨) as a colorless transparent liquid. Preparation of Liquid Crystal Aligning Agent&gt; [Example 1] A solution containing polyimine (PI_丨) obtained in Synthesis Example 6 was taken as [B] other polymer' and the amount thereof was equivalent to that contained therein. Polyimine (wherein 1000 parts by mass), 1 part by mass of the [A] photo-aligned polyorganosiloxane (s-1) obtained in Synthesis Example 4 was added thereto, and NMP and the mixture were further mixed. Diethylene glycol decyl ethyl ether (DEGME), the solvent composition is NMP: DEGME = 90: l 〇 (mass ratio), solid concentration -75- 201219934 A filter crystal alignment agent (Α-1) having a pore size of 1 μηη. A solution of 3.5% by mass of the solution was used. The liquid of Example 1 was prepared [Example 2] & a 'r's solution containing poly(indenyl)propene (MA-1) as a copolymer of sulphuric acid vinegar is [B] other polymers, and is included in the polypotentium contained therein: μ:, the amount is equivalent to 1,000 parts by mass of the (meth) acrylate, and 100 parts by mass of the synthetic [Α] light is added to the complex Λ λ and the complex (ΜΑ-1). The ethylene-alcohol monobutyl I () passed in the oriented polyorganic i 5 is mixed with NMP and B-butyl butyl (EGMB) to form a dissolved NMP: EGMB = 5〇-5〇r@ - - x Then, the solution was obtained. The concentration of the solid component was 3.5 mass. The solution was filtered through the filter of (4) to prepare the liquid crystal alignment agent (A_2) of Example 2. &lt;Production of Cholesteric Liquid Crystal Display&gt; A liquid crystal alignment agent prepared in the above Synthesis Example was used, and a cholesteric liquid crystal display was produced in the following manner. [Example 3] Each of two transparent glass substrates a and On one side, a strip-shaped transparent electrode (ITO electrode) was produced in the following order. In the high-speed sputtering apparatus SH-550-C12 manufactured by Japan Vacuum Technology Co., Ltd., a ruthenium target was used (the ruthenium filling ratio was 95% or more, In2〇3/Sn〇2 = 90/l〇 mass ratio), ITO sputtering was carried out at 6 ° C. At this time, the pressure was ι·〇χ 1() 5pa 'Ar gas flow rate was 3.12x10_3m3/hr The gas flow rate of 02 was 1 ^xl (T5m3/hre, the substrate after sputtering was heated in a clean oven at 24 ° C &gt; c for 6 minutes, and annealing was performed.

S-76-201219934 The transparent electrode is formed on the surface of the transparent glass substrate b on which the strip-shaped transparent electrode is placed, and the grid-shaped partition wall is formed. This partition wall was formed by exposing, developing, and solidifying through a photomask by a photo-resist material (product name: manufactured by JSR Corporation, OPTOMER NN7 77). In each of the regions formed by the above-mentioned partition walls, the liquid crystal alignment agent (A_1)' was applied by an ink-jet method and pre-baked for 1 minute on a hot plate at 80 °C. Then, in an oven which was internally purged with nitrogen, after j 5 〇 &lt;&gt;c; t, L 3 0 was a clock, and a coating film having a film thickness of 〇 ^ was formed. Next, using a Hg-Xe lamp and a Glan Taylor prism, the surface of the coating film was irradiated perpendicularly from the substrate normal to 300 J/m 2 of polarized ultraviolet light containing a 313 nm glow line to form a liquid crystal alignment film. Further, in addition to the roll coating method, In the same manner as described above, the same liquid crystal alignment film was formed on the entire surface of the transparent glass substrate (b). In a nematic liquid crystal material E7 (manufactured by Merck Co., Ltd.), 40 mass of a chiral agent CB 1 5 (manufactured by Merck) was mixed and filtered through a filter having a pore size of 〇.2 μηι to prepare a cholesteric liquid crystal. In each of the regions where the liquid crystal alignment film is formed on the transparent glass substrate (a), the cholesteric liquid crystal is filled with a pipette. Next, baking was performed on a hot plate of 6 (TC) for 1 minute, and then a non-polarizing ultraviolet ray containing 365 nm of 365 nm glow was irradiated with an Hg-Xe lamp to cure the liquid crystal. The glass substrate (a) filled with the liquid crystal was used. On the liquid crystal side surface, the surface of the glass substrate (b) on the liquid crystal alignment film side was superposed and joined to each other to obtain a cholesteric liquid crystal display device of Example 3. -77 - 201219934 [Example 4] In the third embodiment, a cholesteric liquid crystal display device of Example 4 was obtained in the same manner as in Example 3 except that the liquid crystal alignment agent (A-2) was used instead of the liquid crystal alignment agent (A-1). <Evaluation> For the production The cholesteric liquid crystal display was evaluated by the following method. [Orientation] For the liquid crystal alignment film portion on the substrate (a) side before the final substrate (a) and the substrate (b) in the above Examples 3 and 4, a polarizing microscope was used. The presence or absence of the abnormal region was observed, and the case where the abnormal region was not observed was evaluated as the liquid crystal alignment "A", and the abnormal region was observed, and the liquid crystal alignment "B" was evaluated. Both of Examples 3 and 4 were liquid crystal alignment. Sex In addition, in the third embodiment and the fourth embodiment, a liquid crystal alignment film having no coating defects and uneven coating can be uniformly formed by an inkjet method. [Industrial Applicability] According to the present invention, it is possible to provide The invention relates to a cholesteric liquid crystal display with good uniformity of liquid crystal alignment and excellent display performance. The cholesteric liquid crystal display can be used for various liquid crystal display devices, and particularly can be applied to a flexible display headed by electronic paper. 1 is a schematic cross-sectional view showing a cholesteric liquid crystal display according to an embodiment of the present invention. Fig. 2 is a schematic view showing one step in a method of manufacturing a cholesteric liquid crystal display according to Fig. 1.

-78- 201219934 [Explanation of main component symbols] 1 Cholesteric liquid crystal display 2a ' 2b Substrate 3 Cholesteric liquid crystal 4a, 4b Liquid crystal alignment film 5 Partition wall 6a, 6b Transparent electrode 7 Nozzle -79-

Claims (1)

3 201219934 VII. Patent application scope 1. A method for producing a cholesteric liquid crystal display comprising: a pair of opposed substrates; and cholesteric liquids respectively disposed in a direction perpendicular to the respective substrates And a liquid crystal alignment film which is laminated between each of the substrates and the alcohol liquid crystal, wherein the manufacturing includes: (1) a plurality of regions in which at least one of the substrates is divided into radiation. a liquid crystal alignment agent and a step of forming a coating film; (2) a step of forming a liquid crystal by irradiating the coating film with radiation; and a step of forming a cholesteric liquid crystal. 2. A method of cholesteric liquid crystal display according to the scope of the patent application of the present invention, which is carried out by an inkjet method. A cholesteric liquid crystal display comprising: a facing plate; and a cholesteric liquid crystal in which a plurality of regions are disposed in a plurality of regions between the substrates cut in a direction perpendicular to each of the substrates, and laminated on each of the substrates And a cholesteric liquid liquid crystal alignment film, wherein at least one of the liquid films is formed of a radiation sensitive liquid crystal alignment agent. 4 · If the scope of the patent application is the first * eve 7 and the third cholesteric liquid crystal display, the above-mentioned area will be carried out by the shape of the virtual. ^ ^ will be made into a grid-like partition wall. The luminosity-type liquid crystal display of the above-mentioned three types of sensible radiation linear liquid crystal A ta from the daily alignment agent contains "A" and has a polyorganosiloxane. La LL, page aligning liquid crystal, substrate sizing method Filling and manufacturing the alignment between the base and the typed liquid, !_J. ^, group -80- 201219934 6. As described in the patent scope, the first alignment of the cholesteric liquid crystal display of the fifth item Its cocoon g, _ 暴 疋 has a cinnamic acid structure. Ή:: Scope of the "Cholesterol type liquid crystal display,", the eight cinnamic acid structure of the group is composed of (1) group of the group (2) at least one selected from the group consisting of the compounds π, H~(-R1__R2 H~{-R4__r5 COOH (2) (1) 环环义' R 4 is a phenyl group, a biphenyl group, a terphenyl group or a hexyl group; a dibasic group, a biphenyl group, a terphenyl group or a stretching ring, 虱The atom may be a fluorine atom or an atom having a carbon number of 丨1 to 10... an alkoxy group of 10 to 10 is a single bond, and a chain a having a carbon number of 1 to 3 is 0 to 'sulfur atom, _CH=CH_ , ship or -C00-, R2 can be an integer of phase, where 'when 4 2 or more, each R1 and ~4 can also be different, R3 is a fluorine atom or a cyano group, U0 珲 ί ί (2) R4 is a phenyl or a cyclohexyl group. The phenyl group or the extended chain = some or all of the hydrogen atoms may be a chain of 1 to 10 carbon atoms or a chain, a chain of carbon atoms (7) or Ring 201220124 Alkoxy group, fluorine atom or cyano group substituted, R5 is a single bond, a chain of 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or _NH_, e is an integer of 1 to 3, However, when c is 2 or more, R4 and R5 may each be the same 'may be different', R6 is a fluorine atom or a cyano group, and d is an integer of 〇~4', and R7 is an oxygen atom, 〇〇〇-* or - OCO- *, among them, with * The bond is bonded to R8, and R8 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, and R9 is a single bond, _0C0_(CH2 ) f_* or ·〇((:Η2)β_*, wherein the bond with * is connected to the carboxyl group, f and g are each an integer of 1 to 1 ,, and e is an integer of 0 to 3, but when e is When it is 2 or more, R7 and R8 may be the same or different. The cholesteric liquid crystal of any one of items 5 to 7 of the σ-methyl 岣 derivative range is unfavorable, wherein [Α] polyorganosiloxane is a reaction. a product obtained by reacting at least one selected from the group consisting of a compound represented by the above formula (1) and a compound represented by the above formula (7) with a polyorganosiloxane having a decyl group. 9. According to the fifth display of the patent application scope, wherein any of the above-mentioned cholesteric liquid crystals.rRltb ^ , the above-mentioned radiation-sensitive liquid crystal alignment agent further contains [B] from poly-proline, polyphthalamide a compound and a polyorganismite selected from the group consisting of apricot kappa / ethylenically unsaturated compound poly group J. 乂 乂 种 种 种 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. The daily alignment agent further contains ruthenium, /, two or more, ketal esters of carboxylic acid, acetal ester structure of hydrazine, 1 ·, 1 ^ U To 1 &amp; A compound selected from the group consisting of a base ester structure and a ternary butyl ester structure of carboxylic-82-201219934 acid. 1 1. A liquid crystal alignment agent which is a liquid crystal alignment agent for a cholesteric liquid crystal display crystal alignment film, wherein the display device includes: a pair of opposite substrates; and the cholesterol is disposed in a direction perpendicular to the substrate In a plurality of regions; and a liquid crystal alignment film that is laminated between the respective liquid crystals described above, the characteristic is that the radiation is linear. The above liquid-solid alcohol type liquid crystal display liquid crystal in at least one structure's divided plate between substrates and cholesteric liquid crystal alignment agent S-83