KR20120090752A - Liquid crystal display device and manufacturing method thereof, and liquid crystal aligning agent - Google Patents

Abstract

PURPOSE: A liquid crystal display device, a manufacturing method thereof, and a liquid crystal aligning agent are provided to obtain superior response features of liquid crystal molecules about a voltage change. CONSTITUTION: A first aligning film(13) is formed on one of a pair of substrates. The first aligning film aligns liquid crystal molecules at an angle against a direction vertical to a surface of one substrate. A second aligning film(15) is formed on a surface of the other surface. The second aligning film perpendicularly aligns liquid crystal molecules. The first aligning film is formed by using liquid crystal aligning materials. The liquid crystal aligning materials comprise a radiation-sensitive compound with photo aligning features.

Description

Liquid crystal display element, its manufacturing method, and liquid crystal aligning agent {LIQUID CRYSTAL DISPLAY DEVICE AND MANUFACTURING METHOD THEREOF, AND LIQUID CRYSTAL ALIGNING AGENT}

This invention relates to a liquid crystal display element, its manufacturing method, and a liquid crystal aligning agent, Specifically, The liquid crystal display element which has a liquid crystal aligning film provided with the liquid-crystal orientation ability by the photo-alignment method, its manufacturing method, and the said liquid crystal display It relates to a liquid crystal aligning agent for obtaining an element.

Conventionally, as a liquid crystal display element, VA (Vertical Alignment) type liquid crystal display element etc. which vertically orientate a liquid crystal molecule with respect to a board | substrate are known, for example. In a VA type liquid crystal display element, liquid crystal molecules are oriented perpendicular to the substrate surface in a state where no voltage is applied, and liquid crystal molecules are oriented in a horizontal direction with respect to the substrate surface in a state where a voltage is applied. In such VA type, the inclination direction of the liquid crystal molecules of the vertically aligned state is conventionally performed by providing a rib and an electrode slit, for example.

Moreover, as a liquid crystal aligning technique, the optical alignment method which gives a liquid crystal aligning ability to the coating film by attracting light to the coating film formed on the board | substrate surface instead of the conventional rubbing method attracts attention in recent years. According to this method, the performance of tilting (tilting) the liquid crystal can be exhibited on the coating film itself, and there is an advantage that the response speed of the liquid crystal molecules to voltage changes can be improved. In addition, at that time, there is also an advantage that the pretilt angle of the liquid crystal molecules with respect to the substrate surface can be controlled with high accuracy.

Various liquid crystal display elements which have a liquid crystal aligning film formed by such a photo-alignment method are proposed (for example, refer patent document 1 and patent document 2). For patent documents 1 and 2, the coating film is formed in the surface of each of two board | substrates using the liquid crystal aligning agent containing a radiation sensitive polyorganosiloxane, and the board | substrate provided with the photo-alignment film irradiated to those coating films is used. And manufacturing a liquid crystal display element is disclosed.

Japanese Patent No. 4416054 Japanese Laid-Open Patent Publication No. 2010-185001

In recent years, the demand for higher quality of liquid crystal display devices is increasing, and in order to realize this, it is necessary to further improve the response (response speed) of liquid crystal molecules to voltage changes in liquid crystal display elements.

This invention is made | formed in view of the said subject, Comprising: It aims at providing the liquid crystal display element excellent in the response characteristic of the liquid crystal molecule with respect to a voltage change, its manufacturing method, and the liquid crystal aligning agent used for manufacturing this.

The present invention employs the following means to achieve the above object.

The liquid crystal display element of this invention is a liquid crystal display element provided with a pair of board | substrate, Comprising: The 1st which inclines orients liquid crystal molecules with respect to the direction perpendicular | vertical to the said board | substrate surface on one of the said board | substrate surfaces. An alignment film is formed, and on the other substrate surface, a second alignment film for vertically aligning liquid crystal molecules is formed, and the first alignment film uses a liquid crystal aligning agent containing a radiation sensitive compound having a photoalignment group. The photo-alignment group is formed, azobenzene, stilbene, α-imino-β-ketoester, spiropyran, spiroxazine, cinnamic acid, chalcone, stilazole, benzylidene phthalimidine, coumarin, diphenylacetylene And it has a structure derived from at least 1 compound chosen from the group which consists of anthracene.

Moreover, the manufacturing method of the liquid crystal display element of this invention is a manufacturing method of the liquid crystal display element provided with a pair of board | substrate, in the board | substrate surface of one of said pair of board | substrates, with respect to the direction perpendicular | vertical to the said board | substrate surface. A manufacturing process of manufacturing the liquid crystal display element in which the 1st alignment film which inclines orients a liquid crystal molecule, and formed the 2nd alignment film which vertically orients a liquid crystal molecule in the other substrate surface is provided, Comprising: The said 1st alignment film, It forms using the liquid crystal aligning agent for photoalignments containing the radiation sensitive compound which has a photo-alignment group, The said photo-alignment group is azobenzene, stilbene, (alpha)-imino- (beta)-ketoester, spiropyran, spiroxazine, At least one compound oil selected from the group consisting of cinnamic acid, chalcone, stilbazole, benzylidenephthalimidine, coumarin, diphenylacetylene and anthracene And the structure characterized in that a characteristic.

According to this invention, in a liquid crystal display element, one of the liquid crystal aligning film which a pair of board | substrate has is made into the alignment film which inclines orients liquid crystal molecules with respect to the direction perpendicular | vertical to the surface of a board | substrate, and the other is made into a vertical alignment film, About the former alignment film, by forming with the liquid crystal aligning agent containing the radiation sensitive compound which has a specific photo-alignment group, the liquid crystal display element excellent in the response characteristic of the liquid crystal molecule with respect to a voltage change can be obtained.

In the present invention, the photo-alignment group may have a structure derived from cinnamic acid. In addition, the radiation sensitive compound may include a polyorganosiloxane having the photoalignable group, and in this case, it is possible to further provide excellent durability (light resistance) against long-term light irradiation.

Here, the following two aspects are mentioned specifically as a manufacturing method of the liquid crystal display element of this invention. First, as a 1st structure, the said manufacturing process is the 1st film formation process which forms a 1st coating film on the surface of one of said pair of board | substrates using the said liquid crystal aligning agent for photoalignments, and the said 1st By irradiating a coating film, the said 2nd light irradiation process makes a said 1st coating film the said 1st alignment film, and the said 2nd using the liquid crystal aligning agent which can form a vertical alignment film in the other substrate surface among the said pair of board | substrates. A second film forming step of forming a second coating film as an alignment film; and a cell construction in which the pair of substrates are disposed so that the first alignment film and the second coating film face each other, and a liquid crystal cell filled with liquid crystal molecules is formed between the substrates. The thing including a process is mentioned.

Moreover, as a 2nd structure, the said manufacturing process is the 1st film formation process which forms a coating film in the surface of one of said pair of board | substrates using the said liquid crystal aligning agent for photoalignments, and the said pair of board | substrates. The second film formation process of forming the said 2nd alignment film using the liquid crystal aligning agent which does not contain the radiation sensitive compound which has a photo-alignment group substantially on the other substrate surface of the said board | substrate, and the said coating film and the said 2nd alignment film are A cell construction step of constructing a liquid crystal cell in which the pair of substrates are disposed so as to face each other, and a liquid crystal molecule is filled therebetween, and a voltage between the pair of substrates with respect to the liquid crystal cell constructed by the cell construction step. It includes the light irradiation process of irradiating light in the state which applied. Among these two configurations, from the viewpoint of the responsiveness of the liquid crystal molecules to the voltage change, the first configuration is more preferable.

1 is a longitudinal cross-sectional view of a liquid crystal display element.
It is a figure which shows the pattern shape of a transparent conductive film.

(Form to carry out invention)

[Liquid Crystal Display Element]

Hereinafter, the liquid crystal display element of this invention is demonstrated, referring drawings suitably. 1: is a schematic diagram which shows an example of the liquid crystal display element of this invention.

As shown in FIG. 1, the liquid crystal display element 10 has a pair of board | substrates 11a and 11b, and they are mutually spaced apart. The substrates 11a and 11b are, for example, glass such as float glass and soda glass; It is comprised by the transparent substrate which consists of plastics, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, and a poly (alicyclic olefin).

The first electrode 12 is provided in one board | substrate 11a among the pair of board | substrates on the surface of the side facing the other board | substrate 11b. The first electrode 12 is not particularly limited as long as it is generally used as an electrode of a liquid crystal display element. For example, a transparent conductive film can be used. Examples of the transparent conductive film include an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. .

In the 1st electrode 12, the 1st alignment film 13 is formed in the surface of the side facing the board | substrate 11b. The 1st alignment film 13 is comprised by the organic thin film which can orientate liquid crystal molecules with respect to the direction perpendicular | vertical to the substrate surface. That is, in the first alignment film 13, as shown in FIG. 1, the rising angle (pretilt angle) of the liquid crystal molecules from the substrate surface is θ (0 <θ <90 °). It is preferable that it is 0.001-1 micrometer, and, as for the film thickness of the 1st alignment film 13, it is more preferable that it is 0.005-0.5 micrometer.

In the board | substrate 11b, the 2nd electrode 14 is provided in the surface of the side facing the board | substrate 11a. As this 2nd electrode 14, the thing similar to the transparent conductive film illustrated by the 1st electrode 12 can be used. For example, when the liquid crystal display element of this invention is applied to the system using TFT, one of the 1st electrode 12 and the 2nd electrode 14 can be made into a counter electrode, and the other can be made into a pixel electrode. have.

In the second electrode 14, a second alignment film 15 is formed on the surface of the side facing the substrate 11a. The 2nd alignment film 15 is comprised by the organic thin film which orientates a liquid crystal molecule with respect to the surface of a board | substrate. It is preferable that it is 0.001-1 micrometer, and, as for the film thickness of the 2nd alignment film 15, it is more preferable that it is 0.005-0.5 micrometer.

The liquid crystal layer 17 filled with the liquid crystal molecules 16 is formed between the first alignment film 13 and the second alignment film 15. As the liquid crystal molecules 16, for example, nematic liquid crystals, smectic liquid crystals, or the like can be preferably used. Especially, the nematic liquid crystal which has negative induction anisotropy is preferable, For example, dicyano benzene type liquid crystal, a pyridazine type liquid crystal, a siphon base liquid crystal, a cyan clock liquid crystal, a biphenyl type, for example. A liquid crystal, a phenyl cyclohexane type liquid crystal, etc. can be used. It is preferable that the thickness of the liquid crystal layer 17 is 1.2-8.0 micrometers, It is more preferable that it is 1.3-5.5 micrometers, It is further more preferable that it is 1.4-4.0 micrometers.

The polarizing plates 18 and 19 are attached to the outer surface of the pair of board | substrates 11a and 11b, respectively. As the polarizing plates 18 and 19, a polarizing plate or a polarizing plate made of a polarizing plate sandwiched between a cellulose acetate protective film and a polarizing film called &quot; H film &quot; in which iodine is absorbed while extending and oriented polyvinyl alcohol can be used.

Next, the 1st alignment film 13 and the 2nd alignment film 15 in this invention are demonstrated. The 1st alignment film 13 and the 2nd alignment film 15 in this invention are liquid crystal aligning agents (1st aligning agent, 2nd aligning agent) containing the polymer of at least any one of a polyamic acid and a polyimide as a polymer component. Are each formed using

[First alignment agent]

The 1st aligning agent for forming the 1st aligning film 13 is comprised including the radiation sensitive compound which has a photo-alignment group.

<Radiation Compound>

The photo-alignment group which the radiation sensitive compound in this invention has is an anisotropy to a film | membrane by light irradiation, In this invention, an anisotropic property to a film | membrane is produced especially by generating at least any one of a photoisomerization reaction and a photodimerization reaction. Is to give.

Specifically as a photo-alignment group applied at the time of formation of the 1st oriented film 13, azobenzene, stilbene, (alpha)-imino- (beta)-ketoester, spiropyran, spiroxazine, cinnamic acid, chalcone, stilazole It is group which has a structure derived from at least 1 compound chosen from the group which consists of a benzylidene phthalimidine, coumarin, diphenyl acetylene, and anthracene. As said photo-alignment group, group which has a structure derived from cinnamic acid is especially preferable among these. As a structure derived from cinnamic acid, it can be represented by following formula (c1) specifically.

(Wherein R is an alkyl or alkoxy group having 1 to 6 carbon atoms, a fluorine atom or a cyano group; a is an integer of 0 to 4, and when a is 2 to 4, a plurality of R's are each independently defined above) "*" Represents a bonding hand).

As a C1-C6 alkyl group in R of said Formula (c1), a methyl group, an ethyl group, a butyl group, etc. are mentioned, for example. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

As a, 0 or 1 is preferable and 0 is more preferable.

Specifically as a photo-alignment group which has a structure represented by said formula (c1), it is preferable to represent by following formula (c1-1) or formula (c1-2).

(Wherein, R ¹ and R ^3, each independently represents a hydrogen atom, 3 carbon atoms having an alicyclic group 40 monovalent organic group, or may have a fluorine atom having 1 alkyl group of 40, and;?? R ^2, and R ⁴ is each independently a methylene group, —Si (CH ₃ ) ₂ —, —CH═CH—, —C≡C— or a divalent group having a cyclic structure; X ¹ , X ^2, and X ³ are , each independently, a single bond, an oxygen ^{atom, -CO-, -COO-, -NR a -} , -CO-NR a -, -NR a -CO-O-, -NR a -CO-NR a -, -O-CO-O-, provided that R ^a is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X ⁴ is a single bond or an oxygen atom; b and c are each independently, When b and c are 2 or 3, a plurality of R ² , R ⁴ , X ² , and X ⁴ each independently have the above definition; and R, a and "*" are each Meaning the same as formula (c1)).

R ¹ of the formula (c1-1) And as a C3-C40 monovalent organic group which has an alicyclic group in R <^3> of said Formula (c1-2), For example, cyclohexyl methyl group, cyclohexyl propyl group, cyclohexyl pentyl group, cyclohex A silheptyl group, a cyclooctyl group, an adamantyl group, a cholestanyl group, a cholesteryl group, a lanostanyl group, etc. are mentioned.

As a C1-C40 alkyl group in R <^1> and R <^3> , it may be linear or branched form. The alkyl group is preferably 1 to 20 carbon atoms, and specifically, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. From the viewpoint of expressing good liquid crystal alignment, the alkyl group is preferably a linear alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear alkyl group having 4 to 12 carbon atoms.

At least 1 hydrogen atom which a carbon atom has in the alkyl group in R <^1> and R <^3> may be substituted by the fluorine atom. As a specific example of such a fluoroalkyl group, it is a 3,3,3- trifluoropropyl group, a 4,4,4- trifluoro butyl group, 4,4,5,5,5- pentafluorophene, for example. Tyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoro A roethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group, etc. Can be mentioned. Especially as a fluoroalkyl group in R <^1> and R <^3> , it is preferable that it is C3-C6 linear from a viewpoint which can make liquid crystal alignability favorable.

R ² of the formula (c1-1) And divalent groups having a cyclic structure in R ⁴ of Formula (c1-2) include divalent aromatic groups, alicyclic groups, heterocyclic groups, and condensed cyclic groups. The bivalent group which consists of these may be sufficient.

Of these, examples of the divalent aromatic group include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5, 6-tetrafluoro-1,4-phenylene group;

As a bivalent alicyclic group, it is a 1, 4- cyclohexylene group, 2-fluoro- 1, 4- cyclohexylene group, 3-fluoro- 1, 4- cyclohexylene group, 2, 3, for example. , 5,6-tetrafluoro-1, 4-cyclohexylene group, etc .;

As a bivalent heterocyclic group, For example, a 1, 4- pyridylene group, a 2, 5- pyridylene group, a 1, 4- furanylene group, etc .;

As a bivalent condensed cyclic group, a naphthylene group etc. are mentioned, respectively.

As X <^1> , X <^2> and X <^3> , it is preferable that they are a single bond, an oxygen atom, or -COO-, respectively.

The integer of 0-2 is preferable, and, as for b, 1 or 2 is more preferable.

As group represented by said formula (c1-1), group represented by following formula (c1-1-1) (c1-1-28) can be illustrated specifically ,.

(In formula, R <^1> and "*" are the same meaning as Formula (c1-1), respectively, and d is an integer of 1-10.

As group represented by said formula (c1-2), group represented by following formula (c1-2-1)-(c1-2-4) can be illustrated.

(In formula, R <^3> and "*" respectively have the same meaning as Formula (c1-2).

As a radiation sensitive compound which has a photo-alignment group, it is preferable that it is a polymer in which the said photo-alignment group was couple | bonded directly or through the coupling group. Examples of the polymer include those in which the photoalignable group is bonded to a polymer of at least one of polyamic acid and polyimide, and those in which the photoalignable group is bonded to a polymer different from polyamic acid and polyimide. In the latter case, examples of the basic skeleton of the polymer having a photo-alignment group include poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, polyolefin, polyorganosiloxane and the like. In addition, in this specification, "(meth) acryl" means an acryl and methacryl.

As a radiation sensitive compound, since the reaction speed of the liquid crystal molecule with respect to a voltage change can be made quick in a liquid crystal display element, it is preferable to make polyamic acid, polyimide, or polyorganosiloxane as a basic skeleton. Among these, polyorganosiloxane is especially preferable. By containing polysiloxane which has the said photo-alignment group in a 1st aligning agent, in the liquid crystal display element, in addition to the reaction rate of the liquid crystal molecule with respect to a voltage change, durability (light resistance) with respect to long-term light irradiation can be made more favorable. .

<Specific polyorganosiloxane>

The polyorganosiloxane (hereinafter also referred to as a specific polyorganosiloxane) having the photo-alignment group includes, for example, a polyorganosiloxane (polysiloxane precursor) having an epoxy group, a group reacting with an epoxy group, and the photo-alignment group. It can obtain by making a radiation sensitive compound (henceforth a reactive compound X1) react.

(Polysiloxane precursor)

The polysiloxane precursor can be obtained by, for example, hydrolyzing and condensing the silane compound (1) having an epoxy group and a hydrolyzable group in the presence of an organic solvent, water, and a catalyst.

As the silane compound (1), for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycol Cydyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyl Oxyethyltriethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyl Dimethylethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldie Methoxysilane, 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxy Ecyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4 -Epoxycyclohexyl) propyl triethoxysilane, etc. can be mentioned, One or more types selected from these can be used.

Although the silane compound used for synthesizing a polysiloxane precursor may be only a silane compound (1), in addition to the silane compound (1), the silane compound which does not have an epoxy group (henceforth a "silane compound (2)") may be included. .

As a silane compound (2) which can be used here, in the silane compound which has one silicon atom, and a brand name, for example, KC-89 and X-21-3153 (all are the Shin-Etsu Chemical Co., Ltd. make). And partial condensates. Preferable specific examples of the silane compound (2) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth) Acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane.

It is preferable that the epoxy equivalent of a polysiloxane precursor is 100-10,000 g / mol, It is more preferable that it is 150-1,000 g / mol, It is especially preferable that it is 150-300 g / mol. Therefore, in synthesizing a polysiloxane precursor, it is preferable to prepare the use ratio of a silane compound (1) and a silane compound (2) so that the epoxy equivalent of the polyorganosiloxane obtained may become said range. In the synthesis | combination of the said polysiloxane precursor, it is preferable to use only a silane compound (1).

As an organic solvent which can be used for the synthesis | combination of a polysiloxane precursor, hydrocarbon, ketone, ester, ether, alcohol, etc. are mentioned, for example, It is preferable that they are water-insoluble. Moreover, as said organic solvent, it can use individually or in mixture of 2 or more types. The amount of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight based on 100 parts by weight of the total silane compounds.

The amount of water used when synthesizing the polysiloxane precursor is preferably 0.5 to 100 times mole, and more preferably 1 to 30 times mole with respect to all the silane compounds.

As a catalyst used for the synthesis | combination of a polysiloxane precursor, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. Among these, examples of the alkali metal compound include sodium hydroxide, potassium hydroxide and the like; Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine and piperazine: tertiary organic amines such as triethylamine, pyridine and 4-dimethylaminopyridine: tetramethylammonium hydroxide And quaternary organic amines such as side. As said catalyst, an alkali metal compound or an organic base is especially preferable, and an organic solvent is more preferable. Moreover, as an organic base, tertiary organic amine or quaternary organic amine is especially preferable.

When using an organic base as a catalyst, the usage-amount may be set suitably according to reaction conditions, such as the kind of organic base, temperature, etc., For example, Preferably it is 0.01-3 molar moles with respect to a whole silane compound, More preferable Preferably it is 0.05-1 molar.

Synthesis reaction (hydrolysis-condensation reaction) of a polysiloxane precursor, for example, dissolves a silane compound (1) and the silane compound (2) used as needed in an organic solvent, and this solution is an organic base as a catalyst. And mixing with water, for example, by heating in an oil bath or the like. At the time of this hydrolysis-condensation reaction, heating temperature becomes like this. Preferably it is 130 degrees C or less, More preferably, it is 40-100 degreeC, Preferably it is 0.5-12 hours, More preferably, it heats 1-8 hours. Do. During heating, the mixed liquid may be stirred or placed under reflux. In addition, after completion | finish of reaction, it is preferable to wash the organic solvent layer fractionated from the reaction liquid with water. Washing is performed until the water layer after washing | cleaning becomes neutral, and after that an organic solvent layer is dried with desiccants, such as anhydrous calcium sulfate and molecular sieves, as needed, a solvent is removed. Thereby, the target polysiloxane precursor can be obtained.

It is preferable that it is 1,000-1,000,000, and, as for the polysiloxane precursor, the weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography, it is more preferable that it is 1,500-300,000.

In addition, when using a commercial item as a polysiloxane precursor, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Chisso Corp. make) etc. can be used, for example.

(Reactive compound X1)

Reactive compound X1 has group which reacts with the epoxy group which a polysiloxane precursor has, and the said photo-alignment group. As a group which reacts with an epoxy group, a carboxyl group is preferable. As a specific example of such a reactive compound X, the bond in the group represented by said formula (c1-1-1) (c1-1-28) couple | bonded with a hydroxyl group, said formula (c1-2-1)? (C1 The bond hand in group represented by -2-4) couple | bonded with the carboxyl group.

It is preferable that it is 5-80 mol% with respect to the silicon atom which a polysiloxane precursor has, and, as for the ratio of the reactive compound X1 used at the time of the synthesis | combination of polyorganosiloxane, it is more preferable that it is 10-65 mol%, and it is 15-50. It is more preferable that it is mol%.

In the reaction of the polysiloxane precursor with the reactive compound X1, a compound having a group which does not have a photo-alignment group but reacts with an epoxy group (hereinafter referred to as other reactive compound X2) may be contained together with the reactive compound X1. As other reactive compound X2, the structure which generate | occur | produces a radical by the other reactive compound (X2-1), [2] light irradiation which contributes to the pretilt angle expression in the liquid crystal aligning film obtained by [1], for example, [1] Other reactive compound (X2-2) which has at least 1 sort (s) of the structure which has a function, [3] Other reactive compound (X2-3) of that excepting the above is mentioned.

[1] other reactive compounds (X2-1)

As another reactive compound (X2-1), the compound represented, for example by following formula (x2-1) can be used.

[In formula, A <^1> is a C3-C10 cycloalkyl group which may be substituted by a C1-C30 alkyl group, a C1-C20 alkyl group, or an alkoxy group, or a C1-C51 hydrocarbon group which has a steroid skeleton. ; Provided that at least some of the hydrogen atoms in the alkyl group and the alkoxy group in A ¹ may be substituted; L ⁰ is a single bond, * -O-, * -COO- or * -OCO-, and, and the coupling hand tagged "*" combined with A ^1; L ¹ is a single bond, an alkanediyl group having 1 to 20 carbon atoms, a phenylene group, a biphenylene group, a cyclohexylene group, a bicyclohexylene group, or the following formula (L ¹ -1) or (L ¹ -2) :

(In the formula, "*" represents a bonding hand bonded to Z.)

A group represented by; Z is a monovalent organic group capable of reacting with an epoxy group to form a bonding group; Provided that when L ¹ is a single bond, L ⁰ is a single bond.

As a C1-C30 alkyl group in A <^1> of said Formula (4), it may be linear or branched form, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylphene Methyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl Group, 1,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2 -Methylhexyl group, 1-methylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group , 2,3-dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group , 1,3,3-trimethylbutyl group, 1, 2,3-trimethyl butyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1-methylheptyl group, 2 -Ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-heptadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, etc. are mentioned.

In A <^1> , as a C3-C10 cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononanyl group, a cyclodecyl group, etc. are mentioned, for example. These cycloalkyl groups may be substituted with a C1-C20 alkyl group or an alkoxy group. As a specific example of a C1-C20 alkyl group, the specific example mentioned in the description of the said C1-C30 alkyl group is applicable, As a C1-C20 alkoxy group, the specific example mentioned in the description of the said C1-C30 alkyl group Examples in which an oxygen atom is bonded to an alkyl group of the example are mentioned.

Alkyl group and an alkoxy group in A ^1, good optionally substituted with at least part of the hydrogen atom, may be mentioned as the substituent in this case, a cyano group, a fluorine atom, a methyl group such as trifluoromethyl.

As a C17-51 hydrocarbon group which has a steroid skeleton, group represented by following formula (s-1)-(s-3) is mentioned, for example.

(In the formula, "*" represents a bonding hand bonded to L ⁰ ).

Examples of A ^1, inter alia, C 1? A fluoroalkyl group of alkyl group, having 1? 20 of 20, is preferably a selected from the group represented by the formula group and the formula (s-3) represented by (s-1) .

It is preferable that Z is a carboxyl group.

As a C1-C20 alkanediyl group in L <^1> , the group remove | excluding one hydrogen atom in each group mentioned in the description of the said C1-C30 alkyl group is mentioned.

As a compound represented by said formula (x2-1), the compound represented by either of following formula (x2-1-1) (x2-1-8) is preferable.

 (Wherein u is an integer from 1 to 5, v is an integer from 1 to 18, w is an integer from 1 to 20; k is an integer from 1 to 5, p is 0 or 1, and q is 1 An integer of? 18; r is an integer of 0 to 18, j is an integer of 1 to 18; s and t are each independently an integer of 0 to 2, provided that s and t become 0 at the same time Is none).

As v of the said Formula (x2-1-1), the integer of 1-15 is preferable, and the integer of 1-12 is more preferable.

About w, as w of said formula (x2-1-2), the integer of 5-20 is preferable and the integer of 10-18 is more preferable. Moreover, as w of said formula (x2-1-3), the integer of 1-17 is preferable and the integer of 3-12 is more preferable. As w of said (x2-1-4), the integer of 1-15 is preferable and the integer of 1-8 is more preferable. As w of said (x2-1-8), the integer of 1-15 is preferable, and the integer of 1-8 is more preferable.

As r of said Formula (x2-1-5) and Formula (x2-1-6), the integer of 0-15 is preferable and the integer of 0-8 is more preferable.

As q of Formula (x2-1-6), the integer of 1-12 is preferable and the integer of 1-5 is more preferable.

As j of Formula (x2-1-7), the integer of 1-15 is preferable and the integer of 1-8 is more preferable.

Among these compounds, compounds represented by at least any of the formulas (x2-1-2) to (x2-1-5), (x2-1-7) and (x2-1-8) are preferable, and specifically, And the compound represented by following formula (x2-2-1)? (X2-2-8) are preferable.

 The compound represented by said formula (x2-1) is a compound which becomes a site | part which provides pretilt angle expression property to the liquid crystal aligning film obtained by reacting with the polyorganosiloxane which has an epoxy group with reactive compound X1. In this specification, the compound represented by said formula (x2-1) may be called "other pretilt-angle expressing compound" below.

The use ratio of the other pretilt-angle expressing compound is preferably 0 to 50 mol%, more preferably 0 to 35 mol%, more preferably 0? To the silicon atom of the polyorganosiloxane. 20 mol%. The other pretilt-expressing compound is preferably used in a range of 75 mol% or less, more preferably 50 mol% or less, based on the total amount of the reactive compound X1. By setting the use ratio of other pretilt-angle expressing compounds to 75 mol% or less, the high speed response of a liquid crystal can be made more favorable.

[2] other reactive compounds (X2-2)

In other reactive compounds (X2-2), examples of the structure that generates radicals by light irradiation and a structure having a photosensitizing function include, for example, a benzophenone structure, a 1,3-dinitrobenzene structure, and a 9,10-di Oxodihydroanthracene structure, 1,4-dioxocyclohexa-2,5-diene structure, etc. are mentioned. Here, the photosensitivity function is a singlet excited state by irradiation of light, and then rapidly crosses a term and transitions to a triplet excited state, and collides with other molecules in this triplet excited state to excite an opponent. It is a function of changing to a state and returning to a base state by itself. This photosensitization function may coexist with the function which generate | occur | produces a radical by light irradiation.

Specific examples of the compound having such a structure include 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3- (4-diethylamino-2-hydroxybenzoyl) benzoic acid and 4- (2-hydroxybenzoyl). Benzoic acid, 3- (2-hydroxybenzoyl) benzoic acid, 2- (2-hydroxybenzoyl) benzoic acid, 4- (4-methylbenzoyl) benzoic acid, 4- (3,4-dimethylbenzoyl) benzoic acid, 3- (4 -Benzoyl-phenoxy) propionic acid, 9,10-dioxodiohydroanthracene-2-carboxylic acid (anthraquinone-2-carboxylic acid), 3- (9,10-dioxo-9,10-dihydroanthracene- 2-yl) propionic acid, 3- (4,5-dimethoxy-3,6-dioxocyclohexa-1,4-dienyl) propoxy] acetyl acid, 3,5-dinitrobenzoic acid, 4-methyl- 3,5-dinitrobenzoic acid, 3- (3,5-dinitrophenoxy) propionic acid, 2-methyl-3,5-dinitrobenzoic acid, etc. are mentioned.

The use ratio of the sum total of other reactive compound (X2-2) is 0-10 mol% with respect to the silicon atom which polyorganosiloxane has, More preferably, it is 0-5 mol%.

[3] other reactive compounds (X2-3)

As other reactive compound (X2-3), carbonic acid, such as formic acid, acetic acid, a propionic acid, benzoic acid, etc. are mentioned, for example. The use ratio of other reactive compound (X2-3) is 0-25 mol% with respect to the silicon atom which polyorganosiloxane has, Preferably it is 0-10 mol%.

It is preferable that the usage-amount of the reactive compound X1 in the case of containing other reactive compound X2 is 10 mol% or more with respect to the total amount of reactive compound X1 and other reactive compound X2. Moreover, it is preferable that it is 5-90 mol% with respect to the silicon atom which polysiloxane precursor has, and, as for the total amount Q1 of reactive compound X1 and other reactive compound X2, it is more preferable that it is 10-70 mol%. Moreover, when using other reactive compound (X2-2), it is preferable that it is 30 mol% or less with respect to the said total amount Q1, and, as for the usage-amount, to ensure better afterimage characteristic, it is more preferable that it is 15 mol% or less.

The reaction of the polysiloxane precursor with the reactive compound X1 can be carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.

As a catalyst used here, the organic base illustrated as a catalyst used for the synthesis | combination of a polysiloxane precursor can be used, for example, the reaction of the epoxy group which a polysiloxane precursor has, and the group which can react with the epoxy group which the reactive compound X1 has A well-known compound can be used as a so-called hardening accelerator which accelerates | stimulates.

It is preferable that the usage-amount of a catalyst is 100 weight part or less with respect to 100 weight part of polysiloxane precursors, It is more preferable that it is 0.01-100 weight part, It is further more preferable that it is 0.1-20 weight part.

As an organic solvent used for reaction of a polysiloxane precursor and reactive compound X1, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound, etc. are mentioned, for example. Among these, an ether compound, an ester compound, and a ketone compound are preferable from a viewpoint of the solubility of a raw material, a product, and the ease of purification of a product. The solvent is used in an amount such that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5-50% by weight. .

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) about specific polyorganosiloxane is 1,000-500,000. By setting it as 1,000 or more, proper anisotropy can be provided to a film, and by making it 500,000 or less, it becomes easy to form a uniform coating film. More preferably, it is 2,000-200,000. Moreover, it is preferable that ratio (Mw / Mn) of Mw with respect to the polystyrene conversion number average molecular weight (henceforth also called "Mn") by GPC is 1.0-5.0, It is more preferable that it is 1.0-3.5, It is 1.0? It is more preferable that it is 2.5.

In the polymer component contained in a 1st aligning agent, the content rate of a specific polyorganosiloxane is 0.1-100 weight part, when the total amount of the polyamic acid and polyimide contained in a 1st aligning agent is 100 weight part. It is preferable, It is more preferable that it is 1-50 weight part, It is still more preferable that it is 5-15 weight part. By setting it as the said range, an appropriate pretilt angle can be expressed, maintaining the applicability | paintability and printability of the liquid crystal aligning agent obtained.

<Specific polyamic acid>

On the other hand, when the 1st aligning agent in this invention contains the polyamic acid (henceforth a specific polyamic acid) which has the said photo-alignment group as a radiation sensitive compound, the said specific polyamic acid is, for example, tetra It can obtain by making carbonic acid dianhydride and the diamine which has the said photo-alignment group react.

(Tetracarbonic acid 2 anhydride)

As tetracarboxylic dianhydride used for the synthesis | combination of specific polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. About these specific examples, As aliphatic tetracarboxylic dianhydride, For example, butane tetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. are mentioned, for example, In addition, tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used.

As tetracarboxylic dianhydride, what contains alicyclic tetracarboxylic dianhydride among these is preferable, Especially, 2,3,5- tricarboxy cyclopentyl acetic acid dianhydride, 3,5,6- tricarboxy-2 Group consisting of carboxymethylnorbornane-2: 3,5: 6-2 anhydride and 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride It is preferable that it is at least 1 sort (s) chosen from.

(Diamine)

Diamine used for the synthesis | combination of specific polyamic acid includes the diamine (henceforth a specific diamine) which has the said photo-alignment group. As the photo-alignment group in this case, one having a structure derived from cinnamic acid is preferable.

The specific diamine should just have one or more said photo-alignment groups in 1 molecule, and it is preferable to have one or two. As such a specific diamine, for example, the optical orientation of groups, for example, _{* -COO- (CH 2) r -O-} , * - (CH 2) r- ( However, r is an integer of 1 10, "? And "*" represents a bond to be bonded to the diamine structure).

As a specific example of specific diamine, what is represented by following formula (d1-1) (d1-15) is mentioned.

As a diamine used for synthesize | combining a specific polyamic acid, diamines other than a specific diamine (henceforth other diamine) can be used together. Specifically as said other diamine, As an aliphatic diamine, For example, 1, 1- methaxylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .; As aromatic diamine, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1 , 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7 -Diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropyl Liden) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) ratio Phenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3 , 6-diaminocarbazole, N- Ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl ) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy- 2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2, 5-diaminobenzene, tetradecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5- Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2, 4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis ( 4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4 -(4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((amino phenyl) methyl) phenyl) -4-butylcyclohexane, 1, 1-bis (4-((aminophenyl) methyl) phenyl) -4-heptyl cyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1 -Bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3- Aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3-diamine, 1,3-bis (N- ( 4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene and the like;

As the diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be cited, and the diamine described in JP 2010-97188 A can be used. Can be.

Moreover, as a diamine used for the synthesis | combination of a specific polyamic acid, the compound represented by following formula (A-1) and the compound represented by following formula (A-2) with a specific diamine for the purpose of making a pretilt characteristic favorable. At least any of these may be included.

(Wherein, X ^Ⅰ, X and X ^{Ⅱ Ⅲ} are, each independently, a single bond, * -O-, * -COO- or * -OCO- bond hand affixed (However, the "*" is bonded to the benzene ring R ¹ is an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1) .

(In formula, R <^III> is respectively independently a hydrogen atom or a C1-C12 alkyl group, and R <^IV> and R <^V> are each independently a hydrogen atom or a methyl group.).

The formula -X ^Ⅰ in _{(A-1) - n (} R I -X Ⅱ) -? As the divalent group represented by, C 1 of 3 alkanediyl group, * -O-, * -COO- or * It is preferable that -O-CH ₂ CH ₂ -O- (wherein the bond to which "*" is attached is bonded to a diaminophenyl group). Group C _c H _{2c +1} - Specific examples of, for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. The two primary amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

As a specific example of a compound represented by said formula (A-1), the compound etc. which are represented by each of following formula (d2-1) (d2-7) are mentioned, for example.

As a compound represented by said formula (A-2), N, N- diallyl-2, 4- diamino aniline is preferable.

It is preferable that the content rate of the specific diamine with respect to all the diamine is 50-100 mol%, and, as for the diamine used for synthesize | combining a specific polyamic acid, it is more preferable that it is 80-100 mol%.

Synthesis of Specific Polyamic Acid

As for the use ratio of tetracarboxylic dianhydride and diamine provided for the synthesis reaction of polyamic acid, the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2-2 equivalent with respect to 1 equivalent of amino group of diamine is 0.3, The ratio of? 1.2 equivalent is more preferable.

The synthesis reaction of polyamic acid is preferably in an organic solvent, Preferably it is -20 degreeC-150 degreeC, More preferably, it is 0-100 degreeC, Preferably it is 0.1-120 hours, More preferably, it is 0.5-48 Time is done.

Here, as an organic solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, Aprotic polar solvents such as hexamethylphosphotriamide; Phenolic solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, are mentioned. It is preferable that the total amount (b) of tetracarboxylic dianhydride and diamine is an amount which will be 0.1-50 weight% with respect to the total amount (a + b) of a reaction solution, as for the usage-amount (a) of an organic solvent.

About specific polyamic acid, it is preferable that it is 1,000-500,000, and, as for the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC), it is more preferable that it is 5,000-300,000. By setting it as the said range, while providing appropriate anisotropy to a film, a more uniform coating film can be formed.

<Specific polyimide>

When the 1st aligning agent in this invention contains the polyimide (henceforth a specific polyimide) which has the said photo-alignment group as a radiation sensitive compound, the said specific polyimide dehydrates said specific polyamic acid. It can obtain by ring-closing and imidizing.

The specific polyimide may be a complete imide obtained by dehydrating and ring-closing all of the dark acid structures possessed by the polyamic acid as its precursor, or by partially dehydrating and ring-closing a part of the dark acid structure, and partially imidized by the dark acid structure and the imide ring structure. It may be. It is preferable that the imidation ratio is 30% or more, and, as for a specific polyimide, it is more preferable that it is 40 to 90%. In addition, this imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. . Among these, it is preferable to depend on the latter method.

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0? 180 占 폚, more preferably 10? 150 占 폚. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

When the content rate of specific polyamic acid and a specific polyimide makes 100 weight part of polyamic acid and polyimide contained as a polymer component, it is preferable that it is 5-100 weight part, It is more preferable that it is 10-100 weight part Do.

<Polyamic acid and polyimide>

The first alignment agent is an essential component when the radiation sensitive compound is a specific polyorganosiloxane, or an optional component when the radiation sensitive compound is a specific polyamic acid or a specific polyimide, and has no photoalignment group. At least any one of polyamic acid and polyimide. As said polyamic acid, the reaction product of the compound illustrated as carboxylic acid dianhydride used for the synthesis | combination of specific polyamic acid, and the compound illustrated as other diamine can be used, for example. As the polyimide, one obtained by dehydrating and ring-closing polyamic acid as the reaction product can be used.

(Other components of the first alignment agent)

It is preferable that a 1st orientation agent is prepared as a solution composition in which the polymer component contained in the said orientation agent melt | dissolved in the suitable organic solvent. As such an organic solvent, what is necessary is just to melt | dissolve the said polymer component and not to react with these, For example, the organic solvent illustrated as what is used for the synthesis | combination of the said specific polyorganosiloxane is mentioned.

In addition, a 1st aligning agent may arbitrarily contain other components other than a polymer component. Examples of the other components include polymers other than polyorganosiloxane, polyamic acid, and imidized polymers, curing agents, curing catalysts, curing accelerators, epoxy compounds, functional silane compounds, surfactants, photosensitizers, and the like. Can be.

[Second alignment agent]

The second alignment agent for forming the second alignment film 15 is capable of forming a vertical alignment film in which the liquid crystal molecules are vertically aligned. As a 2nd aligning agent, any of (1) the aligning agent which does not contain the radiation sensitive compound which has a photo-alignment group substantially, and (2) the aligning agent containing said radiation sensitive compound may be sufficient. In the case of (1), for example, a polyamic acid obtained by the reaction of a compound exemplified as a carboxylic acid dianhydride used in the synthesis of the specific polyamic acid as a polymer component and a compound exemplified as the other diamine or the like The thing containing an imidation polymer can be used. In addition, in the case of (2), the thing similar to what was illustrated by the said 1st aligning agent can be used. In addition, at the time of formation of a 2nd alignment film, which liquid crystal aligning agent is used in (1) and (2) is suitably selected according to the process of manufacturing the said liquid crystal display element.

[Method of Manufacturing Liquid Crystal Display Element]

In the manufacturing method of the liquid crystal display element of this invention, the 1st alignment film 13 which inclines orients liquid crystal molecules with respect to the direction perpendicular | vertical to the said substrate surface is formed in one of the pair of board | substrates, and the other The process of manufacturing the liquid crystal display element 10 in which the 2nd alignment film 15 which vertically orientates a liquid crystal molecule is formed in the board | substrate surface is included. Specifically as this manufacturing method, the following two aspects are preferable.

[First Manufacturing Method]

The 1st manufacturing method for manufacturing the liquid crystal display element 10 of this invention manufactures the liquid crystal display element 10 of this invention by building up a liquid crystal cell using the board | substrate with which the 1st alignment film 13 was formed, Specifically, the following steps are included.

{First film formation process}

This process is a process of forming a 1st coating film in the surface of one of a pair of board | substrates using the said 1st aligning agent as a liquid crystal aligning agent for photoalignments. Specifically, first, the first alignment agent is applied to an appropriate coating method such as a roll coater method, a spinner method, a printing method, an inkjet method, and the like on the electrode surface side of the substrate 11a having the first electrode 12. By coating. The substrate 11a used here may be capable of regulating the tilting direction of the liquid crystal molecules by slit electrodes or ribs (protrusions) patterned in a slit shape, or may not be provided with slit electrodes or ribs. . In addition, when using the conductive film patterned in the slit shape as the 1st electrode 12, in order to obtain this, for example, after forming a conductive film without a pattern, the method of forming a pattern by photo-etching and a conductive film When forming, it can be based on a method using a mask having a desired pattern.

Subsequently, the coated surface is preheated (prebaked), and then calcined (postbaked) to form a coating film. Prebaking conditions are 0.1-5 minutes, for example at 40-120 degreeC, Post-baking conditions are preferably 120-300 degreeC, More preferably, it is 150-250 degreeC, Preferably it is 5-200 minutes. More preferably, it is 10-100 minutes. The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

Solid content concentration of the liquid crystal aligning agent used when apply | coating a liquid crystal aligning agent on a board | substrate (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) takes into consideration viscosity, volatility, etc. Although it selects suitably, Preferably it is 1 to 10 weight% of range. When solid content concentration is less than 1 weight%, the film thickness of a coating film becomes small and it is difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and it is difficult to obtain a favorable liquid crystal aligning film, and there exists a possibility that the viscosity of a liquid crystal aligning agent may increase and coating characteristics may fall.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable by the spin coating method. When using the offset printing method, it is especially preferable to make solid content concentration into the range of 3-9 weight%, and to make solution viscosity into the range of 12-50 mPa * s. When using inkjet printing method, it is especially preferable to make solid content concentration into the range of 1-5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

Moreover, before apply | coating a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface (1st electrode 12) and a coating film more favorable, a functional silane compound in the surface which should form a coating film in the board | substrate surface, You may perform the pretreatment which apply | coats a functional titanium compound etc. beforehand.

{Light irradiation process}

This process is a process of making the 1st coating film into the 1st alignment film 13 as a photo-alignment film by irradiating light to the 1st coating film formed on the board | substrate 11a. As the irradiation light to the first coating film, any of polarized radiation and non-polarized radiation may be used, and in the case of polarized radiation, linearly polarized light, partial polarized light, and the like can be used, but preferably linearly polarized light. As the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used. Of these, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable.

The irradiation direction of light to the first coating film is in a direction oblique to the substrate surface in order to give a pretilt angle. What is necessary is just to set the irradiation angle in this case suitably according to the pretilt angle to express in a 1st coating film. By such light irradiation, it is preferable to make the pretilt angle in the 1st alignment film 13 into 85 to 89.5 degrees, and it is more preferable to set to 87 to 89 degrees.

As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a mercury xenon lamp, a deuterium lamp, a halogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using a light source together with a filter, a diffraction grating, or the like, for example.

As an irradiation amount of radiation, Preferably they are 1 J / m <2> or less than 10,000 J / m <2>, More preferably, it is 10-3,000 J / m <2>.

{Second film formation process}

This process uses a 2nd aligning agent as a liquid crystal aligning agent which can form a vertical alignment film in the surface of one board | substrate 11b which does not form a 1st coating film among a pair of board | substrates 11a and 11b. 2 It is a process of forming a coating film. Formation of a 2nd coating film can be basically performed by the method similar to the coating film formation in the said 1st film formation process. In addition, also about the board | substrate 11b used here, the inclination direction of liquid crystal molecules may be regulated with a slit electrode or a rib, and they may not be provided.

As a 2nd aligning agent in this manufacturing method, you may use either (1) what does not contain a radiation sensitive compound which has a photo-alignment group substantially, and (2) contains the said radiation sensitive compound. When using the thing of (2) as a 2nd aligning agent, you may use the thing similar to what was illustrated as said 1st aligning agent, In that case, the same kind as used for formation of a 1st coating film, or a different kind may be used. However, even when using the thing of (2) as a 2nd aligning agent, light irradiation is not performed about the 2nd coating film formed in the said board | substrate 11b.

In addition, although the 2nd coating film formed as mentioned above can be used as a vertical alignment film (2nd alignment film 15) as it is, the formed coating film is rubbed in a fixed direction with the roll wound the cloth which consists of fibers, such as nylon, rayon, and cotton, for example. You may perform a process (rubbing process).

{Cell building process}

Subsequently, two board | substrates 11a and 11b in which the liquid crystal aligning film was formed respectively are arrange | positioned so that the 1st alignment film 13 and the vertical alignment film (2nd alignment film 15) as a 2nd coating film may face, and a liquid crystal cell is built up. do. To construct a liquid crystal cell, the following two methods are mentioned, for example.

In a 1st method, first, two board | substrates 11a and 11b are opposingly arranged through gap | interval (cell gap) so that each liquid crystal aligning film may oppose, and a sealing compound will be made into the peripheral part of two board | substrates 11a and 11b. To join. Next, the liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the sealing agent, and then the injection hole is sealed. As a result, a liquid crystal cell is constructed.

The second method is a method called an ODF (One Drop Fill) method. That is, an ultraviolet-ray curable sealing compound is apply | coated to predetermined | prescribed place on one board | substrate among two board | substrates 11a and 11b in which the liquid crystal aligning film was formed, and the liquid crystal was dripped further on the liquid crystal aligning film surface. Thereafter, the other substrate is bonded to face the liquid crystal alignment film. Subsequently, ultraviolet light is irradiated to the entire surface of the substrate to cure the sealing agent. As a result, a liquid crystal cell is constructed.

Moreover, also in the case of any method, it is preferable to cool gradually to room temperature after heating the liquid crystal cell produced above to the temperature which a liquid crystal used takes an isotropic phase for the purpose of removing the flow orientation at the time of liquid crystal filling. .

About the constructed liquid crystal cell, the liquid crystal display element 10 of this invention is obtained by contacting the polarizing plates 18 and 19 on each outer surface of two board | substrates 11a and 11b. At this time, the polarization directions of the polarizing plates 18 and 19 are perpendicular to each other, and in the substrate on which the first alignment layer 13 is formed, the angle of 45 ° to the projection direction of the optical axis of the optical axis to the substrate surface is formed. Bond the polarizing plate.

As said sealing agent, the epoxy resin etc. containing the aluminum oxide sphere as a spacer, a hardening | curing agent, etc. can be used, for example.

Second Production Method

The 2nd manufacturing method for manufacturing the liquid crystal display element 10 of this invention forms a coating film on the surface of each board | substrate using a liquid crystal aligning agent, and after constructing a liquid crystal cell using the board | substrate with which the said coating film was formed, the liquid crystal By irradiating light to a cell, the liquid crystal display element 10 of this invention is manufactured. Specifically, the following process is included.

{First film formation process}

This process is a process of forming a coating film on the surface of one board | substrate 11a among a pair of board | substrates 11a and 11b using the 1st aligning agent as a liquid crystal aligning agent for photoalignments. However, in this manufacturing method, the board | substrate provided with the electrode (1st electrode 12 and the 2nd electrode 14) which has a slit-shaped pattern is used as the board | substrate 11a, 11b which forms a coating film. In addition, about the formation method of a coating film, the thing described in the 1st film formation process in the said 1st manufacturing method is applicable.

{Second film formation process}

This process is a process of forming the 2nd alignment film 15 using the 2nd alignment agent on the surface of the other board | substrate 11b among the pair of board | substrates 11a and 11b. At this time, as a 2nd aligning agent, the liquid crystal aligning agent which does not contain the radiation sensitive compound which has a photo-alignment group substantially, ie, the 2nd aligning agent (1) illustrated by the 2nd film formation process in the said 1st manufacturing method (1) of (2) is used.

In addition, although the 2nd alignment film 15 formed as mentioned above can be used as it is, you may perform a rubbing process with respect to the formed coating film.

{Cell building process}

In this step, the film-formed two substrates 11a and 11b are arranged so that the respective films face each other to form a liquid crystal cell. As a method of constructing a liquid crystal cell, the two methods demonstrated by the cell construction process in the said 1st manufacturing method are mentioned.

{Light irradiation process}

In this process, the liquid crystal aligning property is provided to the coating film formed by the 1st aligning agent by irradiating light to the said liquid crystal cell in the state which applied the voltage between a pair of board | substrates. Thereby, this coating film is made into the film (1st aligning film 13) which can align liquid crystal molecules inclined with respect to the direction perpendicular | vertical to the surface of a board | substrate.

The voltage to be applied can be, for example, a direct current or an alternating current of 5 to 50 V. In this case, when the patterned conductive film partitioned into a plurality of regions is formed as the conductive film on the substrate surface, this voltage is used. By applying a different voltage in each region at the time of application, the inclination direction of the liquid crystal molecules can be changed for each region in the coating film. Thereby, it becomes possible to make viewing angle characteristic wider.

Although the light irradiated to a liquid crystal cell may use either polarized radiation or non-polarization radiation, non-polarization is preferable. In addition, when irradiating non-polarization radiation, it is preferable to carry out from a perpendicular direction with respect to the board | substrate surface.

As the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. As a light source of irradiation radiation, the thing similar to the light source illustrated in the said 1st manufacturing method can be illustrated.

As an irradiation amount of radiation, Preferably it is 1,000 J / m <2> or more and less than 100,000 J / m <2>, More preferably, it is 1,000 J / m <2> or more and 50,000 J / m <2> or less.

By such light irradiation, it is preferable to make the pretilt angle in the 1st alignment film 13 into 85 to 89.5 degrees, and it is more preferable to set to 87 to 89 degrees.

About the liquid crystal cell after light irradiation, the liquid crystal display element of this invention is bonded by bonding the polarizing plates 18 and 19 to each outer surface of two board | substrates 11a and 11b by the method similar to the said 1st manufacturing method. (10) can be obtained.

The liquid crystal display element of the present invention can be effectively applied to various devices as a VA type liquid crystal display element. For example, a clock, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, a PDA And display devices such as digital cameras, mobile phones, various monitors, and liquid crystal televisions.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

In addition, below, the weight average molecular weight (Mw), the number average molecular weight (Mn), the epoxy equivalent, the solution viscosity of a polymer solution, and the imidation ratio of polyimide were measured as follows.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by the gel permeation chromatography (GPC) which makes monodisperse polystyrene the standard on condition of the following.

Column: Tosoh Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68㎏f / ㎠

Epoxy equivalent was measured according to the "hydrochloric acid methyl methyl ketone method" of JIS C2105.

The solution viscosity (mPa? S) of the polymer solution is 25 in N-methyl-2-pyrrolidone (NMP) solvent by using an E-type rotational viscometer with a viscosity at a concentration of 20% by weight of each polyamic acid. Measured at ℃.

Imidization ratio of the polyimide is added to an NMP solution of the polyimide in a pure, dissolved the resulting precipitate in sufficiently dried under reduced pressure and then, deuterated dimethyl sulfoxide at room temperature, with tetramethylsilane as a standard substance, ^one at room temperature H-NMR was measured. H-NMR spectrum obtained from the ^first, to the imidization ratio was calculated according to the equation represented by the formula (1).

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (1)

(In Formula (1), A <^1> is the peak area derived from the proton of the NH group represented by 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. Number ratio of other protons to one proton of NH group).

¹ H-NMR analysis was performed using a nuclear magnetic resonance apparatus (trade name: JNM-ECX400, manufactured by Nihon Denshi Corporation).

The synthesis | combination of a raw material compound and a polymer was repeated as needed with the following synthesis scale, and the necessary amount used for subsequent synthesis was ensured.

[Synthesis of polyorganosiloxane having an epoxy group]

Synthesis Example E-1

Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 5OOg of methyl isobutyl ketone, and 10.0 g of triethylamine were added thereto. Mix at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After the completion of the reaction, the organic layer was taken out and washed with an aqueous 0.2% by weight ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group ( EPS-1) was obtained as a viscous transparent liquid.

As a result of ¹ H-NMR analysis of this polyorganosiloxane (EPS-1), a peak based on an epoxy group was obtained according to the theoretical strength in the vicinity of chemical shift (δ) = 3.2 ppm. This confirmed that side reactions of epoxy groups did not occur during the reaction.

The weight average molecular weight (Mw) of the obtained polyorganosiloxane (EPS-1) was 2,200, and the epoxy equivalent was 186 g / mol.

[Synthesis of cinnamic acid derivative (A)]

Synthesis Example A-1

Cinnamic acid derivative (A-1) was synthesized according to the following Scheme 1.

 91.3 g of 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone were added to a 1 L branched flask, followed by stirring at room temperature for 1 hour, followed by 1-iodine-4,4, 157.1 g of 4-trifluorobutane were added, and it stirred at 100 degreeC for 5 hours. After the reaction was completed, reprecipitation was carried out with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to perform a hydrolysis reaction. After completion | finish of reaction, it neutralized with hydrochloric acid and recrystallized the precipitate which generate | occur | produced, and obtained 110g of white crystals of a compound (A-1-1).

12.41 g of this compound (A-1-1) was taken out in the reaction container, 100 mL of thionyl chloride and 77 microliters of N, N- dimethylformamide were added to this, and it stirred at 80 degreeC for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution.

Next, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran and 100 mL of water were placed in a 500 mL three-neck flask different from the above. The aqueous solution was ice-cooled, and the tetrahydrofuran solution was slowly added dropwise, and the reaction was further performed under stirring for 2 hours. After completion of the reaction, hydrochloric acid was added to neutralize, extracted with ethyl acetate, dried over magnesium sulfate, concentrated, and recrystallized with ethanol to obtain 10.0 g of white crystals of cinnamic acid derivative (A-1).

Synthesis Example A-2

According to the following scheme 2, cinnamic acid derivative (A-2) was synthesized.

In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 31 g of compound (A-2-1), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, and acrylic acid 8.2 mL and 200 mL of N, N-dimethylacetamide were added thereto, and the reaction was carried out at 120 ° C. for 3 hours with stirring. After the completion of the reaction, the organic layer obtained by adding 1 L of ethyl acetate to the filtrate obtained by filtering the reaction mixture was washed twice with dilute hydrochloric acid and three times with water, and dried over magnesium sulfate. Then, 15 g of crystals of cinnamic acid derivative (A-2) were obtained by recrystallizing the solid obtained by removing a solvent under reduced pressure from the mixed solvent of ethyl acetate and tetrahydrofuran.

Synthesis Example A-3

Cinnamic acid derivatives (A-3) were synthesized according to Scheme 3 below.

Into a 300 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, 21 g of a compound (A-3-1), 80 mL of thionyl chloride, and 0.1 mL of N, N-dimethylformamide were added and the reaction was stirred at 80 ° C. for 1 hour. Done. After completion of the reaction, thionyl chloride was distilled off from the reaction mixture, and then the organic layer obtained by adding 150 mL of methylene chloride was washed three times with water. After drying this organic layer with magnesium sulfate, 400 mL of tetrahydrofuran was added to the solid obtained by removing a solvent under reduced pressure.

Meanwhile, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water, and 100 mL of tetrahydrofuran were placed in a 1 L three-necked flask equipped with a dropping lot and a thermometer, and ice-cooled to 5 ° C. or lower. . Here, the said tetrahydrofuran solution was dripped over 3 hours, and also reaction was performed under stirring for 1 hour. After completion | finish of reaction, after adding diluted hydrochloric acid to the reaction mixture to pH 4 or less, the organic layer obtained by adding 3 L of toluene and 1 L of tetrahydrofuran was wash | cleaned 3 times with water. After drying this organic layer with magnesium sulfate, the solvent was removed under reduced pressure and the solid obtained was recrystallized from the mixed solvent of ethanol and tetrahydrofuran, and 21g of compounds (A-3) were obtained as a cinnamic acid derivative.

[Synthesis of radiation sensitive polyorganosiloxane]

Synthesis Example S-1

In a 300 mL three-necked flask, 30.1 g of the compound (EPS-1) obtained in Synthesis Example E-1 as a polyorganosiloxane having an epoxy group, 140 g of methyl isobutyl ketone, and the cinnamic acid derivative obtained in Synthesis Example A-1 ( A-1) 31.9 g (equivalent to 50 mol% of the silicon atom of the compound (EPS-1)), 4.60 g of stearic acid (equivalent to 10 mol% of the silicon atom of the compound (EPS-1) ), 0.0686 g of 3,5-dinitrobenzoic acid (corresponding to 0.2 mol% of the silicon atom of the compound (EPS-1)) and 3.00 g of tetrabutylammonium bromide were added, and the reaction was stirred at 80 ° C. for 5 hours. Done. After completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution, and the solution was washed with water five times, and then the solvent was distilled off to obtain a weight average molecular weight (as a radiation sensitive polyorganosiloxane). 55.6 g of a white powder of compound (S-1) having Mw) of 12,600 (Mw / Mn = 1.42) was obtained.

Synthesis Example S-2

In a 200 mL three-necked flask, 10.0 g of the compound (EPS-1) obtained in Synthesis Example E-1 as a polyorganosiloxane having an epoxy group, 60 g of methyl isobutyl ketone, and the cinnamic acid derivative obtained in Synthesis Example A-2 ( A-2) 1.62 g (equivalent to 10 mol% of the silicon atom of the compound (EPS-1)), 3.45 g of the cinnamic acid derivative (A-3) obtained in Synthesis Example A-3 (compound (EPS- Corresponding to 15 mol% of the silicon atom of 1)) and 1.00 g of tetrabutylammonium bromide were added, and the reaction was performed at 80 ° C under stirring for 2 hours. After completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution, and the solution was washed with water five times, and then the solvent was distilled off to obtain a weight average molecular weight (as a radiation sensitive polyorganosiloxane). 12.8g of white powder of compound (S-2) whose Mw) is 11,200 (Mw / Mn = 1.13) was obtained.

(Example S-3)

In a 50 mL three-necked flask, 2.01 g of the compound (EPS-1) obtained in Synthesis Example E-1 as a polyorganosiloxane having an epoxy group, 16 g of methyl isobutyl ketone, and the cinnamic acid derivative obtained in Synthesis Example A-2 ( A-2) 1.61 g (equivalent to 50 mol% of the silicon atom of the compound (EPS-1)), 0.356 g of 4-tert-butoxycarbonylbenzoic acid (to the silicon atom of the compound (EPS-1)) Equivalent to 15 mol%) and tetrabutylammonium bromide were added thereto, and the reaction was performed at 80 ° C under stirring for 2 hours. After completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution, and the solution was washed with water five times, and then the solvent was distilled off to obtain a weight average molecular weight (as a radiation sensitive polyorganosiloxane). 3.46 g of white powder of compound (S-3) whose Mw) is 14,700 (Mw / Mn = 1.51) were obtained.

[Synthesis of polyamic acid and polyimide]

Synthesis Example P-1

19.61 g (0.1 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino 2,2'-dimethylbiphenyl are N-methyl-2- It dissolved in 367.6 g of pyrrolidone and reacted for 6 hours at room temperature. The reaction mixture was then poured into a large excess of methanol and the reaction product precipitated out. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-1).

Synthesis Example P-2

21.81 g (0.0973 mol) of 2,3,5-tricarboxycyclopentyl acetic anhydride and 19.29 g (0.0390 mol) of 5ξ-cholestan-3-yl 2,4-diaminophenyl ether represented by the following formula (p1), 8.90 g (0.0585 mol) of 3,5-diaminobenzoic acid was dissolved in 200 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 5 hours. It was 1450 mPa * s when the viscosity of this polymerization solution was measured. Subsequently, 250 g of N-methyl-2-pyrrolidone was added to this solution, followed by stirring for some time, followed by addition of 11.55 g of pyridine and 14.90 g of acetic anhydride, followed by dehydration and ring closure at 110 ° C. for 4 hours. Thereafter, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 37.5 g of polyimide (PI-1) having an imidation ratio of 69%.

Synthesis Example P-3

23.38 g (0.104 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 15.50 g (0.0313 mol) of 5ξ-cholestan-3-yl 2,4-diaminophenyl ether represented by the formula (p1), 11.12 g (0.0731 mol) of 3,5-diaminobenzoic acid was melt | dissolved in 200 g of N-methyl- 2-pyrrolidone, and it was made to react at 60 degreeC for 5 hours. Subsequently, 250 g of N-methyl-2-pyrrolidone was added to this solution, followed by stirring for some time, followed by addition of 12.37 g of pyridine and 15.97 g of acetic anhydride, followed by dehydration and closing for 4 hours at 110 ° C. Thereafter, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 36.4 g of polyimide (PI-2) having an imidation ratio of 71%.

Synthesis Example P-4

2,3,5-tricarboxycyclopentylacetic acid dianhydride 26.73 g (0.119 mol) and 6-{[((2E) -3- {4-[(4- (3,3, 3-trifluoropropoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} hexyl-3,5-diaminobenzoate 73.27 g (0.119 mol) was converted to N-methyl-2-pyrroli It was dissolved in 185.7 g of pigs and allowed to react at 60 ° C for 24 hours. It was 4800 mPa * s when the viscosity of this polymerization solution was measured. The reaction mixture was then poured into a large excess of methanol and the reaction product precipitated out. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 70 g of polyamic acid (PA-2).

Synthesis Example P-5

2,3,5-tricarboxycyclopentylacetic acid dianhydride 27.07 g (0.121 mol) and 6-{[((2E) -3- {4-[(4- (3,3, 3-trifluoropropoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} hexyl-3,5-diaminobenzoate 66.79 g (0.109 mol), 5ξ represented by the formula (p1) 2.99 g (0.00604 mol) of -cholestan-3-yl 2,4-diaminophenyl ether and 3.16 g (0.00604) of 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl represented by the following formula (p3): Mole) was dissolved in 185.7 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 24 hours. It was 2100 mPa * s when the viscosity of this polymerization solution was measured. The reaction mixture was then poured into a large excess of methanol and the reaction product precipitated out. 68g of polyamic acid (PA-3) was obtained by wash | cleaning a deposit with methanol and drying at 40 degreeC under reduced pressure for 15 hours.

Synthesis Example P-6

18.75 g (0.0836 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 7.359 g (0.0681 mol) of p-phenylenediamine as a diamine compound, and 3 represented by said Formula (p3) 8.895 g (0.0170 mol) of, 5-diaminobenzoic acid = 5ξ-cholestan-3-yl was dissolved in 140 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 5 hours. It was 2000 mPa * s when the viscosity of this polymerization solution was measured. Subsequently, 325 g of N-methyl-2-pyrrolidone was added to this solution, followed by stirring for some time, and then 6.61 g of pyridine and 8.54 g of acetic anhydride were added and dehydrated and closed for 4 hours at 110 ° C. Thereafter, the reaction solution was poured into a large amount of methyl alcohol, and the reaction product was precipitated. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 26.6 g of polyimide (PI-3) having an imidation ratio of 51%.

[Preparation of liquid crystal aligning agent]

(Preparation Example 1)

Radiation-sensitive poly obtained in Synthesis Example S-1 to 30 parts by weight of polyamic acid (PA-1) obtained in Synthesis Example P-1 and 70 parts by weight of polyimide (PI-1) obtained in Synthesis Example P-2. 10 parts by weight of organosiloxane (S-1), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added so that the solvent composition was NMP: BC = 45: 55 (weight ratio), Solid content concentration was made into the 3.5 weight% solution. The liquid crystal aligning agent (AF-1) was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

(Formulation Examples 2-7)

A liquid crystal aligning agent (AF- was prepared in the same manner as in Preparation Example 1 except that the kind and amount of radiation-sensitive polyorganosiloxane, the kind and amount of polyamic acid and polyimide, and the solvent composition were as described in Table 1, respectively. (AF-7) was prepared respectively.

(Preparation Example 8)

20 parts by weight of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane based on 100 parts by weight of the polyimide (PI-3) obtained in Synthesis Example P-6, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added so that a solvent composition might be NMP: BC = 50: 50 (weight ratio), and solid content concentration was made into the solution of 3.5 weight%. The liquid crystal aligning agent (AF-8) was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

[Manufacture of Liquid Crystal Display Element]

(Example 1)

After apply | coating the liquid crystal aligning agent (AF-1) prepared by the said preparation example 1 with the spinner on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, and prebaking for 1 minute on 80 degreeC hotplate, In the oven which nitrogen-substituted the inside, it heated at 200 degreeC for 1 hour, and formed the coating film of 80 nm in film thickness. Subsequently, the coating film surface was irradiated with a polarized ultraviolet ray of 200 J / m 2 containing 313 nm of bright lines using a Hg-Xe lamp and a gland taylor prism from a 40 ° tilted direction with respect to the direction perpendicular to the substrate surface. Made.

In addition, on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, the liquid crystal aligning agent (AF-1) prepared by the said preparation example 1 was apply | coated with a spinner, and it was carried out by 1 with an 80 degreeC hotplate. After prebaking for minutes, the board | substrate B which heated at 200 degreeC for 1 hour in oven which nitrogen-substituted the inside, and formed the coating film with a film thickness of 80 nm was produced. In addition, polarizing UV irradiation was not performed to the board | substrate B side.

After screen-printing the aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter to the outer periphery of the surface which has the coating film of the said board | substrate B, it is made to face the coating film surface of the board | substrate A, and it crimped, and it is 150 degreeC over 1 hour. The adhesive was thermoset. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between a board | substrate from a liquid crystal injection port, the liquid crystal injection hole was sealed with the acryl-type photocuring adhesive agent. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating at 150 degreeC for 10 minutes, it cooled gradually to room temperature. Next, the polarizing plate is bonded to the outer both surfaces of the board | substrates A and B so that the polarization directions may mutually orthogonally cross, and the board | substrate A may make an angle of 45 degrees with the projection direction to the board | substrate surface of the optical axis of an ultraviolet-ray, liquid crystal display The device was manufactured.

(Examples 2-7)

A liquid crystal cell was produced by the same method as in Example 1, except that the liquid crystal aligning agent was used in Table 2 below.

(Example 8)

1. Construction of evaluation cell [1]

First, the liquid crystal aligning agent (AF-1) prepared in the said Preparation Example 1 was apply | coated with the spinner on the transparent electrode surface of the glass substrate which has the transparent conductive film (ITO film) patterned in the slit shape. As a pattern of a transparent electrode, the thing of the slit-shaped 5 micrometers of lines and space as shown in FIG. 2 was used, respectively. Subsequently, after prebaking was performed for 1 minute on the 80 degreeC hotplate, the board | substrate A which heated at 200 degreeC for 1 hour in the oven which carried out the nitrogen substitution inside, and formed the coating film of 80 nm in thickness was produced. Similarly, the liquid crystal aligning agent (AF-8) prepared in the said Preparation Example 8 was apply | coated with the spinner on the transparent electrode surface of the glass substrate which has the ITO film patterned in the slit shape shown in FIG. After prebaking for 1 minute on the plate, the board | substrate B which heated at 200 degreeC for 1 hour in the oven which carried out the nitrogen substitution inside, and formed the liquid crystal aligning film of film thickness 80nm was produced.

After apply | coating by screen printing the aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter to the outer periphery of the surface which has the liquid crystal aligning film of the said board | substrate B, the liquid crystal aligning film surface of the board | substrate A is faced and crimped | bonded, and it is crimped at 150 degreeC for 1 hour. The adhesive was thermoset over. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between a board | substrate from a liquid crystal injection port, the liquid crystal injection port was sealed with the acryl-type photocuring adhesive agent, and the liquid crystal cell was constructed. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating at 150 degreeC for 10 minutes, it cooled gradually to room temperature. Furthermore, after irradiating 50,000 J / m <2> of light to a liquid crystal cell in the state which applied AC voltage of 10V using a halogen lamp, the polarizing plate is orthogonal to each other on both outer sides of a cell board | substrate, and In the board | substrate A, the liquid crystal display element was manufactured by joining so that the angle of 45 degree with the projection direction to the board | substrate surface of an optical axis of an ultraviolet-ray was manufactured, and this was set as the evaluation cell [1].

2. Preparation of evaluation cell [2]

Except having used the thing without patterning as a glass substrate with a transparent electrode, the coating film was formed on the board | substrate by the method similar to the said cell 1 for evaluation, and board | substrates A and B were produced. Subsequently, using these board | substrates A and B, in order to build a liquid crystal cell by the same method as the said cell 1 for evaluation, and to remove the flow orientation at the time of liquid crystal injection, after heating this at 150 degreeC for 10 minutes, it gradually rose to room temperature. After cooling, 50,000 J / m <2> light irradiation was performed to the liquid crystal cell of a voltage free state using the halogen lamp. Thereafter, the polarizing plates are bonded to both outer surfaces of the cell substrate so that their polarization directions are perpendicular to each other, and that the liquid crystal display device is bonded to form an angle of 45 ° with the projection direction to the substrate surface of the optical axis of the ultraviolet ray in the substrate A. It produced and made this the cell for evaluation [2].

(Examples 9-14)

Two types of liquid crystal display elements (cells [1] and [2] for evaluation) were produced like Example 8 except having used the thing of the following Table 2 as a liquid crystal aligning agent.

(Comparative Example 1? 3)

While using the thing described in following Table 2 as a liquid crystal aligning agent, the liquid crystal display element was produced like Example 1 except not having performed polarizing UV irradiation of both the board | substrate A and the board | substrate B.

(Comparative Examples 4 and 5)

Except having used what was shown in following Table 2 as a liquid crystal aligning agent, the coating film was formed on each surface of two board | substrates by the method similar to Example 1. Subsequently, each coating film surface was irradiated with a polarized ultraviolet light 200J / m 2 containing 313 nm of bright lines using a Hg-Xe lamp and a gland taylor prism from a direction inclined at 40 ° to the direction perpendicular to the substrate surface to form a liquid crystal alignment film. Substrate A and B which were used were produced.

Subsequently, after apply | coating by screen printing the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5 micrometers to the outer periphery of the surface which has the liquid crystal aligning film of the said board | substrate A, the liquid crystal aligning film surface of the board | substrate B is opposed, and the ultraviolet-ray of each board | substrate is carried out. It crimp | bonded so that the projection direction to the board | substrate surface of the optical axis might become antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between board | substrates from a liquid crystal injection port, the liquid crystal injection hole was sealed with the acryl-type photocuring adhesive, shielding a cell part. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating at 150 degreeC, it cooled gradually to room temperature. Next, the liquid crystal display element was manufactured by bonding the polarizing plate to the outer both surfaces of a board | substrate so that the polarization directions may mutually orthogonally cross, and to make the angle of 45 degrees with the projection direction to the substrate surface of the optical axis of the ultraviolet-ray of a liquid crystal aligning film. .

[Evaluation of Liquid Crystal Display Device]

About the manufactured liquid crystal display element, the characteristic evaluation was performed about each item by the following method.

(1) Evaluation of Voltage Integrity

After applying the voltage of 5V to 60 microseconds application time and the span of 167 milliseconds to the liquid crystal display element manufactured above, the voltage preservation ratio (VHR) after 167 milliseconds after application | release cancellation was measured. As a measuring device, VHR-1 was manufactured by Toyo Technica Co., Ltd. In addition, about Examples 8-14, it carried out using the cell for evaluation [2].

(2) Evaluation of response speed (electro-optical responsiveness at the time of rise)

The time of rise of a liquid crystal response was measured with the apparatus containing a polarizing microscope, a photodetector, and a pulse generator. Herein, the liquid crystal response speed is the time required to change from 10% transmittance to 90% transmittance when a voltage of 5V is applied to the produced liquid crystal display element for up to 1 second from a voltage-free state (unit: milliseconds (msec). .)) Was defined and evaluated. In addition, about Examples 8-14, it carried out using the cell for evaluation [1].

(3) light resistance evaluation

The VHR after 3000-hour irradiation was measured by the weather meter which uses a carbon arc as a light source similarly to said (1). Evaluation was performed by making the thing within 1% of VHR change amount into (circle), 1 ~ 3% thing as (triangle | delta), and 3% or more as x compared with the measured value before irradiation. In addition, about Examples 8-14, it carried out using the cell for evaluation [2].

(4) contrast evaluation

By evaluating the degree of light leakage based on the orientation defect in the produced liquid crystal cell as follows, black level was evaluated and it was set as the replacement evaluation of contrast evaluation. First, it observed with the polarization microscope of cross nicol condition, the liquid crystal cell was arrange | positioned so that it might become the dark field most, and the image was photographed. The obtained data was divided into 0.2 mm square x 25 pixels, and the luminance of each pixel was digitized in 255 gradations using image processing software. Even when the system of each pixel (25 pixels) was 30 or less, the contrast was good ((circle)) and the case where the system was larger than 30 was evaluated as contrast defect (x). In addition, about Examples 8-14, it carried out using the cell for evaluation [1].

The evaluation results of said (1)-(4) are shown in following Table 2.

As shown in Table 2, in the liquid crystal display elements of Examples 1-14, while showing the high voltage holding ratio, the response characteristic of the liquid crystal molecule with respect to a voltage change was favorable. Moreover, in these liquid crystal display elements, also about contrast It was good. In particular, it was excellent also in light resistance about the liquid crystal display element (Examples 1-3, 8-10) using the liquid crystal aligning agent containing a radiation sensitive polyorganosiloxane.

In addition, in Examples 1 to 14, when Examples 1 to 7 in which a liquid crystal cell was constructed after light irradiation on the coating film and Examples 8 to 14 in which light irradiation was constructed after the construction of the liquid crystal cell were compared, the former was a liquid crystal. The response characteristic of the molecule was better.

On the other hand, in Comparative Examples 1-5, the response speed was fast all, and the response characteristic of the liquid crystal molecule with respect to a voltage change was not very good.

Claims (9)

A liquid crystal display device comprising a pair of substrates,
On one of the substrate surfaces of the pair of substrates, a first alignment film for inclining the liquid crystal molecules to be inclined with respect to the direction perpendicular to the substrate surface is formed, and the agent for vertically orienting the liquid crystal molecules on the other substrate surface. 2 alignment film is formed,
The said 1st alignment film is formed using the liquid crystal aligning agent containing the radiation sensitive compound which has a photo-alignment group,
The photo-alignment group is composed of azobenzene, stilbene, α-imino-β-ketoester, spiropyran, spiroxazine, cinnamic acid, chalcone, stilazole, benzylidene phthalimidine, coumarin, diphenylacetylene and anthracene. A liquid crystal display device having a structure derived from at least one compound selected from the group. The method of claim 1,
The liquid crystal display element in which the said photo-alignment group has the structure derived from cinnamic acid. The method according to claim 1 or 2,
A liquid crystal display device comprising the polyorganosiloxane having the photoalignment group as the radiation sensitive compound. As a manufacturing method of a liquid crystal display element provided with a pair of board | substrate,
On one of the substrate surfaces of the pair of substrates, a first alignment film for inclining the liquid crystal molecules to be inclined with respect to the direction perpendicular to the substrate surface is formed, and the agent for vertically orienting the liquid crystal molecules on the other substrate surface. It includes the manufacturing process of manufacturing the liquid crystal display element in which the 2 orientation film was formed,
The first alignment film is formed using a liquid crystal aligning agent for photoalignment containing a radiation sensitive compound having a photoalignment group,
The photo-alignment group is composed of azobenzene, stilbene, α-imino-β-ketoester, spiropyran, spiroxazine, cinnamic acid, chalcone, stilazole, benzylidene phthalimidine, coumarin, diphenylacetylene and anthracene. The manufacturing method of the liquid crystal display element which has a structure derived from at least 1 compound chosen from a group. The method of claim 4, wherein
The manufacturing process,
A first film formation step of forming a first coating film on the surface of one of the pair of substrates using the liquid crystal aligning agent for photo-alignment;
A light irradiation step of making the first coating film the first alignment film by light irradiation with respect to the first coating film,
A second film formation step of forming a second coating film as the second alignment film by using a liquid crystal aligning agent capable of forming a vertical alignment film on the surface of the other one of the pair of substrates;
And a cell building step of arranging the pair of substrates so that the first alignment layer and the second coating layer face each other, and constructing a liquid crystal cell filled with liquid crystal molecules therebetween. The method of claim 4, wherein
The manufacturing process,
A first film forming step of forming a coating film on the surface of one of the pair of substrates using the liquid crystal aligning agent for photoalignment;
A second film formation step of forming the second alignment film on a surface of the other one of the pair of substrates using a liquid crystal aligning agent that does not substantially include a radiation sensitive compound having a photo-alignment group;
A cell building step of constructing a liquid crystal cell in which the pair of substrates are disposed so that the coating film and the second alignment layer face each other, and the liquid crystal molecules are filled between the substrates;
And a light irradiation step of irradiating the liquid crystal cell constructed by the cell building step with light in a state where a voltage is applied between the pair of substrates. 7. The method according to any one of claims 4 to 6,
The said photo-alignment machine has the structure derived from cinnamic acid, The manufacturing method of the liquid crystal display element. 7. The method according to any one of claims 4 to 6,
The manufacturing method of the liquid crystal display element containing the polyorganosiloxane which has the said photo-alignment group as said radiation sensitive compound. The liquid crystal aligning agent used for manufacturing the liquid crystal display element in any one of Claims 1-3.

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