KR20140037830A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element - Google Patents

Abstract

Polyimide which has a side chain which orientates a liquid crystal perpendicularly, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least 1 sort (s) of polymer chosen from a precursor and the polyimide obtained by imidating this polyimide precursor, At least 1 sort (s) of mother nucleus chosen from following formula (i-1)-(i-3), and 1 or more It is set as the liquid crystal aligning agent which has group which photopolymerizes or photocrosslinks at the terminal, and the said photopolymerization or photocrosslinking group is couple | bonded with the said mother core directly or via a coupling group, and a solvent.

Description

Liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and a manufacturing method of a liquid crystal display element

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and a method for manufacturing a liquid crystal display element, which can be used for the production of a liquid crystal display element of a vertical alignment method produced by irradiating ultraviolet rays in a state where voltage is applied to liquid crystal molecules. will be.

Among the liquid crystal display elements of the system (also referred to as a vertical alignment (VA) system) in which the liquid crystal molecules vertically aligned with respect to the substrate are caused to respond by an electric field, a process of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules .

In the liquid crystal display element of such a vertical alignment system, the photopolymerizable compound is previously added to a liquid crystal composition, and it uses together with a vertical alignment film, such as polyimide, and irradiates an ultraviolet-ray, applying a voltage to a liquid crystal cell, and the response speed of a liquid crystal is improved. Techniques for speeding up (for example, see Patent Document 1 and Non-Patent Document 1) are known (PSA (Polymer Sustained Alignment) type liquid crystal display). Usually, the direction in which the liquid crystal molecules in response to the electric field are inclined is controlled by protrusions formed on the substrate, slits formed on the display electrodes, and the like, but the ultraviolet rays are irradiated while applying a voltage to the liquid crystal cell by adding a photopolymerizable compound to the liquid crystal composition. Since a polymer structure in which the direction in which the liquid crystal molecules are tilted is stored is formed on the liquid crystal alignment film, it is known that the response speed of the liquid crystal display element is faster as compared with the method of controlling the inclination direction of the liquid crystal molecules using only projections or slits.

In this PSA type liquid crystal display element, the solubility of the polymerizable compound to be added to the liquid crystal is low, and there is a problem that precipitation occurs at a low temperature when the addition amount is increased. On the other hand, if the amount of the polymerizable compound to be added is reduced, a favorable alignment state can not be obtained. Moreover, since the unreacted polymeric compound remaining in a liquid crystal turns into an impurity (contamination) in a liquid crystal, there also exists a problem of reducing the reliability of a liquid crystal display element.

Here, it is reported that the response speed of a liquid crystal display element becomes quick even if a photopolymerizable compound is added not in a liquid crystal composition but in a liquid crystal aligning film (SC-PVA-type liquid crystal display) (for example, refer nonpatent literature 2).

Japanese Laid-Open Patent Publication 2003-307720

 K.Hanaoka, SID 04 DIGEST, P.1200-1202  K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

In such SC-PVA mode, although a polymeric compound is contained in a liquid crystal aligning agent, the storage stability of this liquid crystal aligning agent is bad, and there exists a problem that a component will precipitate. For example, in the step of manufacturing the liquid crystal aligning agent, even if the component is temporarily dissolved, the component tends to precipitate when the liquid crystal aligning agent is cryopreserved. And when this photopolymerizable compound mixes in a liquid crystal and remains unreacted at the time of manufacturing a liquid crystal display element, it becomes an impurity and becomes a cause which reduces the reliability of a liquid crystal display element.

Moreover, since it is desired to make the response speed of a liquid crystal display element further faster, it is conceivable to increase the response speed of a liquid crystal display element by increasing the addition amount of a photopolymerizable compound. The problem is that the stability becomes worse.

The problem of the present invention is to solve the problems of the prior art described above, and the liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element and liquid crystal which can improve the response speed of the liquid crystal display element of the vertical alignment system and are excellent in storage stability. It is providing the manufacturing method of a display element.

The liquid crystal aligning agent of this invention which solves the said subject is at least 1 sort chosen from the side chain which orientates a liquid crystal perpendicularly, and a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least 1 sort (s) of polymer chosen from the polyimide precursor which has a photoreactive side chain containing this, and the polyimide obtained by imidating this polyimide precursor, and following formula (i-1)-(i-3) At least one selected parent nucleus and a group which is photopolymerized or photocrosslinked at one or more terminals, and the photopolymerized or photocrosslinked group has a polymerizable compound which is bonded to the mother nucleus directly or via a bonding group, and a solvent. It features.

[Formula 1]

And it is preferable that the said polymeric compound is chosen from a following formula.

(2)

(Wherein, R ³¹ represents a single bond or -R ³⁵ O-, R ³⁵ is an alkylene group having a carbon number of 1 to 10 straight-chain, R ³² represents a single bond or -OR ³⁶ - represented by, R ³⁶ is straight An alkylene group having 1 to 10 carbon atoms in the chain, R ³³ and R ³⁴ are each independently a hydrogen atom or a methyl group)

Moreover, the other liquid crystal aligning agent of this invention contains the side chain which orientates a liquid crystal perpendicularly, and at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styrene group, and a cinnamoyl group. At least one polymer selected from a polyimide precursor having a photoreactive side chain and a polyimide obtained by imidating the polyimide precursor, and selected from the following formulas (ii-1) to (ii-3): It is characterized by having at least 1 sort (s) of mother nucleus, group photopolymerized or photocrosslinked in the at least 1 terminal, and the photopolymerization or photocrosslinkable group having the polymeric compound couple | bonded with the said mother nucleus and an oxyalkylene group, and a solvent.

(3)

And it is preferable that the said polymeric compound is chosen from a following formula.

[Chemical Formula 4]

(Wherein, R ⁴¹ represents a single bond or represents a -R ⁴⁵ O-, R ⁴⁵ is a carbon number of 1 to 10 alkylene groups of straight-chain, R ⁴² represents a single bond or -OR ⁴⁶ - represented by, R ⁴⁶ is straight An alkylene group having 1 to 10 carbon atoms in the chain, each of R ⁴³ and R ⁴⁴ is independently a hydrogen atom or a methyl group)

Moreover, it is preferable that the said photoreactive side chain contains the group chosen from following formula (I).

[Chemical Formula 5]

(Wherein R ¹¹ is H or a methyl group)

Moreover, it is preferable that the said photopolymerization or photocrosslinking group is chosen from following formula (II).

[Chemical Formula 6]

(In formula, R <^12> is H or a C1-C4 alkyl group, Z <^1> is a bivalent aromatic ring or heterocyclic ring which may be substituted by the C1-C12 alkyl group or the C1-C12 alkoxyl group, Z is ² is a monovalent aromatic ring or a heterocyclic ring which may be substituted by a C1-C12 alkyl group or a C1-C12 alkoxyl group)

The liquid crystal aligning film of this invention is obtained by apply | coating the said liquid crystal aligning agent to a board | substrate, and baking it.

The liquid crystal display device of the present invention comprises a liquid crystal cell prepared by applying the liquid crystal aligning agent to a substrate and contacting the liquid crystal alignment film obtained by baking to form a liquid crystal layer, and irradiating ultraviolet rays while applying voltage to the liquid crystal layer. It features.

And the manufacturing method of the liquid crystal display element of this invention contacts a liquid crystal aligning film obtained by apply | coating the said liquid crystal aligning agent to a board | substrate, and bakes, and forms a liquid crystal layer, irradiates a liquid crystal cell by irradiating an ultraviolet-ray, applying a voltage to this liquid crystal layer. It is characterized by manufacturing.

According to this invention, the response speed of a liquid crystal display element can be improved and the liquid crystal aligning agent excellent in storage stability can be provided.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of this invention contains the side chain which orientates a liquid crystal perpendicularly, and photoreactivity containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least 1 sort (s) of polymer chosen from the polyimide precursor which has a side chain of, and the polyimide obtained by imidating this polyimide precursor, and at least 1 sort (s) chosen from said Formula (i-1)-(i-3) A polymerizable compound having a parent nucleus of and a group which is photopolymerized or photocrosslinked at one or more terminals, and the photopolymerized or photocrosslinked group is bonded to the mother nucleus directly or via a bonding group, and / or the following formulas (ii-1) to Polymeric compound which has at least 1 sort (s) of mother-nucleus selected from (ii-3), the group photopolymerized or photocrosslinked at one or more terminal, and the group photopolymerized or photocrosslinked is couple | bonded with a mother nucleus and an oxyalkylene group. And a solvent. A liquid crystal aligning agent is a solution for manufacturing a liquid crystal aligning film, and a liquid crystal aligning film is a film for orienting a liquid crystal in a predetermined direction and a vertical direction in this invention.

First, the polymeric compound which the liquid crystal aligning agent of this invention contains is explained in full detail. The liquid crystal aligning agent of this invention has group which photopolymerizes or photocrosslinks at least 1 sort (s) of parent | base nucleus selected from said formula (i-1)-(i-3), and one or more terminal, and this photopolymerization or photocrosslinking group Polymerizable compound bonded to the mother nucleus represented by said Formula (i-1)-(i-3) directly or via a coupling group (the polymerization which has a mother nucleus represented by following "formula (i-1)-(i-3)) At least one or more kinds). That is, the polymeric compound which the liquid crystal aligning agent of this invention contains has one or more terminal which has photopolymerization or photocrosslinking group, and this photopolymerization or photocrosslinking group is selected from said Formula (i-1)-(i-3) It is a compound couple | bonded with at least 1 sort (s) of structure (parent nucleus) directly or via a bonding group.

Moreover, the liquid crystal aligning agent of this invention is represented with said polymeric formula (i-1)-(i-3) with the polymeric compound which has a mother-nucleus represented by said formula (i-1)-(i-3) Instead of the polymerizable compound having a mother nucleus, at least one kind of mother nucleus selected from the formulas (ii-1) to (ii-3) and a group which is photopolymerized or photocrosslinked at one or more terminals, and photopolymerized or photocrosslinked The group may contain at least one polymerizable compound (hereinafter also referred to as "polymerizable compound having a parent nucleus represented by formulas (ii-1) to (ii-3)") in which a group is bonded to a mother nucleus and an oxyalkylene group. .

In addition, the polymeric compound which has group to photopolymerize is a compound which has a functional group which causes superposition | polymerization by irradiating light. Moreover, the compound which has group to photocrosslink is reacted with at least 1 sort (s) of polymer chosen from the polymer of a polymeric compound, a polyimide precursor, and the polyimide obtained by imidating this polyimide precursor by irradiating light, and these It is a compound which has a functional group which can bridge | crosslink with. Moreover, even if the compound which has group to photocrosslink, the compound which has group to photocrosslink react.

The polymeric compound which has a mother nucleus represented by such said Formula (i-1)-(i-3) and the polymeric compound which has a mother nucleus represented by said Formula (ii-1)-(ii-3) in detail Is a side chain for vertically aligning a liquid crystal to be described later, and a photoreactive side chain containing at least one selected from methacryl group, acrylic group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group. Into the liquid crystal aligning agent together with the polyimide precursor which has, and at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor, it contains in the liquid crystal display element of a vertical alignment system, such as an SC-PVA-type liquid crystal display. By using for the production, the response speed is dramatically increased as compared with the case of using a polymer having a side chain and a photoreactive side chain orientating these liquid crystals vertically or these polymerizable compounds alone. Can be improved, the response time to a fast liquid crystal display device. And the addition amount of a polymeric compound can fully improve the response speed at least. Moreover, the liquid crystal aligning agent of this invention has a polymeric compound which has a mother nucleus represented by said formula (i-1)-(i-3), and a mother nucleus represented by said formula (ii-1)-(ii-3). The storage stability at the time of cryopreservation (for example, at -20 ° C about cryopreservation) is lower than that of a polymerizable compound which is not a polymerizable compound, for example, a polymerizable compound having a biphenyl structure as a mother nucleus. It becomes an excellent liquid crystal aligning agent.

As a group photopolymerized or photocrosslinked, the monovalent group represented by said formula (II) is mentioned.

As a specific example of the polymeric compound which has the mother nucleus represented by said formula (i-1)-(i-3), or the polymeric compound which has the mother nucleus represented by said formula (ii-1)-(ii-3), The compound which has group which photopolymerizes to each of two terminal as shown by following formula (III), the terminal which has the terminal which has photocrosslinked group with the terminal which has photopolymerized group as shown by following formula (IV), or the following formula ( The compound which has group photocrosslinked to each of the two terminal as shown by V) is mentioned. Further, according to the following formula (III) ~ (V), R 12, Z 1 and Z ² are the same as R ^12, Z ¹ and Z ² in the formula (II), and Q ¹ is the formula (i -1) to a divalent organic group having a structure represented by (i-3) or a divalent organic group to which an oxyalkylene group is bonded to both ends of the structure represented by the formulas (ii-1) to (ii-3). to be. It is preferable that Q <^1> has an oxyalkylene group and an alkylene group. This is because the interaction with the liquid crystal tends to become large.

[Formula 7]

[Formula 8]

[Chemical Formula 9]

As a specific example of the polymeric compound which has a mother nucleus represented by said formula (i-1)-(i-3), the compound represented by a following formula is mentioned.

[Formula 10]

(Wherein, R ³¹ represents a single bond or -R ³⁵ O-, R ³⁵ is an alkylene group having a carbon number of 1 to 10 straight-chain, R ³² represents a single bond or -OR ³⁶ - represented by, R ³⁶ is straight An alkylene group having 1 to 10 carbon atoms in the chain, R ³³ and R ³⁴ are each independently a hydrogen atom or a methyl group)

Moreover, the compound represented by a following formula is mentioned as a specific example of the polymeric compound which has the mother nucleus represented by said formula (ii-1)-(ii-3).

[Formula 11]

(Wherein, R ⁴¹ represents a single bond or represents a -R ⁴⁵ O-, R ⁴⁵ is a carbon number of 1 to 10 alkylene groups of straight-chain, R ⁴² represents a single bond or -OR ⁴⁶ - represented by, R ⁴⁶ is straight An alkylene group having 1 to 10 carbon atoms in the chain, each of R ⁴³ and R ⁴⁴ is independently a hydrogen atom or a methyl group)

In general, the formation process of the liquid crystal alignment film includes a step of baking at high temperature in order to completely remove the solvent, but a polymerizable compound having an α-methylene-γ-butyrolactone group, which is a polymerizable group (photopolymerized group) at both ends. If it is a structure inferior in thermal polymerization property, it can fully tolerate high temperature, for example, baking temperature 200 degreeC or more. Moreover, even if it is a polymeric compound which has an acrylate group and a methacrylate group instead of (alpha)-methylene- (gamma) -butyrolactone group as photopolymerization or photocrosslinking group, this acrylate group and a methacrylate group are interposed through spacers, such as an oxyalkylene group. If it is a polymeric compound which has a structure couple | bonded with a phenylene group, like the polymeric compound which has a (alpha)-methylene- (gamma)-(butyrolactone) group at the said terminal, it is because stability to heat improves, or it is high temperature, for example 200 It can withstand a calcination temperature of not lower than ℃.

The method for producing such a polymerizable compound is not particularly limited and can be produced, for example, according to a synthesis example described later. For example, a polymeric compound can be synthesize | combined by combining the method in organic synthetic chemistry. For example, Taraga et al., Which are represented by the following schemes, employs Sn (Cl ₂ ) by 2- (bromomethyl) by a method proposed in P. Talaaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990). It can be synthesized by reacting acrylic acid (2- (bromomethyl) propenoic acid) with aldehyde or ketone. In addition, Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.

[Chemical Formula 12]

(Wherein R 'represents a monovalent organic group)

In addition, 2- (bromomethyl) acrylic acid is proposed by Ramaran and the like represented by the following reaction scheme in K.Ramarajan, K.Kamalingam, DJO 'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). It can be synthesized by the method.

[Chemical Formula 13]

In addition, the liquid crystal aligning agent of this invention is a polymeric compound which has the mother nucleus represented by such said Formula (i-1)-(i-3), and the mother nucleus represented by said Formula (ii-1)-(ii-3) You may contain two or more types of polymeric compounds which have a.

Moreover, in addition to the polymeric compound which has the mother nucleus represented by said formula (i-1)-(i-3), and the polymeric compound which has the mother nucleus represented by said formula (ii-1)-(ii-3), A polymerizable compound which is not a polymerizable compound having a mother nucleus represented by the formulas (i-1) to (i-3) or a polymerizable compound having a mother nucleus represented by the formulas (ii-1) to (ii-3). Hereinafter, it may describe as "other polymerizable compound", 1 type, or 2 or more types.

As group which photopolymerizes or photocrosslinks the said other polymeric compound, monovalent group represented by said Formula (II) is mentioned.

As a specific example of the said other polymeric compound, the compound which has group photopolymerized to each of two terminal as shown by following formula (XV), and the terminal and photocrosslinking which have group which photopolymerizes as shown by following formula (XVI) The compound which has a terminal which has a terminal which has a group to group, and the group which photocrosslinks to each of two terminal as shown by following formula (XVII) is mentioned. In the following formulas (XV) to (XVII), R ¹⁷ is H or an alkyl group having 1 to 4 carbon atoms, and Z ³ may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Z ⁴ is a monovalent aromatic ring or heterocyclic ring which may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Q ² does not have a structure represented by the formulas (i-1) to (i-3), and an oxyalkylene group is bonded to both ends of the structure represented by the formulas (ii-1) to (ii-3). It is a bivalent organic group which is not made. Q ² has a ring structure such as a phenylene group (-C ₆ H _4- ), a biphenylene group (-C ₆ H ₄ -C ₆ H _4- ), or a cyclohexylene group (-C ₆ H _10- ) It is preferable. This is because the interaction with the liquid crystal tends to become large.

[Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

As a polymeric compound represented by a formula (XV), the polymeric compound represented by a following formula (XVIII) is mentioned. In the following formula (XVIII), V ¹ is represented by a single bond or -R ²¹ O-, R ²¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, and W ¹ is a single bond or -OR ^22- R <^22> is a linear or branched C1-C10 alkylene group and R <^18> is a hydrogen atom or a methyl group.

[Chemical Formula 17]

As a specific example of the compound represented by said formula (XVIII), the polymeric compound represented by a following formula is mentioned.

[Chemical Formula 18]

(Wherein R ¹⁸ is H or a methyl group)

The manufacturing method of such another polymeric compound is not specifically limited, for example, A polymeric compound can be synthesize | combined by combining the method in organic synthetic chemistry. As a specific synthesis example, if it is Formula (XV), it can synthesize | combine by reaction of the following formula, for example. In addition, in the following reaction formula, R <^19> and R <^20> is a C1-C10 alkylene group which is respectively linear or branched independently. THF is an abbreviation of tetrahydrofuran.

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

Moreover, the liquid crystal aligning agent of this invention is a polyimide precursor and at least 1 sort (s) chosen from the polyimide obtained by imidating this polyimide precursor, The polymer which has a side chain which orientates a liquid crystal perpendicularly, and a side chain of photoreactivity. It contains. Examples of the polyimide precursor include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.

Although the side chain which orientates the liquid crystal which this polymer has perpendicularly | vertically will not be limited if it is a structure which can orientate a liquid crystal perpendicularly to a board | substrate, For example, a ring structure or a branched structure is made in the middle of a long chain alkyl group and a long chain alkyl group. Hydrocarbon groups, such as group which has, a steroid group, and the group which substituted one part or all the hydrogen atoms of these groups with the fluorine atom, etc. are mentioned. Of course, you may have a side chain which orientates two or more types of liquid crystals vertically. The side chain which orientates a liquid crystal perpendicularly may be directly bonded to polyimide precursors, such as a polyamic acid and a polyamic acid ester, or a main chain of a polyimide, ie, a polyamic acid frame | skeleton, a polyimide frame | skeleton, etc., and through an appropriate coupling group. May be combined. As a side chain which orientates a liquid crystal perpendicularly, the hydrocarbon group which the hydrogen atom may be substituted by fluorine has 8-30, Preferably 8-22 hydrocarbon group, Specifically, an alkyl group, a fluoroalkyl group, an alken And a nil group, a phenethyl group, a styryl alkyl group, a naphthyl group, a fluorophenyl alkyl group, and the like. As a side chain which orientates another liquid crystal vertically, what is represented, for example by following formula (a) is mentioned.

[Chemical Formula 22]

(In formula (a), l, m, and n represent the integer of 0 or 1 each independently, and R <^3> is a C2-C6 alkylene group, -O-, -COO-, -OCO-, -NHCO-. , -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, R ⁴ , R ^5, and R ⁶ each independently represent a phenylene group or a cycloalkylene group, and R ⁷ represents a hydrogen atom or 2 to 24 carbon atoms; Alkyl group or fluorine-containing alkyl group, monovalent aromatic ring, monovalent aliphatic ring, monovalent heterocyclic ring, or monovalent large cyclic substituent consisting thereof)

R ³ in the formula (a) is preferably -O-, -COO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, from the viewpoint of ease of synthesis.

R ⁴ , R ⁵ and R ⁶ in the formula (a) are preferably 1, m, n, R ⁴ , R ⁵ and R ⁶ shown in the following Table 1 from the viewpoints of ease of synthesis and ability to orient the liquid crystal vertically ⁶ is preferable.

And when at least one of l, m, and n is 1, R <^7> in Formula (a), Preferably it is a hydrogen atom or a C2-C14 alkyl group or a fluorine-containing alkyl group, More preferably, it is a hydrogen atom or C2 An alkyl group of 12 to 12 or a fluorine-containing alkyl group. In addition, when l, m, and n are all 0, R <^7> , Preferably it is a C12-C22 alkyl group or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, monovalent consisting of them It is a large cyclic substituent, More preferably, it is a C12-20 alkyl group or a fluorine-containing alkyl group.

The amount of the side chain that vertically aligns the liquid crystal is not particularly limited as long as the liquid crystal alignment film can orient the liquid crystal vertically. However, in the liquid crystal display element provided with the said liquid crystal aligning film, the amount of the side chain which orientates a liquid crystal perpendicularly in the range which does not impair display characteristics of an element, such as voltage retention and accumulation of residual DC voltage, is as little as possible. It is more preferable.

In addition, the ability of a polymer having a side chain for vertically aligning the liquid crystal to align the liquid crystal vertically depends on the structure of the side chain for vertically aligning the liquid crystal, but in general, the amount of side chain for vertically aligning the liquid crystal. The greater the value, the higher the ability to align the liquid crystals vertically, and the lower the value. Moreover, when it has a cyclic structure, compared with the thing which does not have a cyclic structure, there exists a tendency for the ability to orientate a liquid crystal perpendicularly.

Moreover, the polymer which consists of at least 1 sort (s) of polyimide precursors, such as polyamic acid and polyamic acid ester, and polyimide which the liquid crystal aligning agent of this invention contains has a photoreactive side chain. A photoreactive side chain is a side chain which has a functional group (henceforth a photoreactive group) which can react by irradiation of light, such as an ultraviolet-ray (UV), and can form a covalent bond, and in this invention, a photoreaction As a sexual group, it contains at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. Thus, the polymer which consists of at least 1 sort (s) of polyimide precursors, such as polyamic acid and polyamic acid ester, and polyimide which are contained in a liquid crystal aligning agent is a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and By having a photoreactive side chain containing at least 1 sort (s) chosen from a cinnamoyl group, and using it for a liquid crystal aligning agent with the said polymeric compound, as shown in the Example mentioned later, a response speed is remarkably improved. You can.

The photoreactive side chain may be directly bonded to the polyimide precursor or the main chain of the polyimide, or may be bonded via a suitable bonding group. As photoreactive side chain, what is represented by following formula (b) is mentioned, for example.

(23)

(In formula (b), R ⁸ is a single bond or -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N Any of (CH ₃ )-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, and R ⁹ is a single bond or an unsubstituted or substituted C1-C20 alkyl A rene group is represented, -CH ₂ -in the alkylene group may be optionally substituted with -CF ₂ -or -CH = CH-, and in the case where any of the following groups are not adjacent to each other, they may be substituted with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring, divalent hetero ring.R ¹⁰ is a methacryl group, an acryl group, a vinyl group, an allyl group, Coumarin group, styryl group, cinnamoyl group)

Further, the formula (b) in R ⁸ is from the point of view of ease of, but can be formed in a conventional organic synthetic method, _{Synthesis, -CH 2 -, -O-, -COO-} , -NHCO-, -NH- , -CH ₂ O- is preferred.

In addition, any of -CH ₂ R ⁹ - in the carbon ring or heterocyclic ring of the divalent carbocyclic or a divalent heterocyclic ring is substituted, there can be a structure as specifically described below, it is not limited thereto .

&Lt; EMI ID =

R ¹⁰ is preferably a methacryl group, an acrylic group or a vinyl group from the viewpoint of photoreactivity.

Moreover, said Formula (b), More preferably, it is a structure containing the group chosen from said Formula (I).

The amount of photoreactive side chains is preferably in a range in which the response speed of the liquid crystal can be made faster by reacting by irradiation with ultraviolet rays to form a covalent bond. As much as possible in the range which does not interfere with is preferable. For example, the introduction amount into the photoreactive side chain polyimide precursor or polyimide is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%.

It has a side chain which orientates such a liquid crystal vertically, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. The method for producing at least one polymer selected from a polyimide precursor and a polyimide obtained by imidating the polyimide precursor is not particularly limited, but for example, by reaction of diamine and tetracarboxylic dianhydride. In the method of obtaining a polyamic acid, tetracarboxylic dianhydride which has a diamine which has a side chain which orientates a liquid crystal perpendicularly, or a side chain which orientates a liquid crystal vertically, a methacryl group, an acryl group, a vinyl group, and an allyl group Diamines or methaks having a photoreactive side chain containing at least one member selected from a coumarin group, a styryl group and a cinnamoyl group What is necessary is just to copolymerize the tetracarboxylic dianhydride which has a photoreactive side chain containing at least 1 sort (s) chosen from a aryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group.

As a diamine which has a side chain which orientates a liquid crystal perpendicularly, the hydrocarbon group, such as the group which has a ring structure, a branched structure, a steroid group, in the middle of a long chain alkyl group, a long chain alkyl group, or some or all hydrogen atoms of these groups The diamine which has group substituted by the fluorine atom as a side chain, for example, the diamine which has a side chain represented by said formula (a) is mentioned. More specifically, For example, the diamine which has a C8-C30 hydrocarbon group etc. which the hydrogen atom may be substituted by fluorine, and the diamine represented by following formula (2), (3), (4), (5) Although it is mentioned, it is not limited to this.

(25)

(Definition of l, m, n, R ³ to R ⁷ in the formula (2) is the same as the formula (a))

(26)

(In Formulas (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, or -NH-. And A ₁₁ represent a single bond or a phenylene group, a represents the same structure as the side chain for orientating the liquid crystal represented by the formula (a) vertically, and a 'orientates the liquid crystal represented by the formula (a) vertically. Divalent group having a structure in which one element such as hydrogen is separated from the same structure as the side chain)

(27)

(In Formula (5), A <_14> is a C3-C20 alkyl group which may be substituted by the fluorine atom, A <_15> is a 1, 4- cyclohexylene group or 1, 4- phenylene group, A <_16> is an oxygen atom Or -COO- * (wherein the bond to which "*" is attached is combined with A ₁₅ ), and A ₁₇ is an oxygen atom or -COO- * (wherein the bond to which "*" is attached is (CH ₂₎ ) is coupled with a ₂ a). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 ~ 10, a ₃ represents an integer of 0 or 1)

The bonding position of two amino groups (-NH ₂ ) in the formula (2) is not limited. Specifically, the 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position, 3, 5 position on a benzene ring is mentioned with respect to the coupling group of a side chain. Especially, from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid, 2, 4 position, 2, 5 position, or 3, 5 position are preferable. If the ease in synthesizing a diamine is also taken into consideration, 2, 4 position, or 3, 5 position is more preferable.

Although the diamine shown by following formula [A-1]-formula [A-24] can be illustrated as a specific structure of Formula (2), It is not limited to this.

(28)

(A <_1> is a C2-C24 alkyl group or a fluorine-containing alkyl group in a formula [A-1]-a formula [A-5].)

[Chemical Formula 29]

(Wherein [A-6] and the formula [A-7] of, A ₂ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 -, or represents a -CH ₂ OCO-, A ₃ Is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group)

(30)

(Wherein [A-8] ~ formula [A-10] of, A ₄ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH _2- , or -CH _2- , A ₅ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

(31)

(Wherein [A-11] and the equation [A-12] of, A ₆ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH _2- , -CH _2- , -O-, or -NH-, and A ₇ represents a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, ace Oxy group or hydroxyl group)

(32)

(In Formula [A-13] and Formula [A-14], A <_8> is a C3-C12 alkyl group and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.)

(33)

(In formula [A-15] and formula [A-16], A <_9> is a C3-C12 alkyl group and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.)

(34)

Although the diamine shown by following formula [A-25]-formula [A-30] is mentioned as a specific example of the diamine represented by Formula (3), It is not limited to this.

(35)

(Wherein [A-25] ~ formula [A-30] of, A ₁₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO-, or - NH-, and A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

Although the diamine shown by following formula [A-31]-formula [A-32] is mentioned as a specific example of the diamine represented by Formula (4), It is not limited to this.

(36)

Among these, [A-1], [A-2], [A-3], [A-4], [A-5], [A] from the viewpoint of the ability to orient the liquid crystal vertically and the response speed of the liquid crystal. A-25], [A-26], [A-27], [A-28], [A-29], and the diamine of [A-30] are preferable.

The said diamine can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as liquid crystal alignability, pretilt angle, voltage retention characteristic, and stored charge, when it sets as a liquid crystal aligning film.

It is preferable to use the amount which becomes 5-50 mol% of the diamine component used for the synthesis | combination of a polyamic acid, and the diamine which has a side chain which orients such a liquid crystal perpendicularly, More preferably, it is 10-40 mol of a diamine component. % Is diamine which has a side chain which orientates a liquid crystal perpendicularly | vertically, Especially preferably, it is 15-30 mol%. Thus, when 5 to 50 mol% of diamine component used for the synthesis | combination of a polyamic acid is used for the diamine which has a side chain which orientates a liquid crystal perpendicularly, it is especially excellent in the response speed improvement and the orientation fixation ability of a liquid crystal.

As a diamine which has a photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, For example, said formula (b The diamine which has a side chain represented by) is mentioned. More specifically, although diamine represented by the following general formula (6) is mentioned, for example, It is not limited to this.

[Formula 37]

(Definitions of R ⁸ , R ⁹ and R ¹⁰ in formula (6) are the same as in formula (b).)

The bonding position of two amino groups (-NH ₂ ) in the formula (6) is not limited. Specifically, the 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position, 3, 5 position on a benzene ring is mentioned with respect to the coupling group of a side chain. Especially, from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid, 2, 4 position, 2, 5 position, or 3, 5 position are preferable. If the ease in synthesizing a diamine is also taken into consideration, 2, 4 position, or 3, 5 position is more preferable.

As a diamine which has a photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, specifically, the following compounds are mentioned. Although it is mentioned, it is not limited to this.

(38)

(Wherein, X is a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, Y is an unsubstituted or a C 1-20 alkylene group substituted by a fluorine atom. Indicates)

The diamine which has a photoreactive side chain containing at least 1 sort (s) chosen from the said methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group is a liquid crystal aligning property when it used as a liquid crystal aligning film, One type or two or more types can also be mixed and used according to the characteristics, such as a pretilt angle, voltage holding characteristic, an accumulated charge, the response speed of the liquid crystal at the time of using a liquid crystal display element, and the like.

Moreover, the diamine which has a photoreactive side chain containing at least 1 sort (s) chosen from such a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group styryl group, and cinnamoyl group is used for the synthesis | combination of a polyamic acid. It is preferable to use the quantity used as 10-70 mol% of a diamine component, More preferably, it is 20-60 mol%, Especially preferably, it is 30-50 mol%.

In addition, the polyamic acid can use together diamine other than the diamine which has a side chain which orientates the said liquid crystal perpendicularly, and the diamine which has a photoreactive group, as long as the effect of this invention is not impaired. . Specific examples include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m- , 4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, , 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy 4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'- Diaminobiphenyl, 3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3'- , 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diamino Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3,4'-diaminodiphenyl ether, Bis (4-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, -Aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'- thiodianiline, 4,4'- diaminodiphenylamine, - diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-dia (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Phenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'- 1,4-diaminonaphthalene, 2,2'-diaminobenzophene , 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 2,6-diaminonaphthalene, 2,6-diaminonaphthalene, Bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, ) Butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [ Phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenanthrene 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3- (3-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, bis , N, N '- (1,4-phenylene) bis (4-aminobenzamide) (4-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- ) Terephthalamide, N, N'-bis (3-aminophenyl) terephthalate Bis (4-aminophenyl) isothiamides, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-amino- Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Heptane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) , 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) 1,10- (3-aminophenoxy) decane, 1,11- (3-aminophenoxy) undecane, 1,12- Aromatic diamines such as bis (4-aminophenoxy) dodecane and 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) ) Methane, alicyclic diamines such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Aliphatic diamines such as 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

The said other diamine can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as liquid crystal aligning property, pretilt angle, voltage retention characteristic, and stored charge, when it sets as a liquid crystal aligning film.

The tetracarboxylic dianhydride reacted with the diamine component in the synthesis of the polyamic acid is not particularly limited. Specific examples include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) Sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid Acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracar Carboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic Acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantate Carboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, Bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic acid, 1,2 , 3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, Bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane -1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tree Carboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, etc. are mentioned. Of course, the tetracarboxylic acid dianhydride may be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

When obtaining a polyamic acid by reaction of a diamine component and tetracarboxylic dianhydride, a well-known synthetic method can be used. Generally, it is a method of making a diamine component and tetracarboxylic dianhydride react in an organic solvent. The reaction of the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

The organic solvent used in the reaction is not particularly limited as long as it dissolves the produced polyamic acid. Moreover, even if it is an organic solvent in which a polyamic acid does not melt | dissolve, you may mix and use with the said solvent in the range which does not precipitate the produced polyamic acid. In addition, since the moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use the organic solvent dehydrated and dried. As an organic solvent used for reaction, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-, for example Pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcapro Lactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone , Methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol , Ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol mono Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol Monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Diisobutylene, ah Mill acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene Carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl ethyl 3-ethoxypropionate, 3-methoxy ethyl propionate, 3-ethoxy propionic acid, 3-methoxy propionic acid, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol etc. are mentioned. These organic solvents may be used alone or in combination.

When reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent, the solution which disperse | distributed or dissolved the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component is disperse | distributed or dissolved in an organic solvent as it is. And a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic dianhydride component and a diamine component, and the like. Any of these methods may be used. Moreover, when a diamine component or tetracarboxylic dianhydride component consists of multiple types of compounds, it may be made to react in the state mixed previously, may be made to react individually one by one, and the low molecular weight reacted separately may mix and react a polymer, It may be a monomer.

The temperature at the time of making a diamine component and the tetracarboxylic dianhydride component react can select arbitrary temperature, for example -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. Moreover, reaction can be performed in arbitrary concentration, For example, the total amount of a diamine component and a tetracarboxylic dianhydride component is 1-50 mass% with respect to a reaction liquid, Preferably it is 5-30 mass%.

The ratio of the total mole number of the tetracarboxylic dianhydride component with respect to the total mole number of the diamine component in the said polymerization reaction can select arbitrary values according to the molecular weight of the polyamic acid to obtain. As in the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid. It is 0.8 to 1.2 if it shows a preferable range.

The method for synthesizing the polyamic acid used in the present invention is not limited to the above method, and similarly to the general method for synthesizing polyamic acid, instead of the above tetracarboxylic dianhydride, tetracarboxylic acid or tetra having a corresponding structure The corresponding polyamic acid can also be obtained by making it react by a well-known method using tetracarboxylic-acid derivatives, such as carboxylic acid dihalide.

As a method of imidating said polyamic acid and making it a polyimide, the heat | fever imidation which heats the solution of a polyamic acid as it is, and the catalyst imidation which adds a catalyst to the solution of a polyamic acid are mentioned. In addition, the imidation rate from polyamic acid to polyimide does not necessarily have to be 100%.

The temperature at the time of thermally imidating a polyamic acid in a solution is 100 degreeC-400 degreeC, Preferably it is 120 degreeC-250 degreeC, It is preferable to carry out, removing the water produced | generated by the imidation reaction out of a system.

Catalytic imidization of polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the solution of polyamic acid, and stirring at -20-250 degreeC, Preferably it is 0-180 degreeC. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst, Especially, since pyridine has suitable basicity for advancing reaction, it is preferable. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among these, when acetic anhydride is used, purification after completion of the reaction is preferred. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

The polyamic acid ester is a reaction of tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, or a diamine similar to the synthesis of tetracarboxylic acid diester and the polyamic acid in the presence of a suitable condensing agent or a base. It can manufacture by making it react etc. Alternatively, the polyamic acid may be synthesized in advance by the above-described method, and the carboxylic acid in the polyamic acid may be esterified using a polymer reaction. Specifically, tetracarboxylic diester dichloride and diamine are, for example, in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably By reacting for 1 to 4 hours, the polyamic acid ester can be synthesized. And polyimide can also be obtained by heating polyamic acid ester at high temperature, promoting de-alcohol, and ring-closing.

When recovering polyimide precursor or polyimide, such as polyamic acid or polyamic acid ester, produced from a reaction solution of a polyimide precursor such as polyamic acid or polyamic acid ester or polyimide, the reaction solution is added to an empty solvent. By precipitation. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by being poured into the poor solvent may be filtered and recovered, and then dried by normal temperature or heating under normal pressure or reduced pressure. Moreover, if the polymer which precipitated and collect | recovered is re-dissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2-10 times, the impurity in a polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more kinds of poor solvents selected from these is preferable because the efficiency of purification is further increased.

As mentioned above, the liquid crystal aligning agent of this invention is a side chain which orientates a liquid crystal perpendicularly, and at least selected from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least 1 sort (s) of polymer chosen from the polyimide precursor which has a photoreactive side chain containing 1 type, and the polyimide obtained by imidating this polyimide precursor, and said Formula (i-1)-(i-3) What is necessary is just to have a polymeric compound which has a mother-nucleus represented by), and / or a polymeric compound which has a mother-nucleus represented by said formula (ii-1)-(ii-3), and a solvent, and is not specifically limited to the compounding ratio, And the sum total of content of the polymeric compound which has a mother-nucleus represented by said formula (i-1)-(i-3), and the polymeric compound which has a mother-nucleus represented by said formula (ii-1)-(ii-3) Side chains for vertically aligning the liquid crystal , A polyimide precursor having a photoreactive side chain containing at least one member selected from methacryl group, acrylic group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group, and this polyimide precursor It is preferable that it is 1-50 mass parts with respect to 100 mass parts of at least 1 sort (s) of polymer chosen from the polyimide obtained by dehydration, More preferably, it is 5-30 mass parts. Thus, the liquid crystal aligning agent of this invention is a polymeric compound which has the mother nucleus represented by said formula (i-1)-(i-3), and the mother nucleus represented by said formula (ii-1)-(ii-3) The addition rate of the polymeric compound which has a thing is a fast response speed at least enough. And since the liquid crystal aligning agent of this invention is excellent in storage stability, in order to improve a response speed further, the polymeric compound which has a mother-nucleus represented by said formula (i-1)-(i-3), or the said formula ( The storage stability is good even if the amount of the polymerizable compound having a parent nucleus represented by ii-1) to (ii-3) is slightly increased. Moreover, light containing the side chain which orientates the liquid crystal contained in a liquid crystal aligning agent vertically, and at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. As for content of the at least 1 sort (s) of polymer chosen from the polyimide precursor which has a reactive side chain, and the polyimide obtained by imidating this polyimide precursor, 1 mass%-20 mass% are preferable, More preferably, it is 3 mass %-15 mass%, Especially preferably, they are 3 mass%-10 mass%.

Moreover, the liquid crystal aligning agent of this invention contains the side chain which orientates a liquid crystal perpendicularly, and at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. You may contain the polymer other than the at least 1 sort (s) of polymer chosen from the polyimide precursor which has photoreactive side chain, and the polyimide obtained by imidating this polyimide precursor. At this time, the content of such another polymer in the entire polymer component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.

The molecular weight of the polymer which a liquid crystal aligning agent has is the weight average measured by GPC (Gel Permeation Chromatography) method, when the intensity | strength of the liquid crystal aligning film obtained by apply | coating a liquid crystal aligning agent, the workability at the time of coating film formation, and the uniformity of a coating film are considered. It is preferable to set it as 5,000-1,000,000 in molecular weight, More preferably, it is 10,000-150,000.

There is no restriction | limiting in particular in the solvent which a liquid crystal aligning agent contains, At least 1 chosen from the side chain which orientates the said liquid crystal perpendicularly, and a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least 1 sort (s) of polymer chosen from the polyimide precursor which has a photoreactive side chain containing a species, and the polyimide obtained by imidating this polyimide precursor, and said Formula (i-1)-(i-3) What is necessary is just to be able to melt | dissolve or disperse | distribute the polymeric compound which has a mother-nucleus shown by this, and polymeric compounds which have a mother-nucleus represented by said formula (ii-1)-(ii-3). For example, the organic solvent as illustrated by the synthesis | combination of said polyamic acid is mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N- Dimethylpropanamide is preferable in view of solubility. Of course, two or more types of mixed solvents may be used.

In addition, it is preferable to use a solvent which improves the uniformity and smoothness of the coating film in a solvent having high solubility of the component containing the liquid crystal aligning agent. As a solvent which improves the uniformity and smoothness of a coating film, for example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and butyl cell Losolve solvent, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol mono Acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, dipropylene glycol monoacetate monomethyl ether, deep Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl- 3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diiso Butyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3- Ethyl oxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1- Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2- Acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1- Hexanol and the like. These solvents may be mixed with a plurality of kinds. When using these solvent, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass%.

The liquid crystal aligning agent may contain other components than those described above. As the example, the compound which improves the film thickness uniformity and surface smoothness at the time of apply | coating a liquid crystal aligning agent, the compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, a polymerization initiator, a polymerization inhibitor, etc. are mentioned. In addition, a polymerization inhibitor is added in order to make handling of the polymeric compound which has high polymerizability easy.

As a compound which improves the uniformity and surface smoothness of a film thickness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. More specifically, for example, F-Top EF301, EF303, EF352 (manufactured by Tochem Products, Inc.), Megapak F171, F173, R-30 (manufactured by Dainippon Ink, Inc.), Florade FC430, FC431 (manufactured by Sumitomo 3M Corporation) ), Asahi Guard AG710, Saflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. are mentioned. When using these surfactant, the use ratio becomes like this. Preferably it is 0.01-2 mass parts with respect to 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent, More preferably, it is 0.01-1 mass part.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) And the like can be given no trimethoxysilane. In order to further increase the film strength of the liquid crystal alignment film, phenol compounds such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane and tetra (methoxymethyl) bisphenol may be added. . When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts.

Moreover, a radical polymerization initiator is mentioned as a polymerization initiator. As a radical polymerization initiator, the compound etc. which consist of a benzoin derivative and a peroxide are mentioned.

Preferred examples of the benzoin derivative include (±) -campaquinone, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthene-9-one, 2-benzoylbenzoic acid, 2-chlorobenzophenone, 2 -Chlorothioxanthone, 2-ethylanthraquinone, 2-isonitrosopropiophenone, 2-isopropylthioxanthone, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 4,4 ' -Dichlorobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoylbenzoic acid, 4-chlorobenzophenone, acetophenone, diphenylethanedione, benzoin, benzoin ethyl ether, benzoin isobutyl ether , Benzoin isopropyl ether, benzoin methyl ether, benzophenone, dibenzosuberon, 9-fluorenone, methyl 2-benzoylbenzoate, 4,4-dimethoxybenzoyl, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methylpropan-1-one, Michler's ketone, Chiba Specialty Co., Ltd. production "Darcure series 1173, 4265", "irgacure series 184, 500, 651, 819, 2959" Field There. As a particularly preferable example of a benzoin derivative, the Chiba Specialty Co., Ltd. product Irgacure 651 is mentioned.

Moreover, as a preferable example of a compound which consists of peroxides, Nichi Oil Co., Ltd. make, Pertetra A, perhexa HC, perhexa C, perhexa V, perhexa 22, perbutyl D, perhexyl D, perroyl 355, Peroyl L, Naper BW, Naper BMT, Perroyl TCP, Percumyl ND, Perocta ND, Perhexyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 25O, Perocta O, Perhexyl O, Perbutyl O, perbutyl L, perbutyl 355, perhexyl I, perbutyl E, perhexa 25Z, perbutyl A, perhexyl Z, perbutyl Z, perbutyl ZT, etc. are mentioned. As a particularly preferable example among the compound which consists of a peroxide, Nichi Oil Co., Ltd. product "Peroyl L, Naper BW, Naper BMT, perocta O, perhexyl O, perbutyl O" is mentioned.

Moreover, you may combine 2 or more types of these polymerization initiators, and the mixture of a benzophenone and Michler's ketone is mentioned as an example of a preferable combination.

When using a polymerization initiator, 10 mass% or less is preferable with respect to the total amount of a polymeric compound, in order that the use ratio may prevent a polymerization initiator from acting as an impurity and the display quality of a display element falls.

Moreover, when adding a polymerization inhibitor, it is preferable that the use ratio is 10 weight% or less with respect to the total amount of a polymeric compound, in order to prevent a polymerization inhibitor from acting as an impurity.

Moreover, in addition to the above, in the liquid crystal aligning agent, as long as the effect of this invention is not impaired, you may add the dielectric and electrically conductive substance for the purpose of changing electrical characteristics, such as dielectric constant and electroconductivity of a liquid crystal aligning film.

By apply | coating and baking this liquid crystal aligning agent on a board | substrate, the liquid crystal aligning film which orientates a liquid crystal perpendicularly | vertically can be formed. The liquid crystal aligning agent of this invention contains the side chain which orientates a liquid crystal perpendicularly, and photoreactivity containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. It has a mother nucleus represented by said Formula (i-1)-(i-3) with the polyimide precursor which has a side chain of and at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor. Since it has a polymeric compound and the polymeric compound which has the parent nucleus represented by said formula (ii-1)-(ii-3), the response speed of the liquid crystal display element using the liquid crystal aligning film obtained can be made quick. Moreover, since the liquid crystal aligning agent of this invention is excellent in storage stability, and precipitation of a component is suppressed even if it is cryopreserved, a liquid crystal aligning film can be manufactured after manufacturing a liquid crystal aligning agent and cryopreserving.

For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, you may dry as needed, and you may use the cured film obtained by baking, as a liquid crystal aligning film as it is. The cured film may be rubbed, irradiated with polarized light or a specific wavelength, or treated with an ion beam, or irradiated with UV light while a voltage is applied to the liquid crystal display element after liquid crystal charging as an alignment film for SC-PVA. It may be.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass plate, polycarbonate, poly (meth) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, and polyether ketone , Trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose and the like can be used. Moreover, it is preferable to use the board | substrate with which the indium tin oxide (ITO) electrode etc. for liquid crystal drive were formed from a viewpoint of the simplification of a process. Moreover, in a reflective liquid crystal display element, as long as it is a board | substrate of one side, it can also be used as an opaque thing, such as a silicon wafer, and the electrode in this case can also use the material which reflects light, such as aluminum.

The coating method of a liquid crystal aligning agent is not specifically limited, Printing methods, such as screen printing, offset printing, and flexographic printing, an inkjet method, a spray method, a roll coating method, a dip, a roll coater, a slit coater, a spinner, etc. are mentioned. have. In terms of productivity, the transfer printing method is widely used industrially, and is also preferably used in the present invention.

The coating film formed by apply | coating a liquid crystal aligning agent by the said method can be baked, and it can be set as a cured film. Although the drying process after apply | coating a liquid crystal aligning agent is not necessarily required, when the time from application | coating to baking is not constant for every board | substrate, or is not immediately baked after application | coating, it is preferable to implement a drying process. The solvent should just be removed to such an extent that a coating film shape does not deform | transform by conveyance of a board | substrate etc., and this drying is not specifically limited about the drying means. For example, the method of drying for 0.5 minutes-30 minutes, Preferably 1 minute-5 minutes is mentioned on the hotplate of temperature 40 degreeC-150 degreeC, Preferably 60 degreeC-100 degreeC.

The baking temperature of the coating film formed by applying the liquid crystal aligning agent is not particularly limited and may be, for example, at any temperature of 100 to 350 ° C, preferably 120 to 300 ° C, 250 ° C. The firing time can be baked at any time of 5 minutes to 240 minutes. Preferably they are 10 minutes-90 minutes, More preferably, they are 20 minutes-90 minutes. Heating can be normally performed by a well-known method, for example, a hotplate, a hot air circulation furnace, an infrared furnace, etc.

Moreover, although the thickness of the liquid crystal aligning film obtained by baking is not specifically limited, Preferably it is 5-300 nm, More preferably, it is 10-120 nm.

And after forming a liquid crystal aligning film in a board | substrate by said method, the liquid crystal display element of this invention can manufacture and obtain a liquid crystal cell by a well-known method. As a specific example of a liquid crystal display element, the liquid crystal which has the said liquid crystal aligning film formed between the two board | substrates arrange | positioned so as to oppose, the liquid crystal layer formed between board | substrates, and the board | substrate and a liquid crystal layer, and the liquid crystal aligning agent of this invention. It is a liquid crystal display element of the vertical alignment system provided with a cell. Specifically, the liquid crystal aligning film of this invention is apply | coated and baked on two board | substrates, a liquid crystal aligning film is formed, two board | substrates are arrange | positioned so that this liquid crystal aligning film opposes, and the liquid crystal layer comprised of liquid crystal between these two board | substrates. It is a liquid crystal display element of the vertical alignment system provided with the liquid crystal cell manufactured by interposing a contact, ie, making it contact a liquid crystal aligning film, forming a liquid crystal layer, and irradiating an ultraviolet-ray, applying a voltage to a liquid crystal aligning film and a liquid crystal layer. Thus, using the liquid crystal aligning film formed by the liquid crystal aligning agent of this invention, while irradiating an ultraviolet-ray and superposing | polymerizing a polymeric compound, applying the voltage to a liquid crystal aligning film and a liquid crystal layer, the photoreactive side chains which a polymer has By reacting the photoreactive side chain which a polymer has, and a polymeric compound, the orientation of a liquid crystal is fixed more efficiently, and it becomes a liquid crystal display element which was remarkably excellent in a response speed.

Although it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate used for the liquid crystal display element of this invention, Usually, it is a board | substrate with the transparent electrode for driving a liquid crystal on the board | substrate. Specific examples include the same substrates as those described in the liquid crystal alignment film. Although the board | substrate with which the conventional electrode pattern and the projection pattern were formed may be used, in the liquid crystal display element of this invention, since the liquid crystal aligning agent of the said invention is used as a liquid crystal aligning agent which forms a liquid crystal aligning film, it is an example for a single side board | substrate. For example, even in a structure in which a line / slit electrode pattern of 1 to 10 mu m is formed, and a slit pattern and a projection pattern are not formed on the opposing substrate, it is possible to operate. It can be simplified and high transmittance can be obtained.

In a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.

In the case of a transmissive liquid crystal display element, it is common to use the above-mentioned board | substrate, but in a reflective liquid crystal display element, it is possible to also use opaque board | substrates, such as a silicon wafer, as long as it is a board | substrate of one side. At this time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and then firing, and the details are the same as described above.

The liquid crystal material which comprises the liquid crystal layer of the liquid crystal display element of this invention is not specifically limited, The liquid crystal material used by the conventional vertical alignment system, for example, negative type, such as MLC-6608 and MLC-6609 by Merck, Inc. Liquid crystals can be used.

A well-known method is mentioned as a method of clamping this liquid crystal layer between two board | substrates. For example, a pair of board | substrates with which the liquid crystal aligning film was formed is prepared, the spacers, such as a beads, are spread | dispersed on the liquid crystal aligning film of one board | substrate, so that the surface of the side in which the liquid crystal aligning film was formed may be inward, and the other board | substrate is made into The method of bonding together, inject | pouring a liquid crystal under reduced pressure, and sealing is mentioned. Moreover, a pair of board | substrates with which the liquid crystal aligning film was formed is prepared, after spreading spacers, such as a beads, on the liquid crystal aligning film of one board | substrate, a liquid crystal is dripped, and the surface of the side in which the liquid crystal aligning film was formed after that is inside, A liquid crystal cell can also be manufactured by the method of bonding together another board | substrate and sealing. The thickness of the spacer at this time becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

The process of manufacturing a liquid crystal cell by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal aligning film and a liquid crystal layer, for example, applies an electric field to a liquid crystal aligning film and a liquid crystal layer by applying a voltage between the electrodes provided on the board | substrate, The method of irradiating an ultraviolet-ray, maintaining this electric field is mentioned. Here, as a voltage applied between electrodes, it is 5-30 Vp-p, Preferably it is 5-20 Vp-p. The irradiation amount of ultraviolet rays is 1-60 J, for example, Preferably it is 40 J or less, More preferably, it is 20 J or less. It is preferable that the amount of ultraviolet irradiation is less because the decrease in reliability caused by the destruction of the liquid crystal or the member constituting the liquid crystal display element can be suppressed, and the production efficiency is increased by reducing the ultraviolet irradiation time.

Thus, when ultraviolet-ray is irradiated, applying a voltage to a liquid crystal aligning film and a liquid crystal layer, a polymeric compound will react and form a polymer, and the response speed of the liquid crystal display element obtained by storing the direction in which a liquid crystal molecule inclines by this polymer is memorized. To speed up. Moreover, when ultraviolet-ray is irradiated, applying a voltage to a liquid crystal aligning film and a liquid crystal layer, in a side chain which vertically orients a liquid crystal, a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, The photoreactive side chains which a polyimide precursor which has a photoreactive side chain containing at least 1 sort (s) chosen, and the at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor, or a polymer Since the photoreactive side chain which has the polymerizable compound reacts, the response speed of the liquid crystal display element obtained can be made quick.

Moreover, the said liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for manufacturing the liquid crystal display element of the vertical alignment system, such as a PSA type liquid crystal display or SC-PVA type liquid crystal display, but is manufactured by a rubbing process or a photo-alignment process, It can also be used suitably also for the use of a liquid crystal aligning film.

Example

Hereinafter, although it demonstrates further in detail based on an Example, this invention is not limited at all by this Example.

The polymerizable compound added to the liquid crystal aligning agent has the following structure.

[Chemical Formula 39]

[Formula 40]

(41)

(42)

(43)

(44)

[Chemical Formula 45]

RM7 is ADAMANTATE X-DA manufactured by Idemitsu Kosan Co., Ltd.

(46)

RM8 is DCP manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

(Synthesis of polymeric compound RM1 (5,5- (biphenyl-4,4'-diylbis (oxy)) bis (pentane-5,1-diyl) bis (2-methacrylate))

In a 500 ml eggplant flask equipped with a cooling tube, 14.9 g (80.0 mmol) of biphenol, 35 g (167.0 mmol) of 5-bromopentyl acetate, 41.5 g (300 mmol) of potassium carbonate, and 250 ml of acetone were added. It added and it was made into the mixture, and it reacted at 60 degreeC, stirring for 48 hours. After the reaction was completed, the reaction solution was poured into 600 mL of pure water to obtain 33.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a compound (RM1-A) shown by following Reaction Formula. The yield was 95%.

(47)

250 ml of ethanol, 18.0 g (41 mmol) of the compound (RM1-A) obtained above, and 100 ml of 10% aqueous sodium hydroxide solution were added to a 1-liter flask equipped with a cooling tube to prepare a mixture. The reaction was stirred at 5 hours. After completion of the reaction, 500 ml of water and the reaction solution were added to a 1000 ml beaker, and after stirring at room temperature for 30 minutes, 80 ml of a 10% HCl aqueous solution was added dropwise, followed by filtration to obtain 12.2 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a compound (RM1-B) shown by following Reaction Formula. The yield was 83%.

(48)

5.0 g (14.0 mmol) of the compound (RM1-B) obtained above was added with 3.2 g of triethylamine (Et ₃ N) and a small amount of 2,6-di-tert-butyl-p-cresol (BHT). It was dissolved in 30 ml of hydrofuran (THF), stirred at room temperature, and a solution obtained by dissolving 3.3 g (32 mmol) of methacryloyl chloride in 20 ml of THF was added dropwise over 15 minutes while cooling with a water bath. It was. After dripping, it stirred for 30 minutes, and continued stirring overnight, removing a water bath and returning to room temperature. After completion of the reaction, the reaction solution was poured into 200 ml of pure water and filtered to obtain a white solid. This solid was dissolved in chloroform and precipitated using hexane (hexane / chloroform = 2/1) to give 2.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is polymeric compound RM1 shown by following Reaction Formula. The yield was 38%.

(49)

(Synthesis of Polymerizable Compound RM4)

(50)

(Wherein Ac represents CH ₃ CO-)

In a 1 L four-neck flask, Compound [A] (17.00 g, 79.2 mmol), Compound [B] (50.00 g, 239 mmol), Potassium Carbonate (66.09 g, 239 mmol), N, N'-dimethylform Amide (DMF) (200 g) was added and nitrogen-substituted, and heat-stirring was performed at 100 degreeC. Reaction tracking was performed by high performance liquid chromatography (HPLC), and after completion | finish confirmation of reaction, the reaction solution was poured into distilled water (1.6 L), and the precipitated solid was filtered and washed with distilled water, and the crude material was obtained.

Next, the obtained crude substance was moved to the reaction container, ethanol (350g) and 10 wt% sodium hydroxide aqueous solution (245g) were added, and it stirred at 85 degreeC by heating and stirring. Reaction tracking was performed by HPLC, and after confirming completion | finish of reaction, the reaction solution was poured into 10 wt% hydrochloric acid aqueous solution (500g), and the precipitated solid was filtered. 14.53g of compounds [C] were obtained by wash | cleaning one by one by distilled water, methanol, and ethyl acetate sequentially and drying under reduced pressure (yield 51%).

Next, the compound [C] (14.53 g, 37.6 mmol), triethylamine (5.33 g, 52.6 mmol) and THF (200 g) obtained as described above were introduced into a 1 L four-neck flask, followed by nitrogen substitution. The solution was cooled to 10 ° C. or less. There, a THF (25 g) solution of methacryloyl chloride (6.87 g, 52.6 mmol) was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction solution was returned to 23 ° C and further stirring was continued. Reaction tracking was performed by HPLC, and after confirming completion | finish of reaction, the reaction solution was poured into distilled water (1.7 L). The ethyl acetate / hexane mixed solvent was added there and the water layer was removed by liquid separation operation. Furthermore, after wash | cleaning an organic layer three times sequentially with 10 wt% potassium carbonate aqueous solution and brine, and drying an organic layer with magnesium sulfate, the solvent was distilled off by filtration and an evaporator, and the crude substance of polymeric compound RM4 was obtained. . 13.1g of polymeric compounds RM4 were obtained by wash | cleaning the obtained crude substance with 2-propanol / hexane, and drying the obtained solid under reduced pressure (yield 66%).

&Lt; Preparation of liquid crystal aligning agent &

The abbreviations used in the preparation of the following liquid crystal aligning agent are as follows.

BODA: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

DBA: 3,5-diaminobenzoic acid

PCH: 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene

BEM-S: 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula

(51)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

The conditions for measuring the molecular weight of the polyimide are as follows.

Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Corporation,

Column: Column (KD-803, KD-805) manufactured by Shodex Co.,

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydro Furan (THF) 10 ml / l)

Flow rate: 1.0 ml / min

Standard for the production of calibration curve Sample: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

The imidization rate of the polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube (NMR sampling tube standard Φ 5 manufactured by Kusano Scientific Inc.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS (tetramethylsilane) mixed product) was added, Ultrasonic was added to complete dissolution. The proton NMR of 500 MHz was measured for this solution by the NMR measuring machine (JNW-ECA500) by the Nippon Electron Datum company. The imidation ratio sets a proton derived from the structure which does not change before and after imidization as a reference proton, and uses the peak integrated value of this proton and the proton peak integrated value derived from the NH group of the amic acid which appears in the vicinity of 9.5-10.0 ppm. It calculated | required by the following formula. In addition, in the following formula, x is a proton peak integrated value derived from NH group of an amic acid, y is a peak integrated value of a reference proton, and alpha is amic acid in the case of polyamic acid (imidization ratio is 0%). Number ratio of reference protons to one proton of NH group.

Imidization ratio (%) = (1 -? X / y) x 100

(Example 1)

BODA (17.01 g, 68.0 mmol), DBA (10.35 g, 68.0 mmol), PCH (19.41 g, 51.0 mmol), BEM-S (13.48 g, 51.0 mmol) was dissolved in NMP (239.75 g) After reacting at 80 degreeC for 5 hours, CBDA (19.67g, 100.3 mmol) and NMP (79.92g) were added, and it reacted at 40 degreeC for 10 hours, and obtained the polyamic-acid solution. After adding NMP to this polyamic-acid solution (399g) and diluting to 6 mass%, acetic anhydride (43.33g) and pyridine (134.33g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (5300 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (A). The imidation ratio of this polyimide was 60%, the number average molecular weight was 20000 and the weight average molecular weight was 55000.

NMP (64.0g) is added to the obtained polyimide powder (A) (6.0g), and it stirred for 12 hours and made it melt | dissolve at 50 degreeC. BCS (30.0g) was added to this solution, and the liquid crystal aligning agent (B) was obtained by stirring at 50 degreeC for 5 hours.

Moreover, 0.06g (10 mass% with respect to solid content) was added with respect to 10.0 g of said liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B1).

(Example 2)

0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B2).

(Example 3)

0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B3).

(Example 4)

0.06g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B4).

(Example 5)

0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B5).

(Example 6)

0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B6).

(Example 7)

0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B7).

(Comparative Example 1)

0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of liquid crystal aligning agents (B), and it stirred for 3 hours and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B8).

&Lt; Production of liquid crystal cell &

(Example 8)

The liquid crystal cell was produced by the procedure shown below using the liquid crystal aligning agent (B1) obtained in Example 1. The liquid crystal aligning agent (B1) obtained in Example 1 was spin-coated to the ITO surface of the ITO electrode substrate in which the ITO electrode pattern whose pixel size is 100 micrometers x 300 micrometers, and the line / space is 5 micrometers, respectively, is formed, and 80 degreeC After drying for 90 seconds on the hotplate of, it baked in 30 degreeC hot-air circulation type oven for 30 minutes, and formed the liquid crystal aligning film of 100 nm in film thickness.

Moreover, after spin-coating a liquid crystal aligning agent (B1) to the ITO surface in which the electrode pattern is not formed, and drying for 90 second on a 80 degreeC hotplate, it bakes for 30 minutes in 200 degreeC hot-air circulation type oven, A liquid crystal aligning film with a film thickness of 100 nm was formed.

After spread | dispersing a 6 micrometers bead spacer on the liquid crystal aligning film of one board | substrate with respect to said two board | substrates, the sealing compound (Kyoritsu Chemical make XN-1500T) was printed on it. Subsequently, the surface of the side in which the liquid crystal aligning film of the other board | substrate was formed was made inside, and after bonding together with the previous board | substrate, the sealing compound was hardened and the empty cell was manufactured. Liquid crystal MLC-6608 (Merck & Co., Ltd. brand name) was injected into this empty cell by the pressure reduction injection method, the Isotropic process (reorientation process of the liquid crystal by heating) was performed in 120 degreeC oven, and the liquid crystal cell was produced.

The response speed immediately after manufacture of the obtained liquid crystal cell was measured by the following method. Then, 20J was irradiated with UV which passed the 313 nm band pass filter from the outer side of this liquid crystal cell in the state which applied the voltage of 20 Vp-p to this liquid crystal cell. Thereafter, the response speed was again measured, and the response speeds before and after the UV irradiation were compared. Table 2 shows the results of the response speed immediately after the liquid crystal cell production (in the table, denoted as "initial") and after irradiating UV (in the table, denoted as "after UV").

How to measure the response speed

First, in the measuring apparatus comprised by the order of one set of polarizing plates and a light quantity detector which were made into the backlight and the cross nicol state, the liquid crystal cell was arrange | positioned between one set of polarizing plates. At this time, the pattern of the ITO electrode in which the line / space was formed was made into the angle of 45 degrees with respect to cross nicol. Then, a square wave having a voltage of ± 4 V and a frequency of 1 Hz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is put into the oscilloscope, and the luminance when no voltage is applied. The time taken for the luminance to change from 10% to 90% was defined as the response speed by setting the value of the saturated luminance by applying a voltage of 0% and ± 4 V to 100%.

(Example 9)

Except having used the liquid crystal aligning agent (B2) instead of the liquid crystal aligning agent (B1), operation similar to Example 8 was performed and the response speed in UV irradiation back and front was compared.

(Example 10)

Except having used the liquid crystal aligning agent (B3) instead of the liquid crystal aligning agent (B1), operation similar to Example 8 was performed and the response speed in UV irradiation back and front was compared.

(Example 11)

The baking temperature was changed from 200 degreeC to 140 degreeC, except having used the liquid crystal aligning agent (B4) instead of the liquid crystal aligning agent (B1), operation similar to Example 8 was performed and the response speed in UV irradiation back and front was compared. .

(Example 12)

The baking temperature was changed from 200 degreeC to 140 degreeC, operation similar to Example 8 was performed except having used the liquid crystal aligning agent (B5) instead of the liquid crystal aligning agent (B1), and compared the response speed in UV irradiation back and front. .

(Example 13)

The baking temperature was changed from 200 degreeC to 140 degreeC, operation similar to Example 8 was performed except having used the liquid crystal aligning agent (B6) instead of the liquid crystal aligning agent (B1), and compared the response speed in UV irradiation back and front. .

(Example 14)

The baking temperature was changed from 200 degreeC to 140 degreeC, except having used the liquid crystal aligning agent (B7) instead of the liquid crystal aligning agent (B1), operation similar to Example 8 was performed and the response speed in UV irradiation back and front was compared. .

(Comparative Example 2)

Except having used the liquid crystal aligning agent (B8) instead of the liquid crystal aligning agent (B1), operation similar to Example 8 was performed and the response speed in UV irradiation back and front was compared.

<Storage stability test>

(Example 15)

The storage stability test of the liquid crystal aligning agent was implemented in the procedure shown below using the liquid crystal aligning agent (B1) obtained in Example 1. The liquid crystal aligning agent (B1) obtained in Example 1 was preserve | saved in the freezer maintained at minus 20 degreeC, and the liquid crystal aligning agent after 24 hours was observed. When the polymeric compound added to the liquid crystal aligning agent was melt | dissolved, the case where it melt | dissolves and it precipitates as "precipitation" is shown in Table 2, and a result is shown.

(Example 16)

Except having used the liquid crystal aligning agent (B2) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

(Example 17)

Except having used the liquid crystal aligning agent (B3) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

(Example 18)

Except having used the liquid crystal aligning agent (B4) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

(Example 19)

Except having used the liquid crystal aligning agent (B5) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

(Example 20)

Except having used the liquid crystal aligning agent (B6) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

(Example 21)

Except having used the liquid crystal aligning agent (B7) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

(Comparative Example 3)

Except having used the liquid crystal aligning agent (B8) instead of the liquid crystal aligning agent (B1), operation similar to Example 15 was performed and the storage stability test was done.

As a result, as shown in Table 2, in all of Examples 8-14, the response speed was very fast. Moreover, the polymeric compound which has a mother nucleus represented by said formula (i-1)-(i-3) which is a specific polymeric compound, and the polymeric property which has a mother nucleus represented by said formula (ii-1)-(ii-3) In Examples 15 to 21 containing the compound, the polymerizable compound did not precipitate even when cryopreserved, but precipitation occurred in Comparative Example 3 containing the other polymerizable compound.

Therefore, the polymerizable compound which has polymers, such as a polyimide which has a photoreactive side chain, and the parent nucleus represented by said Formula (i-1)-(i-3), and said Formula (ii-1)-(ii-3) By using the liquid crystal aligning agent containing the polymeric compound which has the mother-nucleus represented by (), it was confirmed that it becomes the liquid crystal aligning agent which can make a response speed very fast and is excellent also in storage stability.

Moreover, except having changed the mass ratio NMP / BCS of NMP and BCS at the time of obtaining a liquid crystal aligning agent (B) to the value of following Table 3, it carried out similarly to Examples 1-6 and Comparative Example 1, Liquid crystal aligning agents were prepared, respectively. In addition, the compounding ratio of the polymeric compound of each liquid crystal aligning agent is 10 mass% with respect to solid content also in any polymeric compound similarly to the above.

About the liquid crystal aligning agent which changed this solvent composition, the result of having carried out storage stability test by the method similar to the above is shown in Table 3. As a result, as shown in Table 3, the polymeric compound which has the mother nucleus represented by said formula (i-1)-(i-3), and the mother nucleus represented by said formula (ii-1)-(ii-3) In the liquid crystal aligning agent containing the polymeric compound which has, even if it preserve | save frozen in any solvent composition, the polymeric compound did not precipitate, but precipitation occurred in the liquid crystal aligning agent containing RM1 which is another polymeric compound.

Claims (9)

Polyimide which has a side chain which orientates a liquid crystal perpendicularly, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least one polymer selected from a precursor and a polyimide obtained by imidating the polyimide precursor,
At least one parent nucleus selected from the following formulas (i-1) to (i-3) and a group which is photopolymerized or photocrosslinked at one or more terminals, and the photopolymerized or photocrosslinked group is directly or via a linking group A polymerizable compound bound to the mother core,
It has a solvent, The liquid crystal aligning agent characterized by the above-mentioned.
[Chemical Formula 1]

The method of claim 1,
The said polymeric compound is selected from a following formula, The liquid crystal aligning agent characterized by the above-mentioned.
(2)

(Wherein, R ³¹ represents a single bond or -R ³⁵ O-, R ³⁵ is an alkylene group having a carbon number of 1 to 10 straight-chain, R ³² represents a single bond or -OR ³⁶ - represented by, R ³⁶ is straight An alkylene group having 1 to 10 carbon atoms in the chain, R ³³ and R ³⁴ are each independently a hydrogen atom or a methyl group) Polyimide which has a side chain which orientates a liquid crystal perpendicularly, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group. At least one polymer selected from a precursor and a polyimide obtained by imidating the polyimide precursor,
At least one kind of nucleus selected from the following formulas (ii-1) to (ii-3) and a group which is photopolymerized or photocrosslinked at one or more terminals, wherein the photopolymerized or photocrosslinked group is the mother nucleus and the oxyalkylene group. A polymerizable compound bound thereto,
It has a solvent, The liquid crystal aligning agent characterized by the above-mentioned.
(3)

The method of claim 3, wherein
The said polymeric compound is selected from a following formula, The liquid crystal aligning agent characterized by the above-mentioned.
[Chemical Formula 4]

(Wherein, R ⁴¹ represents a single bond or represents a -R ⁴⁵ O-, R ⁴⁵ is a carbon number of 1 to 10 alkylene groups of straight-chain, R ⁴² represents a single bond or -OR ⁴⁶ - represented by, R ⁴⁶ is straight An alkylene group having 1 to 10 carbon atoms in the chain, each of R ⁴³ and R ⁴⁴ is independently a hydrogen atom or a methyl group) 5. The method according to any one of claims 1 to 4,
Said photoreactive side chain contains group chosen from following formula (I), The liquid crystal aligning agent characterized by the above-mentioned.
[Chemical Formula 5]

(Wherein R ¹¹ is H or a methyl group) 6. The method according to any one of claims 1 to 5,
The group photopolymerized or photocrosslinked is selected from the following formula (II).
[Chemical Formula 6]

(In formula, R <^12> is H or a C1-C4 alkyl group, Z <^1> is a bivalent aromatic ring or heterocyclic ring which may be substituted by the C1-C12 alkyl group or the C1-C12 alkoxyl group, Z is ² is a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms) The liquid crystal aligning film in any one of Claims 1-6 is apply | coated to a board | substrate, and is obtained by baking, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning agent of any one of Claims 1-6 was apply | coated to a board | substrate, it contacted the liquid crystal aligning film obtained by baking, and formed a liquid crystal layer, and manufactured by irradiating an ultraviolet-ray, applying a voltage to this liquid crystal layer A liquid crystal cell is provided, The liquid crystal display element characterized by the above-mentioned. The liquid crystal aligning agent of any one of Claims 1-6 is apply | coated to a board | substrate, it contacts with the liquid crystal aligning film obtained by baking, and forms a liquid crystal layer, irradiates an ultraviolet-ray, apply a voltage to this liquid crystal layer, and a liquid crystal cell The manufacturing method of the liquid crystal display element characterized by the above-mentioned.