KR20130122931A - Liquid crystal-aligning agent, liquid crysat-aligning film, liquid crystal display element and method for producing liquid crystal display elements - Google Patents

Abstract

The polyimide precursor which has a side chain which orientates a liquid crystal perpendicularly | vertically, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group, and this polyimide precursor A liquid crystal aligning agent which has at least 1 sort (s) of polymer chosen from the polyimide obtained by dehydration, the polymeric compound which has group photopolymerized or photocrosslinked at 2 or more terminal, respectively, 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 {LIQUID CRYSTAL-ALIGNING AGENT, LIQUID CRYSAT-ALIGNING FILM, LIQUID CRYSTAL DISPLAY ELEMENT AND METHOD FOR PRODUCING LIQUID CRYSTAL DISPLAY ELEMENTS}

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). In general, 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 in the display electrode, and the like. However, ultraviolet rays are emitted by adding a photopolymerizable compound to the liquid crystal composition and applying a voltage to the liquid crystal cell. Since the polymer structure in which the direction in which the liquid crystal molecules are tilted are stored is formed on the liquid crystal alignment film by irradiation, 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. Moreover, in the UV irradiation process required in PSA mode, when the irradiation amount is large, the component in a liquid crystal will decompose | distribute, and will cause the fall of reliability.

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

However, it is desired to make the response speed of liquid crystal display elements faster. In addition, it is conceivable to increase the response speed of the liquid crystal display element by increasing the amount of the photopolymerizable compound added. However, if the photopolymerizable compound remains unreacted in the liquid crystal, it becomes an impurity and causes the reliability of the liquid crystal display element to decrease. Since it becomes this, the polymeric compound which can make a response speed quick with a small addition amount is preferable.

The subject of this invention is solving the problem of the prior art mentioned above, and manufacture of the liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, and liquid crystal display element which can improve the response speed of the liquid crystal display element of a vertical alignment system. To provide a method.

The liquid crystal aligning agent of this invention which solves the said subject is a side chain which orientates a liquid crystal perpendicularly, and photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and cinnamoyl group. At least one polymer selected from a polyimide precursor having a polyimide precursor and a polyimide obtained by imidating the polyimide precursor, a polymerizable compound each having a group polymerized or photocrosslinked at two or more terminals, and a solvent It features.

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

[Formula 1]

(Wherein R ¹¹ is H or a methyl group)

Moreover, it is preferable that the group photopolymerized or photocrosslinked is selected from following formula (II).

(2)

(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, and 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 element of this invention comprises the liquid crystal cell manufactured by apply | coating the said liquid crystal aligning agent to a board | substrate, making it contact a liquid crystal aligning film obtained by baking, and forming a liquid crystal layer, and irradiating an ultraviolet-ray, applying a voltage to this liquid crystal layer. It is characterized by.

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 forms a liquid crystal layer, irradiates an ultraviolet-ray, applying a voltage to this liquid crystal layer, and a liquid crystal cell It characterized in that the manufacturing.

According to this invention, the liquid crystal display element of the vertical alignment system with a quick response speed can be provided. And in this liquid crystal aligning agent, even if the addition amount of a polymeric compound is small, a response speed can fully be improved.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of this invention has a side chain which orientates a liquid crystal perpendicularly, and the polyimide precursor which has a photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and cinnamoyl group. And at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor, the polymeric compound which has group photopolymerized or photocrosslinked at 2 or more terminals, and a solvent, respectively. 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 contains the polymeric compound which has group photopolymerized or photocrosslinked at two or more terminals, respectively. That is, the polymeric compound which the liquid crystal aligning agent of this invention contains is a compound which has two or more terminal which has group photopolymerized or photocrosslinked. Here, 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. In addition, the compound which has group to photocrosslink reacts even if the compound which has group to photocrosslink.

It has a side chain which orientates the liquid crystal mentioned later in this polymerizable compound perpendicularly | vertically, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group. Production of the liquid crystal display element of a vertical alignment system, such as an SC-PVA-type liquid crystal display, by making it contain in a liquid crystal aligning agent with the polyimide precursor and at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor. When used in the above, the response speed can be dramatically improved as compared with the case where the polymer having the side chain and the photoreactive side chain orientated vertically to the liquid crystal or the polymerizable compound alone is used, and the polymerizable compound is less. The addition amount of can also sufficiently improve the response speed.

As group which photopolymerizes or photocrosslinks, monovalent group represented by said formula (II) is mentioned.

As a specific example of a polymeric compound, it has a compound which has a group which photopolymerizes to each of two terminal as shown by following formula (III), and the terminal which photocrosslinks with the terminal which has a photopolymerizable group as shown by following formula (IV). The compound which has a terminal and the group which photocrosslinks to each of the two terminal as shown by following formula (V) are 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 a divalent organic group to be. Q ¹ has a cyclic 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 -) . This is because the interaction with the liquid crystal tends to become large.

(3)

[Formula 4]

[Chemical Formula 5]

As a specific example of the polymeric compound represented by Formula (III), the polymeric compound represented by following formula (1) is mentioned. According to the following formula (1), V represents a single bond or -R ¹ O-, R ¹ is a straight-chain or alkylene group of 1 to 10 carbon atoms in the branch, and preferably represents a -R ¹ O-, R ¹ is a linear or branched C2-C6 alkylene group. Moreover, W is represented by a single bond or -OR <^2> -, R <^2> is a linear or branched C1-C10 alkylene group, Preferably it is represented by -OR <^2> -, and R <^2> is a linear or branched carbon number. It is an alkylene group of 2-6. In addition, although V and W may have the same structure and may differ, if it is the same, synthesis | combination is easy. In addition, since it is filing separately about the polymeric compound represented by following formula (1), you may remove it from this invention.

[Chemical Formula 6]

Since the polymerizable compound represented by the said Formula (1) is a compound of the specific structure which has the (alpha)-methylene- (gamma) -butyrolactone group which is a polymeric group (group which photopolymerizes) at the sock end, it takes the structure which a polymer was rigid, and a liquid crystal It is because the orientation immobilization ability of this is excellent, as shown in the Example mentioned later, at least 1 sort (s) of polymer chosen from the polyimide precursor and the polyimide obtained by imidating this polyimide precursor are used as a material of a liquid crystal aligning film. By using for manufacture of the liquid crystal display element of the vertical alignment system, such as said SC-PVA-type liquid crystal display, especially, a response speed can be improved significantly. In general, the formation process of the liquid crystal alignment film includes a step of baking at a high temperature in order to completely remove the solvent, but a compound having a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, and an epoxy group. In thermal stability, it is hard to endure the baking at high temperature. On the other hand, the polymeric compound represented by the said Formula (1) can fully endure the high temperature, for example, the baking temperature of 200 degreeC or more, whether it is because of the structure inferior in thermal polymerization property.

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. In the case of the polymerizable compound having a structure bonded to the phenylene group, the response speed can be significantly improved particularly in the same manner as the polymerizable compound each having an α-methylene-γ-butyrolactone group in the sock end. Moreover, if it is a polymeric compound which has a structure which the acrylate group and the methacrylate group couple | bond with the phenylene group via spacers, such as an oxyalkylene group, it is because stability with respect to heat improves, high temperature, for example, 200 degreeC or more baking It can withstand temperature enough.

In such a polymeric compound, the compound represented by a following formula is a novel compound.

[Formula 7]

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, the polymeric compound represented by the said Formula (1) 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.

[Formula 8]

(Wherein R 'represents a monovalent organic group)

In addition, 2- (bromomethyl) acrylic acid is proposed by Ramaran and the like represented by the following 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 9]

Specific synthesis examples, V is -R ¹ O-, W is -OR ² - ² a, R ¹ and R ² are represented by the following, the case of synthesizing the polymeric compound represented by the same formula (1) Scheme There are two methods.

[Formula 10]

[Formula 11]

In the case of synthesizing a polymerizable compound represented by the above formula (1) in which R ¹ and R ² are different from each other, a method represented by the following reaction formula can be mentioned.

[Chemical Formula 12]

In the case of synthesizing a polymerizable compound represented by the above formula (1) in which V and W are single bonds, the following reaction scheme can be mentioned.

[Chemical Formula 13]

Moreover, the liquid crystal aligning agent of this invention is at least 1 sort (s) chosen from a polyimide precursor and the polyimide obtained by imidating this polyimide precursor, and has a side chain which orientates a liquid crystal perpendicularly, and a side chain of photoreactivity. It contains a polymer. 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 in the middle of a long chain alkyl group and a long chain alkyl group Hydrocarbon groups, such as group which has, and a steroid group, and the group which substituted one part or all part of the hydrogen atom 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 couple | bond directly with the main chain of polyimide precursors, such as a polyamic acid and a polyamic acid ester, or a polyimide, ie, a polyamic acid frame | skeleton, a polyimide frame | skeleton, etc. You may couple | bond through. As a side chain which orientates a liquid crystal perpendicularly, the hydrocarbon group in which a hydrogen atom may be substituted by fluorine is 8-30, Preferably 8-22, Specifically, an alkyl group, a fluoroalkyl group, an alkenyl group , Phenethyl group, styrylalkyl group, naphthyl group, fluorophenylalkyl group and the like. As a side chain which orientates another liquid crystal vertically, what is represented by following formula (a) is mentioned, for example.

[Formula 14]

(1, m, and n each independently represent an integer of 0 or 1, and R ³ represents an alkylene group having 2 to 6 carbon atoms, -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 an alkyl group having 2 to 24 carbon atoms. Or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent large cyclic substituent composed of them).

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 1 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 carbon number It is an alkyl group of 2-12, 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, 1 consisting of them It is a valent big 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 side chains for vertically aligning the liquid crystals to vertically align the liquid crystals depends on the structure of the side chains for vertically aligning the liquid crystals. The greater the amount, the higher the ability to orient 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 and polyimides, such as the polyamic acid and polyamic acid ester 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 It contains at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group as a sexual group. Thus, at least 1 sort (s) chosen from the methacrylic group, the acryl group, the vinyl group, and the cinnamoyl group for 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 By having a photoreactive side chain containing and using for a liquid crystal aligning agent with the said polymeric compound, as shown in the Example mentioned later, a response speed can be improved significantly.

The photoreactive side chain may couple | bond directly with the polyimide precursor or the main chain of a polyimide, and may couple through the appropriate coupling group. As photoreactive side chain, what is represented by following formula (b) is mentioned, for example.

[Formula 15]

(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 Represents a C1-C20 alkylene group substituted by a single bond or unsubstituted or a fluorine atom, -CH ₂ -in the alkylene group may be optionally substituted with -CF ₂ -or -CH = CH-, When any group illustrated next does not adjoin each other, you may substitute by these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent hetero ring. R ¹⁰ represents a methacryl group, an acryl group, a vinyl group, or cinnamoyl group)

Further, the formula (b) in R ⁸ is conventional may be formed by organic synthetic methods, in view of ease of _{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 .

[Chemical Formula 16]

R ¹⁰ is preferably a methacryl group, an acryl 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 affect is preferable.

Polyimide precursor which has a side chain which orientates such 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, and cinnamoyl group, and this polyimide precursor Although the method of manufacturing at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating is not specifically limited, For example, in the method of obtaining a polyamic acid by reaction of a diamine and tetracarboxylic dianhydride, a liquid crystal Tetracarboxylic dianhydride having a diamine having a side chain orthogonally oriented or a liquid chain vertically aligning the liquid crystal or at least one member selected from methacryl, acryl, vinyl and cinnamoyl groups. At least one selected from a diamine or methacryl group, an acryl group, a vinyl group and a cinnamoyl group having a photoreactive side chain What is necessary is just to copolymerize the tetracarboxylic dianhydride which has a photoreactive side chain containing 1 type.

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.

[Chemical Formula 17]

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

[Chemical Formula 18]

(In Formulas (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, or -NH-. , A ₁₁ represents a single bond or a phenylene group, a represents the same structure as the side chain for vertically aligning the liquid crystal represented by the formula (a), and a 'aligns 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)

[Chemical Formula 19]

(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- *, provided that "*" is bonded to A _15, and A ₁₇ represents an oxygen atom or -COO- * (wherein "*" is bonded; a is engaged with (CH ₂₎ a _2). 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.

[Chemical Formula 20]

(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 21]

(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)

[Chemical Formula 22]

(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)

(23)

(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)

&Lt; EMI ID =

(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.)

(25)

(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.)

(26)

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.

(27)

(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.

(28)

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.

Said 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 is set as a liquid crystal aligning film.

It is preferable that the diamine which has a side chain which orients such a liquid crystal perpendicularly uses the quantity used as 5-50 mol% of the diamine component used for the synthesis | combination of a polyamic acid, More preferably, it is 10-40 of a diamine component Mol% 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, and a cinnamoyl group, For example, the diamine which has a side chain represented by said formula (b) is mentioned. Can be mentioned. More specifically, although diamine represented by the following general formula (6) is mentioned, for example, It is not limited to this.

[Formula 29]

(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.

Although the diamine which has a photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and cinnamoyl group specifically, the following compounds are mentioned, It is limited to this no.

(30)

(Wherein X ¹ and X ² are each independently a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y is unsubstituted or carbon number substituted by a fluorine atom) 1-20 alkylene group)

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, and a cinnamoyl group has liquid crystal aligning property, a pretilt angle, voltage retention characteristic, when it sets it as a liquid crystal aligning film, One type or two types or more can also be mixed and used according to the characteristics, such as a stored 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, and cinnamoyl group is 10-70 mol of the diamine component used for the synthesis | combination of a polyamic acid. It is preferable to use the quantity used as%, More preferably, it is 20-60 mol%, Especially preferably, it is 30-50 mol%.

In addition, the polyamic acid can use together other 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. have. 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 Lenbis (methylene)] dianiline, 3,3 '-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4 -Phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone] , 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3- Phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate , N, N '-(1,4-phenylene) bis (4-aminobenzamide), N, N'-(1,3-phenylene) bis (4-aminobenzamide), N, N'- (1,4-phenylene) bis (3-aminobenzamide), N, N '-(1,3-phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl Terephthalamide, N, N'-bis (3-aminophenyl) terephthal 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 to be 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, tetracarboxylic dianhydride may also use together one type or two types or more according to the characteristics, such as liquid crystal alignability, voltage holding characteristic, and stored charge, when it sets as a liquid crystal aligning film.

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. Reaction of a diamine component and tetracarboxylic dianhydride is advantageous at the point which progresses comparatively easily in an organic solvent, and a by-product does not generate | occur | produce.

As an organic solvent used for the said reaction, if the produced polyamic acid melt | dissolves, it will not specifically limit. Moreover, even if it is an organic solvent in which a polyamic acid does not melt | dissolve, you may mix and use it with the said solvent in the range which does not precipitate the produced polyamic acid. In addition, since water in an organic solvent inhibits a polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use what dried the organic solvent. 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 be mixed and polymerized 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, it is -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 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.

Moreover, polyamic acid ester is a suitable condensing agent and base of the reaction of tetracarboxylic-acid diester dichloride and the diamine similar to the synthesis | combination of the said polyamic acid, and the diamine similar to the synthesis | combination of tetracarboxylic-acid diester and said polyamic acid. It can manufacture by making it react under. Alternatively, the polyamic acid may be synthesized in advance by the above-described method, and the carboxylic acid in the amic 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 precursors or polyimide, such as polyamic acid and 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 a poor 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 recovered by filtration, 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 above-mentioned, the liquid crystal aligning agent of this invention contains the side chain which orientates a liquid crystal perpendicularly, and the photoreactive side containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and cinnamoyl group. A polyimide precursor having a chain and at least one polymer selected from a polyimide obtained by imidating the polyimide precursor, a polymerizable compound each having a photopolymerized or photocrosslinked group at two or more terminals, and a solvent The content ratio of the polymerizable compound each having a group polymerized by photopolymerization or photocrosslinking at two or more terminals is not limited to the blending ratio, but the side chain for vertically aligning the liquid crystal, methacryl group, acryl group and vinyl Polyimide precursor which has a photoreactive side chain containing at least 1 sort (s) chosen from 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 imidating a sieve, More preferably, it is 5-30 mass parts. Moreover, the polyimide precursor which has a side chain which orientates perpendicularly the liquid crystal contained in a liquid crystal aligning agent, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and cinnamoyl group. 1 mass%-20 mass% are preferable, and, as for content of the at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor, More preferably, 3 mass%-15 mass% are especially preferable. Is 3 mass%-10 mass%.

Moreover, the liquid crystal aligning agent of this invention is a poly 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, and cinnamoyl group. The polymer other than at least 1 sort (s) of polymer chosen from the mid precursor and the polyimide obtained by imidating this polyimide precursor may be contained. In that case, 0.5 mass%-15 mass% are preferable, and, as for content of this other polymer in the polymer all components, More preferably, they are 1 mass%-10 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, The side chain which orientates the said 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, and cinnamoyl group. And dissolving components containing at least one polymer selected from a polyimide precursor having a polyimide precursor and a polyimide obtained by imidating the polyimide precursor, or a polymerizable compound each having a photopolymerized or photocrosslinked group at two or more terminals. Or what is necessary is just to be able to disperse | distribute. For example, the organic solvent as illustrated by the synthesis | combination of said polyamic acid is mentioned. Among them, N-methyl-2-pyrrolidone,? -Butyrolactone, N-ethyl-2-pyrrolidone, Dimethyl propanamide is preferable from the viewpoint 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. Examples thereof include a compound which improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

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 these compounds are used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent.

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 has a side chain which orientates a liquid crystal perpendicularly, and the polyimide precursor which has a photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and cinnamoyl group. Liquid crystal using a liquid crystal aligning film obtained because it has a polymeric compound which has group photopolymerized or photocrosslinked at two or more terminals with at least 1 sort (s) of polymer chosen from the polyimide obtained by imidating this polyimide precursor, respectively. The response speed of a display element can be made quick.

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. Further, the cured film may be rubbed, irradiated with polarized light or a specific wavelength, or the like, treated with an ion beam, or irradiated with UV light while a voltage is applied to the liquid crystal display element after the liquid crystal filling as an alignment film for PSA. . In particular, it is useful to use it as an oriented film for PSA.

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 And plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, and the like. Moreover, it is preferable to use the board | substrate with which the 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.

The thickness of the liquid crystal alignment film obtained by baking is not particularly limited, but is preferably 5 to 300 nm, and more preferably 10 to 100 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. As a specific example, the thing similar to the board | substrate described by the said liquid crystal aligning film is mentioned. 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. In a reflection type liquid crystal display element, if it is only a single side board | substrate, it is also possible to use opaque board | substrates, such as a silicon wafer. 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 it, and the details are 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 spacer, such as a beads, is 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, injecting a liquid crystal under reduced pressure, and sealing are mentioned. Moreover, a pair of board | substrates with which the liquid crystal aligning film was formed is prepared, liquid crystal is dripped after spreading spacers, such as a beads, on the liquid crystal aligning film of one board | substrate, and after that, the surface of the side in which the liquid crystal aligning film was formed is made inside. The 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, And a method of irradiating ultraviolet rays while maintaining an electric field. 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 ray is 1-60 J, for example, Preferably it is 40 J or less, The one with little ultraviolet irradiation amount can suppress the reliability fall caused by the destruction of the member which comprises a liquid crystal display element, and also the ultraviolet irradiation time It is preferable because the manufacturing efficiency is increased by reducing.

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, the light containing a 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, and a cinnamoyl group. Polyimide precursor having a reactive side chain, and photoreactive side chains of at least one polymer selected from polyimide obtained by imidating the polyimide precursor, or photoreactive side chain and polymerization of the polymer Since a 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 an 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 the liquid crystal aligning film used.

Example

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

<Polymerizable compound>

(Synthesis of polymerizable compound (RM1)

5.0 g (23.8 mmol) of 4,4'-biphenyldicarboxyaldehyde, 7.9 g (47.6 mmol) of 2- (bromomethyl) acrylic acid, 10% hydrochloric acid (aq) in a 300 ml eggplant flask with a cooling tube 33 mL, tetrahydrofuran (THF) 100 mL and tin chloride (II) 9.5 g (50 mmol) were added, it was made into a mixture, and it stirred for 20 hours and made it react at 70 degreeC. After the reaction was completed, the reaction solution was poured into 300 ml of pure water to obtain a white solid. The obtained solid was separated and purified by recrystallization (hexane / chloroform = 2/1) to obtain 3.5 g of a white solid. As a result of measuring this solid by NMR, it was confirmed that this white solid is a polymeric compound (RM1) shown by following target Reaction Formula. The yield was 72%.

(31)

(Synthesis of Polymerizable Compound (RM2))

6.7 g (35.9 mmol) of 4,4'-biphenol, 15.0 g (71.7 mmol) of 2- (4-bromobutyl) -1,3-dioxolane in a 300 ml eggplant flask with a cooling tube, 19.8 g (143 mmol) of potassium carbonate and 150 ml of acetone were added to the mixture, and the mixture was reacted with stirring at 60 ° C for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid and 200 ml of water were mixed, and 80 ml of chloroform was added to extract. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the separated organic layer and dried, and after filtering, the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was purified by recrystallization (hexane / chloroform = 4/1 (volume ratio)) to give 14.6 g of a white solid. The result of measurement of the obtained white solid by NMR is shown below. In addition, the obtained solid was dissolved in deuterated chloroform (CDCl ₃ ) and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Geiole). From this result, it was confirmed that this white solid is a compound (RM2-A) shown by following Reaction Formula. The yield was 92%.

(32)

Next, 13.3 g (30 mmol) of the compound (RM2-A) obtained above, 11.6 g (70 mmol) of 2- (bromomethyl) acrylic acid, and 10% hydrochloric acid were added to a 500 ml eggplant flask equipped with a cooling tube. 50 ml of aq), 160 ml of tetrahydrofuran (THF), and 13.2 g (70 mmol) of tin (II) chloride were added, it was made into a mixture, and it stirred for 20 hours and made it react at 70 degreeC. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 200 ml of pure water, and 100 ml of dichloroform was added thereto to extract. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the separated organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. This solid was recrystallized (hexane / chloroform = 2/1) to obtain 9.4 g of a white solid. As a result of measuring the obtained white solid similarly to the above and by NMR, it was confirmed that this white solid is a polymeric compound (RM2) shown by following target Reaction Formula. The yield was 64%.

(33)

(Synthesis of Polymerizable Compound (RM3))

In a 500 ml eggplant flask with a cooling tube, 11.2 g (60 mmol) of 4,4'-biphenol, 25.0 g (138 mmol) of 2- (2-bromoethyl) -1,3-dioxolane, 35.9 g (260 mmol) of potassium carbonate and 200 ml of acetone were added to the mixture, followed by reacting with stirring at 60 ° C. for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 200 ml of water were mixed, and 100 ml of chloroform was added and extracted. Extraction was carried out three times.

The separated organic layer was dried by adding anhydrous magnesium sulfate, and after filtering, the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in chloroform and precipitated using hexane (hexane / chloroform = 2/1) to give 17.6 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 (RM3-A) shown by following Reaction Formula. The yield was 76%.

(34)

Next, 10.0 g (26 mmol) of the compound (RM3-A) obtained above, 10.0 g (60.6 mmol) of 2- (bromomethyl) acrylic acid, 10% HCl ( aq) 32 ml, tetrahydrofuran (THF) 140 ml and tin chloride (II) 11.4 g (60.6 mmol) were added, it was made into a mixture, and it stirred for 20 hours and made it react at 70 degreeC. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 200 ml of pure waters, and 100 ml of chloroform was added and extracted there. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the white solid was obtained. This solid was dissolved in chloroform and precipitated using hexane (hexane / chloroform = 2/1) to give a white solid. After wash | cleaning this solid with methanol, 4.7 g of white solids were obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a polymeric compound (RM3) shown by following target Reaction Formula. The yield was 42%.

(35)

(Synthesis of Polymerizable Compound (RM4))

To a 500 ml eggplant flask with a cooling tube was added 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. To a mixture, and reacted with stirring at a temperature of 60 ° C. 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 (RM4-A) shown by following Reaction Formula. The yield was 95%.

(36)

250 ml of ethanol, 18.0 g (41 mmol) of the compound (RM4-A) obtained above, and 100 ml of 10% aqueous sodium hydroxide solution were added to a 1 l flask equipped with a cooling tube to prepare a mixture. The reaction was carried out while stirring. 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 (RM4-B) shown by following Reaction Formula. The yield was 83%.

[Formula 37]

5.0 g (14.0 mmol) of the compound (RM4-B) obtained above were dissolved in 30 ml of THF together with 3.2 g of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT), followed by room temperature. The mixture was stirred in a water bath, 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. 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 a polymeric compound (RM4) shown by following Reaction Formula. The yield was 38%.

(38)

(Polymerizable Compound (RM5))

The polymeric compound represented by a well-known following formula was made into polymeric compound (RM5).

[Chemical Formula 39]

(Synthesis of Polymerizable Compound (RM6))

7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate in a 200 mL eggplant flask with a cooling tube , And 70 ml of acetone were added to the mixture, and reacted at 64 ° C. for 24 hours with stirring. After the reaction was completed, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow, wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent was distilled off from the obtained solution and the white solid 11.3g was obtained. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid is a compound (RM6-A) shown by following Reaction Formula. The yield was 90%.

[Formula 40]

Next, in a 100 ml three-necked flask with a cooling tube, 2.2 g (10.0 mmol) of chlorochromate (PCC), and CH ₂ Cl ₂ In a state of putting the mixture stirred for 15.0 ㎖, the compound (RM6-A) 2.5 g ( 10.0 m㏖) obtained with the CH ₂ Cl ₂ The solution dissolved in 15.0 ml was added dropwise, and further stirred at room temperature for 6 hours. Then, 90 ml of diethyl ether was added to the solution from which the oily substance adhering to the flask wall was removed, and it filtered under reduced pressure, and the solvent was distilled off under reduced pressure and the dark green wet solid was obtained. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent of the obtained solution was distilled off and the colorless solid 1.3g was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid is a compound (RM6-B) shown by following Reaction Formula. The yield was 50%.

(41)

Next, 1.25 g (5.0 mmol) of the compound (RM6-B) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered trademark) were obtained in a 50 ml eggplant flask equipped with a cooling tube. ) 15 (8% of Rohm and Haas Co., Ltd.), 8.0 ml of THF, 0.95 g (5.0 mmol) of tin chloride (II), and 2.0 ml of pure water were added to make a mixture, and it stirred for 5 hours and made it react at 70 degreeC. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 40 ml of pure waters, and 50 ml of diethyl ether was added and extracted there. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the colorless solid 1.5g was obtained. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid is a compound (RM6-C) shown by following Reaction Formula. The yield was 94%.

(42)

To a 100 ml eggplant flask with a cooling tube, 35 ml of ethanol, 1.5 g (4.7 mmol) of the compound (RM6-C) obtained above, and 5 ml of 10% aqueous sodium hydroxide solution were added to prepare a mixture. The reaction was carried out while stirring. After completion of the reaction, 300 ml of water and the reaction solution were added to a 500 ml beaker, stirred at room temperature for 30 minutes, and then 5 ml of a 10% aqueous HCl solution was added dropwise, followed by filtration to obtain 1.3 g of a white solid.

Next, 1.1 g of a white solid obtained in a 50 ml eggplant flask with a cooling tube, 1.0 g of Amberlyst (registered trademark) 15 (trade name of Rohm and Haas Co.), and 20.0 ml of THF were added to make a mixture, and it was 5 at 70 ° C. The reaction was stirred for a while. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off from the solution to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1 (v / v)) to obtain 0.9 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid is a compound (RM6-D) shown by following Reaction Formula. The yield was 71%.

(43)

21.1 g (69.3 mmol) of the compound (RM6-D) obtained above, 5.0 g (34.7 mmol) of 1,4-cyclohexanedimethanol, 0.35 g of N, N-dimethyl-4-aminopyridine (DMAP) and a small amount BHT was suspended at room temperature, suspended in 100 ml of methylene chloride, and 15.5 g (75.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of methylene chloride was added thereto, followed by stirring for 48 hours. . After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 mL each of 0.5 N-HCl, saturated aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. It removed and the recrystallization operation by ethanol gave 20.1g of polymeric compounds (RM6) shown by following Reaction Formula. The result measured by NMR is shown below. Moreover, the yield was 81%.

(44)

(Synthesis of Polymerizable Compound (RM7))

6.1 g (20.0 mmol) of the compound (RM6-D) obtained by the above-described method, 5.3 g (20.0 mmol) of 4-[(6-acryloxy) hexyloxy] phenol (from SYNTHON Chemicals), N, N-dimethyl 0.1 g of 4-aminopyridine (DMAP) and a small amount of BHT are suspended in 100 ml of methylene chloride under stirring at room temperature, and there are dissolved 5.1 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC). The solution was added and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 100 ml of 0.5 N-HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Removal to give a yellow solid. This solid was purified by silica column chromatography (column: silica gel 60 0.063-0.200 mm manufactured by Merck, Eluent: hexane / ethyl acetate = 1/1). The solvent of the solution obtained here was distilled off and 4.3 g of polymeric compounds (RM7) shown by following Reaction Formula were obtained. The result measured by NMR is shown below. Moreover, the yield was 39%.

[Chemical Formula 45]

(Synthesis of Polymerizable Compound (RM8))

2.1 g (7.3 mmol) of the compound (RM8-A), 2.5 g (7.3 mmol) of the compound (RM8-B), 0.015 g of DMAP, and a small amount of BHT shown in the following scheme are stirred at room temperature and suspended in 30 ml of methylene chloride. Then, 1.8 g (9.0 mmol) of DCC dissolved in 5 ml of methylene chloride was added thereto, and after stirring overnight, the precipitated DCC urea was separated by filtration, and the filtrate was sequentially saturated with 50 ml of 0.5 N-HCl in each order. After washing twice with an aqueous sodium hydrogen carbonate solution and saturated brine, drying with magnesium sulfate, the solvent was distilled off and recrystallization with ethanol gave 1.3 g of a polymerizable compound (RM8) shown in the following reaction formula. The result measured by NMR is shown below. Moreover, the yield was 30%.

(46)

(Synthesis of Polymerizable Compound (RM9))

In a 100 ml eggplant flask with a cooling tube, 6.1 g (50 mmol) of 4-hydroxybenzaldehyde, 9.1 g (50 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, And 100 ml of acetone were added to make a mixture, and it reacted at 64 degreeC, stirring for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 70 ml of water were mixed, and 50 ml of diethyl ether was added and extracted. Extraction was carried out three times.

The separated organic layer was dried by adding anhydrous magnesium sulfate, and after filtering, the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 5 ml of ethyl acetate and purified by column chromatography (column: silica gel 60 0.063-0.200 mm manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the solution obtained here and 7.4g of white solid was obtained. 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 (RM9-A) shown by following Reaction Formula. The yield was 67%.

[Formula 47]

2.2 g of compound (RM9-A), 1.7 ml of triethylamine, 0.2 mg of BHT, and 10 ml of THF were mixed and dissolved in a 50 ml three-neck flask. Under stirring of this solution, a solution in which 0.8 ml of acrylic acid chloride was dissolved in 10 ml of THF was added dropwise over 15 minutes. At that time, the three neck flask was cooled by water bath (water temperature 20 degreeC). After dripping, after stirring for 30 minutes as it is, the flask was removed from the water bath, nitrogen-substituted, and also it stirred for 3 hours and reacted at room temperature. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to a capacity of 3/4, and then 100 ml of methylene chloride was added. The solution was washed in the order of 100 ml of saturated sodium carbonate solution, 100 ml of 0.5 N hydrochloric acid and 100 ml of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off to obtain a yellow solid. This solid was dissolved in 3 ml of ethyl acetate, and purified by column chromatography (column: silica gel 60 0.063-0.200 mm Merck preparation, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the solution obtained here and 2.0g of white solid was obtained. 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 (RM9-B) shown by following Reaction Formula. The yield was 72%.

(48)

Next, 2.0 g (7 mmol) of the intermediate compounds (RM9-B) and 1.2 g (7.0 mmol) of 2- (bromomethyl) acrylic acid obtained in the same manner to the above in a 50 ml eggplant flask with a cooling tube. 1.2 g of Amberlyst (registered trademark) 15 (trade name of Rohm and Haas), 8.0 ml of THF, 1.4 g (7 mmol) of tin chloride (II), and 2.0 ml of pure water were added to prepare a mixture, and the mixture was stirred at a temperature of 70 캜 for 24 hours. The reaction was stirred. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 60 ml of pure waters, and 50 ml of diethyl ether was added and extracted there. Extraction was carried out three times. Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the pale brown solid was obtained.

This solid was dissolved in 3 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60 0.063-0.200 mm produced by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the solution obtained here and 1.0g of white solid was obtained. As a result of measuring this solid by NMR, it was confirmed that this white solid is a polymeric compound (RM9) shown by following Reaction Formula. The yield was 40%.

(49)

(Synthesis of Polymerizable Compound (RM10))

22.0 g (72.4 mmol) of the compound (RM6-D) obtained in the same manner as above, 5.0 g (36.2 mmol) of 1,4-phenyldimethanol, 0.35 g of N, N-dimethyl-4-aminopyridine (DMAP) And a small amount of BHT was stirred at room temperature, suspended in 100 ml of methylene chloride, 17.0 g (80.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of methylene chloride was added thereto, followed by stirring for 48 hours. Reacted. After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml each of 0.5 N-HCl, saturated aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. It removed and the recrystallization operation by ethanol obtained 16.6g of polymeric compounds (RM10) shown by following Reaction Formula. The result measured by NMR is shown below. Moreover, the yield was 65%.

(50)

(Synthesis of Polymerizable Compound (RM11))

6.1 g (20.0 mmol) of the compound (RM6-D) obtained in the same manner as above, 2.1 g (10.0 mmol) of 4,4'-biphenyldimethanol, N, N-dimethyl-4-aminopyridine (DMAP) 0.15 g and a small amount of BHT were stirred at room temperature, suspended in 50 ml of methylene chloride, and thereto, 5.3 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 25 ml of methylene chloride was added thereto for 48 hours. The reaction was stirred. After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml each of 0.5 N-HCl, saturated aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. 6.4 g of polymeric compounds (RM11) shown by following Reaction Formula were obtained by the removal and recrystallization operation by ethanol. The result measured by NMR is shown below. Moreover, the yield was 81%.

(51)

(Synthesis of Polymerizable Compound (RM12))

6.1 g (20.0 mmol) of the compound (RM6-D) obtained in the same manner as above, 2.1 g (10.0 mmol) of 4,4'-dihydroxybenzophenone, N, N-dimethyl-4-aminopyridine (DMAP ) 0.1 g and a small amount of BHT were stirred at room temperature, suspended in 80 ml of methylene chloride, and a solution of 5.2 g (24.0 mmol) of dicyclohexylcarbodiimide (DCC) was added thereto and stirred overnight. . The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N-HCl, 50 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Removal to give a yellow solid. This solid was refine | purified by recrystallization using ethanol, and 6.2 g of white solids were obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a polymeric compound (RM12) shown by following Reaction Formula. The yield was 79%.

(52)

(Synthesis of Polymerizable Compound (RM13))

In a 500 ml eggplant flask with a cooling tube, 12.2 g (100 mmol) of 4-hydroxybenzaldehyde, 12.2 g (50 mmol) of 1,6-dibromohexane, 16.0 g (116 mmol) of potassium carbonate, 150 mL of acetone was added to make a mixture, and it reacted at the temperature of 64 degreeC, stirring for 48 hours. After filtering the reaction solution, the solvent was distilled off under reduced pressure to obtain 15.4 g of a pale brown wet solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this solid is a compound (RM13-A) shown by following Reaction Formula. The yield was 94%.

(53)

Next, 3.3 g (10.0 mmol) of compound (RM13-A), 3.3 g (20.0 mmol) of 2- (bromomethyl) acrylic acid obtained in the same manner to the above in a 100 ml eggplant flask with a cooling tube, 3.0 g of Amberlyst (registered trademark) (trade name of Rohm and Haas), 32.0 ml of THF, 3.8 g of tin chloride (II) (20.0 mmol), and 8.0 ml of pure water were added to the mixture, followed by stirring at a temperature of 70 ° C. for 24 hours. The reaction was carried out. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 60 ml of pure waters, and 70 ml of diethyl ether was added and extracted there. Extraction was carried out three times. Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the pale brown solid was obtained.

This solid was dissolved in 10 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60 0.063-0.200 mm Merck preparation, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the solution obtained here and 2.6g of white solid was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid is a polymeric compound (RM13) shown by following Reaction Formula. The yield was 55%.

[Formula 54]

(Synthesis of Polymerizable Compound (RM14))

7.5 g (50.0 mmol) of terephthalaldehyde acid, 9.1 g (55.0 mmol) of 2- (bromomethyl) acrylic acid, 80.0 mL of THF, 10.5 g (110.0) of tin chloride (II) in a 300 mL eggplant flask with a cooling tube mmol) and 35.0 mL of aqueous hydrochloric acid solution (10%) were added to make a mixture, and it stirred for 24 hours and made it react at 70 degreeC. After completion of the reaction, the mixture was mixed with 200 ml of pure water, and 100 ml of diethyl ether was added thereto and extracted. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the colorless solid 8.3g was obtained. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid is a compound (RM14-A) shown by following Reaction Formula. The yield was 76%.

(55)

2.4 g (11.0 mmol) of the obtained compound (RM14-A), 0.6 g (5.0 mmol) of 1,6-hexanediol, 0.05 g of N, N-dimethyl-4-aminopyridine (DMAP) and a small amount of BHT The mixture was stirred at room temperature, suspended in 10 ml of methylene chloride, and 2.5 g (12.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 5 ml of methylene chloride was added thereto, followed by stirring for 48 hours. After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml each of 0.5 N-HCl, saturated aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. 1.3 g of polymeric compounds (RM14) shown by following Reaction Formula were obtained by the removal and recrystallization operation by ethanol. The result measured by NMR is shown below. Moreover, the yield was 50%.

(56)

(Synthesis of Polymerizable Compound (RM15))

8.0 g (28.7 m) of the compound (RM15-A) shown in the following reaction formula was added to a 300 ml three-necked flask equipped with a cooling tube with 6.2 g (28.7 mmol) of PCC and 100.0 ml of CH ₂ Cl ₂ stirred and mixed. ㏖) was added dropwise to a solution obtained by dissolving in CH ₂ Cl ₂ (30.0 ㎖), and the mixture was stirred for 2 hours more at room temperature. Then, 150 ml of diethyl ether was added to the solution from which the oily substance adhering to the flask wall was removed, and it filtered under reduced pressure, and the solvent was distilled off under reduced pressure and the dark green wet solid was obtained.

This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the obtained solution was distilled off and the colorless solid 5.7g was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid is a compound (RM15-B) shown by following Reaction Formula. The yield was 72%.

(57)

Next, 5.7 g (20.6 mmol) of the compound (RM15-B) obtained above, 3.4 g (20.6 mmol) of 2- (bromomethyl) acrylic acid, and 10% aqueous hydrochloric acid solution were added to a 100 ml eggplant flask equipped with a cooling tube. 16 ml, 50 ml of THF, and 3.9 g (20.6 mmol) of tin chloride (II) were added to the mixture, and the mixture was stirred at a temperature of 70 ° C. for 20 hours to react. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 100 ml of pure waters, 150 ml of diethyl ether was added and extracted there. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, recrystallization (hexane / ethyl acetate, 1/1) was performed, and the colorless solid 4.6g was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid is a polymeric compound (RM15) shown by following Reaction Formula. The yield was 65%.

(58)

(Synthesis of Polymerizable Compound (RM16))

5.0 g (24.0 mmol) of 4-bromobutyl-1,3-dioxolane, 4.5 g (27.0 mmol) of 2- (bromomethyl) acrylic acid, 10% hydrochloric acid in a 200 ml eggplant flask with a cooling tube 19 mL of aqueous solution, 60 mL of THF, and 4.7 g (27.0 mmol) of tin chloride (II) were added to make a mixture, and it stirred for 20 hours and made it react at the temperature of 70 degreeC. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 100 ml of pure waters, 100 ml of diethyl ether was added and extracted there. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the colorless liquid 5.2g was obtained. The result of having measured this liquid by NMR is shown below. From this result, it was confirmed that this colorless liquid is a compound (RM16-A) shown by following Reaction Formula. The yield was 93%.

[Chemical Formula 59]

4.7 g (20.0 mmol) of the compound (RM16-A) obtained above, 3.6 g (20.0 mmol) of 4-methoxy cinnamic acid, 5.1 g (40.0 mmol) of potassium carbonate, in a 100 ml eggplant flask with a cooling tube, And 50 ml of N, N-dimethylformamide (DMF) were added to make a mixture, and reacted at 110 degreeC for 48 hours, stirring. After completion | finish of reaction, it mixed with 200 ml of pure waters, and added and extracted 50 ml of ethyl acetate there. Extraction was carried out three times. Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the solid was obtained. This solid was dissolved in 10 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60 0.063-0.200 mm Merck preparation, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the solution obtained here and 2.8g of white solid was obtained. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this solid is a polymeric compound (RM16) shown by following Reaction Formula. The yield was 43%.

(60)

(Synthesis of Polymerizable Compound (RM17))

9.4 g (45.0 mmol) of 4-bromobutyl-1,3-dioxolane, 10.0 g (45.0 mmol) of trans-4-phenyl cinnamic acid, 12.0 g of potassium carbonate in a 200 ml eggplant flask with a cooling tube 90.0 mmol) and 100 ml of DMF were added to make a mixture, and reacted at 110 degreeC for 48 hours, stirring. After completion of the reaction, the mixture was mixed with 100 ml of pure water to obtain a solid. The solid was filtered, 50 ml of ethanol was added, the mixture was filtered. The solvent was distilled off from the solution after filtering under reduced pressure, and 6.2 g of solids were obtained. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this solid is a compound (RM17-A) shown by following Reaction Formula. The yield was 40%.

(61)

Next, 6.2 g (18.0 mmol) of the compound (RM17-A) obtained above, 3.3 g (20.0 mmol) of 2- (bromomethyl) acrylic acid, and 10% aqueous hydrochloric acid solution were added to a 100 ml eggplant flask equipped with a cooling tube. 16 ml, 32 ml of THF, and 3.8 g (20.0 mmol) of tin chloride (II) were added to the mixture, and the mixture was stirred at a temperature of 70 ° C. for 20 hours to react. After completion of the reaction, the reaction solution was mixed with 100 ml of pure water, and 50 ml of diethyl ether was added thereto and extracted. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, recrystallization (hexane / ethyl acetate, 2/1) was performed, and the solid 3.6g was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this solid is a polymeric compound (RM17) shown by following Reaction Formula. The yield was 53%.

[Formula 62]

(Synthesis of Polymerizable Compound (RM18))

7.6 g (25.0 mmol) of the compound (RM6-D) obtained by the above method, 4.8 g (25.0 mmol) of ethyl4-hydroxy cinnamate, 0.1 g of N, N-dimethyl-4-aminopyridine (DMAP), and A small amount of BHT was stirred at room temperature, suspended in 100 ml of methylene chloride, and a solution in which 6.7 g (32 mmol) of dicyclohexylcarbodiimide (DCC) was dissolved was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N-HCl, 50 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Removal to give a yellow solid. This solid was purified by recrystallization using ethanol to give 7.1 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 polymeric compound (RM18) shown by following Reaction Formula. The yield was 59%.

(63)

(Synthesis of Polymerizable Compound (RM19))

7.3 g (24.0 mmol) of the compound (RM6-D) obtained by the above method, 5.0 g (24.0 mmol) of methyl4-hydroxy-3-methoxycinnamate, N, N-dimethyl-4-aminopyridine (DMAP ) 0.1 g and a small amount of BHT were stirred at room temperature, suspended in 100 ml of methylene chloride, and a solution of 6.4 g (31.0 mmol) of dicyclohexylcarbodiimide (DCC) was added thereto and stirred overnight. . The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 100 ml of 0.5 N-HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Removal to give a yellow solid. This solid was refine | purified with recrystallization (ethanol), and 6.1g of polymeric compounds (RM19) shown by following Reaction Formula were obtained. The result measured by NMR is shown below. Moreover, the yield was 51%.

&Lt; EMI ID =

(Polymerizable Compound (RM20))

The polymeric compound represented by a well-known following formula was made into the polymeric compound (RM20).

(65)

(Polymerizable Compound (RM21))

The polymeric compound represented by a well-known following formula was made into the polymeric compound (RM21).

[Formula 66]

(Polymerizable Compound (RM22))

The polymeric compound represented by a well-known following formula was made into the polymeric compound (RM22).

(67)

(Polymerizable Compound (RM23))

The polymeric compound represented by a well-known following formula was made into the polymeric compound (RM23).

(68)

&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-cyclobutanetetracarboxylic dianhydride

TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4: 2,3-2 anhydride represented by a following formula

(69)

m-PDA: m-Phenylenediamine

p-PDA: p-phenylenediamine

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

DA-1: 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula

(70)

DA-2: the formula N ^1, N ¹ represents the - diallyl benzene-1,2,4-triamine

(71)

DA-3: 3,5-diaminobenzoic acid cholestanyl represented by a following formula

(72)

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: 30 mmol / l of lithium bromide · hydrate (LiBr · H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide Furan (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation, and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) by Polymer Laboratories.

The imidization rate of the polyimide was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard Φ 5 manufactured by Kusano Scientific Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixed product) was added, and ultrasonic wave was added to complete the process. Dissolved. 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 integration value of this proton and the proton peak integration value derived from the NH group of amic acid appearing around 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 the peak integrated value of a reference proton, and alpha is amic acid in the case of polyamic acid (imidization ratio of 0%). Number ratio of reference protons to one proton of NH group.

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

(Example 1)

BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol), DA-1 (4.76 g, 18.0 mmol) in NMP (81.5 g) After melt | dissolving and making it react at 80 degreeC for 5 hours, CBDA (6.94g, 35.4 mmol) and NMP (27.2g) 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 (135g) and diluting to 6 mass%, acetic anhydride (18.3g) and pyridine (23.6g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (1700 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 12000 and the weight average molecular weight was 39000.

NMP (74.0g) 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 (20.0g) 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) is added to the above-mentioned polymeric compound (RM1) with respect to said liquid crystal aligning agent (B) 10.0g, It stirred for 3 hours, and melt | dissolves at room temperature, The liquid crystal aligning agent (B1 ) Was prepared.

(Example 2)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM2) obtained above 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)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM3) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), 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 to the polymeric compound (RM4) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), it stirred for 3 hours, and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B4). .

(Example 5)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM5) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), it stirred at room temperature for 3 hours, and was prepared to prepare a liquid crystal aligning agent (B5). .

(Comparative Example 1)

BODA (4.38 g, 17.5 mmol), m-PDA (2.65 g, 24.5 mmol) and PCH (4.00 g, 10.5 mmol) were dissolved in NMP (42.8 g) and reacted at 80 ° C for 5 hours, CBDA (3.22 g, 16.5 mmol) and NMP (14.2 g) 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 (70.0g) and diluting to 6 mass%, acetic anhydride (17.6g) and pyridine (5.44g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. This reaction solution was poured into methanol (900 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 (C). The imidation ratio of this polyimide was 73%, the number average molecular weight was 15000 and the weight average molecular weight was 47000.

NMP (74.0g) is added to the obtained polyimide powder (C) (6.0g), and it stirred for 12 hours and made it melt | dissolve at 50 degreeC. BCS (20.0g) was added to this solution, and the polyimide solution (D) was obtained by stirring at 50 degreeC for 5 hours.

Moreover, 0.06 g (10 mass% with respect to solid content) is added to the polymerizable compound (RM2) obtained above with respect to 10.0 g of polyimide solutions (D), it stirred for 3 hours, and melt | dissolves at room temperature, and a liquid crystal aligning agent (D1) is added. It prepared.

&Lt; Production of liquid crystal cell &

(Example 6)

The liquid crystal cell was produced in the order as 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 (solvent type thermosetting type epoxy resin) was printed on it. Subsequently, after making the surface on the side where the liquid crystal aligning film of the other board | substrate was formed inside, and 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 preparation of the liquid crystal cell (initial stage) and after the UV irradiation of 20 J (after UV 20 J).

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 kHz 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 7)

Except having changed the baking temperature from 200 degreeC to 140 degreeC, operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 8)

Except having used the liquid crystal aligning agent (B2) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 9)

Except having changed the calcination temperature from 200 degreeC to 140 degreeC, 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 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 11)

Except having changed the baking temperature from 200 degreeC to 140 degreeC, operation similar to Example 10 was performed and the response speed in UV irradiation back and front was compared.

(Example 12)

Except having used the liquid crystal aligning agent (B4) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 13)

Except having changed the baking temperature from 200 degreeC to 140 degreeC, operation similar to Example 12 was performed and the response speed in UV irradiation back and front was compared.

(Example 14)

Except having used the liquid crystal aligning agent (B5) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 15)

Except having changed the baking temperature from 200 degreeC to 140 degreeC, operation similar to Example 14 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 (B) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Comparative Example 3)

Except having changed the baking temperature from 200 degreeC to 140 degreeC, operation similar to the comparative example 2 was performed and the response speed in UV irradiation back and front was compared.

(Comparative Example 4)

Except having used the liquid crystal aligning agent (D1) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Comparative Example 5)

Except having changed the baking temperature from 200 degreeC to 140 degreeC, operation similar to the comparative example 4 was performed and the response speed in UV irradiation back and front was compared.

As a result, as shown in Table 2, the Example using the liquid crystal aligning agent containing the polymer (polyimide) which has a photoreactive side chain containing a methacryl group, and the side chain which orientates a liquid crystal perpendicularly, and a polymeric compound 6-15 are the comparative examples 4 and 5 which used the liquid crystal aligning agent which contains a polymeric compound but does not contain the polymer which has a photoreactive side chain, and the photoreactive side chain and a liquid crystal which contain a methacryl group perpendicularly. The improvement rate of the response speed before and behind ultraviolet irradiation was remarkably high compared with the comparative examples 2 and 3 which used the liquid crystal aligning agent B which contains the polymer (polyimide) which has the side chain to orientate, but does not add the polymeric compound.

Therefore, by using the liquid crystal aligning agent which used the polymer and polymerizable compound which have a photoreactive side chain containing a methacryl group, and a side chain which orientates a liquid crystal perpendicularly, it can improve a response speed dramatically rather than using each independently. It was confirmed that it was possible to sufficiently improve the response speed even with the addition amount of a small polymerizable compound.

Moreover, Example 6-11 which used the liquid crystal aligning agent containing the polymeric compound which has a (alpha)-methylene- (gamma) -butyrolactone group which is a polymeric group in a sock end, or has a methacrylate group in a sock end, and has this methacrylate In Examples 12-13 using the liquid crystal aligning agent containing a polymeric compound which has a structure which group has couple | bonded with the phenylene group via an oxyalkylene group, even when baking temperature is low (140 degreeC), it is high (200 degreeC) Even though the response speed was dramatically improved.

On the other hand, in Examples 14-15 using the liquid crystal aligning agent which has a methacrylate group and the structure which this methacrylate group has couple | bonded with the phenylene group directly, when baking at 200 degreeC, the improvement rate of a response speed is baked at 140 degreeC It was lower than it did. In Examples 6 to 7 in which only the polymerizable compound used in Examples 14 to 15 and the polymerizable group differed from each other, the calcination temperature dependence was hardly confirmed, and the carbon atom to which the methacryl group was bonded was sp ³ hybrid orbit. It is estimated that the thermal stability of the polymerizable compound was improved by decreasing the calcination temperature dependence of the response rate improvement rate.

(Example 16)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM6) obtained above 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 17)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM7) obtained above 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). .

(Example 18)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM8) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), it stirred for 3 hours, and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B8). .

(Example 19)

0.06 g (10 mass% with respect to solid content) was added to the polymeric compound (RM9) obtained above 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 (B9). .

(Example 20)

0.06 g (10 mass% with respect to solid content) was added to the polymeric compound (RM10) obtained above 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 (B10). .

(Example 21)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM11) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), it stirred for 3 hours, and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B11). .

(Example 22)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM12) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), it stirred for 3 hours, and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B12). .

(Example 23)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM13) obtained above 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 (B13). .

(Example 24)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM14) obtained above 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 (B14). .

(Example 25)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM15) obtained above 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 (B15). .

(Example 26)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM16) obtained above 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 (B16). .

(Example 27)

To the 10.0 g of liquid crystal aligning agent (B), 0.06 g (10 mass% with respect to solid content) was added, and it stirred at room temperature for 3 hours, melt | dissolved, and prepared the liquid crystal aligning agent (B17). .

(Example 28)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM18) obtained above with respect to 10.0 g of liquid crystal aligning agents (B), it stirred for 3 hours, and made it melt | dissolve at room temperature, and prepared the liquid crystal aligning agent (B18). .

(Example 29)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM19) obtained above 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 (B19). .

(Example 30)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM20) obtained above 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 (B20). .

(Example 31)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM21) obtained above 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 (B21). .

(Example 32)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM22) obtained above 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 (B22). .

(Example 33)

0.06g (10 mass% with respect to solid content) was added to the polymeric compound (RM23) obtained above 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 (B23). .

(Example 34)

Except having used the liquid crystal aligning agent (B6) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 35)

Except having used the liquid crystal aligning agent (B7) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 36)

Except having used the liquid crystal aligning agent (B8) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 37)

Except having used the liquid crystal aligning agent (B9) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 38)

Except having used the liquid crystal aligning agent (B10) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 39)

Except having used the liquid crystal aligning agent (B11) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 40)

Except having used the liquid crystal aligning agent (B12) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 41)

Except having used the liquid crystal aligning agent (B13) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 42)

Except having used the liquid crystal aligning agent (B14) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 43)

Except having used the liquid crystal aligning agent (B15) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 44)

Except having used the liquid crystal aligning agent (B16) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 45)

Except having used the liquid crystal aligning agent (B17) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 46)

Except having used the liquid crystal aligning agent (B18) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 47)

Except having used the liquid crystal aligning agent (B19) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 48)

Except having used the liquid crystal aligning agent (B20) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 49)

Except having used the liquid crystal aligning agent (B21) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 50)

Except having used the liquid crystal aligning agent (B22) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 51)

Except having used the liquid crystal aligning agent (B23) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 52)

TCA (3.36 g, 15.0 mmol), p-PDA (1.30 g, 12.0 mmol), DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol) ), The mixture was reacted at 60 ° C for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic-acid solution (68g) and diluting to 6 mass%, acetic anhydride (6.0g) and pyridine (11.7g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (850 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 (E). The imidation ratio of this polyimide was 50%, the number average molecular weight was 18000 and the weight average molecular weight was 58000.

NMP (74.0g) is added to the obtained polyimide powder (E) (6.0g), and it stirred for 12 hours and made it melt | dissolve at 50 degreeC. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (F) was obtained by stirring at 50 degreeC for 5 hours.

Moreover, 0.06g (10 wt% with respect to solid content) was added with respect to 10.0g of said liquid crystal aligning agents (F), and it stirred and dissolved at room temperature for 3 hours, and prepared the liquid crystal aligning agent (F1).

Moreover, 0.06g (10 wt% with respect to solid content) was added with respect to 10.0g of said liquid crystal aligning agents (F), and it stirred and stirred for 3 hours at room temperature, and prepared the liquid crystal aligning agent (F2).

(Example 53)

Except having used the liquid crystal aligning agent (F1) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 54)

Except having used the liquid crystal aligning agent (F2) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

(Example 55)

BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) in NMP (52.7 g) After mixing and reacting at 80 degreeC for 5 hours, CBDA (3.77g, 19.2 mmol) and NMP (17.56g) 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 (75g) and diluting to 6 mass%, acetic anhydride (8.7g) and pyridine (13.5g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (950 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 (G). The imidation ratio of this polyimide was 50%, the number average molecular weight was 20000 and the weight average molecular weight was 86000.

NMP (74.0g) is added to the obtained polyimide powder (G) (6.0g), and it stirred for 12 hours and made it melt | dissolve at 50 degreeC. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (G1) was obtained by stirring at 50 degreeC for 5 hours.

Moreover, 0.06 g (10 mass% with respect to solid content) was added with respect to 10.0 g of said liquid crystal aligning agents (G1), and it stirred and stirred at room temperature for 3 hours, and prepared the liquid crystal aligning agent (G2).

(Example 56)

Except having used the liquid crystal aligning agent (G2) instead of the liquid crystal aligning agent (B1), operation similar to Example 6 was performed and the response speed in UV irradiation back and front was compared.

Table 3 shows the results of Examples 34 to 51, 53, 54, and 56. As shown in Table 3, Example 34 using the polymer (polyimide) which has a photoreactive side chain containing a methacryl group, etc., and the side chain which orientates a liquid crystal perpendicularly, and a liquid crystal aligning agent containing a polymeric compound Although the polymerizable compound and the polymer differ from -51, 53, 54, and 56, respectively, the improvement rate of the response speed before and behind ultraviolet irradiation was remarkably high similarly to Examples 6-15.

Claims (6)

The polyimide precursor which has a side chain which orientates a liquid crystal perpendicularly | vertically, and the photoreactive side chain containing at least 1 sort (s) chosen from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group, and this polyimide precursor It has at least 1 sort (s) of polymer chosen from the polyimide obtained by dehydration, the polymeric compound which has group photopolymerized or photocrosslinked at 2 or more terminals, and a solvent, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
The photoreactive side chain contains the group chosen from following formula (I), The liquid crystal aligning agent characterized by the above-mentioned.
[Chemical Formula 1]

(Wherein R ¹¹ is H or a methyl group) 3. The method according to claim 1 or 2,
The group photopolymerized or photocrosslinked is selected from the following formula (II).
(2)

(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, and 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 obtained by apply | coating and baking the liquid crystal aligning agent in any one of Claims 1-3 on a board | substrate. The liquid crystal manufactured by apply | coating the liquid crystal aligning agent in any one of Claims 1-3 to a board | substrate, contacting the liquid crystal aligning film obtained by baking, and forming a liquid crystal layer, and irradiating an ultraviolet-ray, applying voltage to this liquid crystal layer, and manufacturing it A cell is provided, The liquid crystal display element characterized by the above-mentioned. The liquid crystal aligning agent of any one of Claims 1-3 is apply | coated to a board | substrate, it contacts with the liquid crystal aligning film obtained by baking, forms a liquid crystal layer, irradiates an ultraviolet-ray, applies a voltage to this liquid crystal layer, and makes a liquid crystal cell The manufacturing method of the liquid crystal display element characterized by the above-mentioned.