TWI633375B - Liquid crystal alignment agent, liquid crystal alignment film and method for manufacturing the same, liquid crystal display device, phase difference film and method for manufacturing the same, polymer and compound - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent capable of achieving good applicability to a substrate, friction resistance of a coating film, and afterimage characteristics of a liquid crystal display element. The liquid crystal alignment agent of this invention contains the polymer (P) which has a partial structure represented by following formula (1) in a main chain.

W ¹ and W ² are divalent cyclic groups having a benzene ring, a cyclohexane ring, or the like in a ring skeleton; X ¹ is a single bond, -O-, -COO-, -CO-, etc .; X ² is -O- , -COO-, -CO-, etc .; R ¹ is a single bond, an alkanediyl group having 1 to 20 carbon atoms, etc .; R ² is a single bond, -COO-, an alkanediyl group having 1 to 5 carbon atoms, etc .; p is An integer from 0 to 2. When p = 0, the ring skeleton of W ¹ is not a benzene ring. In the case where W ¹ and W ² are both substituted or unsubstituted phenyl groups, R ^{1 is} not a single bond.

Description

Liquid crystal alignment agent, liquid crystal alignment film, manufacturing method thereof, and liquid crystal display Element, retardation film and manufacturing method thereof, polymer and compound

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a manufacturing method thereof, a liquid crystal display element, a retardation film and a manufacturing method thereof, a polymer, and a compound.

In the past, liquid crystal display elements have developed various driving methods such as electrode structures or physical properties of liquid crystal molecules and manufacturing steps. For example, Twisted Nematic (TN) or Super-Twisted Nematic are known. STN), Vertical Alignment (VA), In-Plane Switching (IPS), Fringe Field Switching (FFS) and other liquid crystal display elements. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. In terms of various properties such as heat resistance, mechanical strength, and affinity with liquid crystals, polyamines are generally used as the material of the liquid crystal alignment film. Acid or polyimide.

In recent years, large-screen and high-definition liquid crystal televisions have become the main body. In addition, the popularity of small display terminals such as smart phones or tablet personal computers has progressed, and the demand for high-definition liquid crystal displays has further increased. In addition, a variety of liquid crystal alignment agents have been proposed for improving the display quality of liquid crystal displays (for example, refer to Patent Document 1). Patent Document 1 discloses a technique for forming a polyimide resin film on a substrate using a polymer composition containing the following polymer, and subjecting the obtained polyimide resin film to a rubbing treatment to form a liquid crystal alignment film. The polymer is composed of a diamine containing a diphenyl structure such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4-bis (4-aminophenoxy) biphenyl, and the like. It is obtained by the reaction of tetracarboxylic dianhydride. In the technique described in Patent Document 1, even when the rubbing treatment is strongly performed, it is possible to suppress a decrease in the tilt alignment angle, and to achieve a uniform liquid crystal display.

In addition, a variety of optical materials are used for liquid crystal display elements. Among them, a retardation film is used for the purpose of eliminating the coloring of the display, or for the purpose of eliminating the dependence of the viewing color on the display color and the contrast ratio depending on the visual direction. The retardation film is known as a film having a liquid crystal alignment film and a liquid crystal layer. The liquid crystal alignment film is formed on a surface of a substrate such as a triacetyl cellulose (TAC) film. The liquid crystal layer is formed on the surface of the substrate. The surface of the liquid crystal alignment film is formed by curing a polymerizable liquid crystal. In addition, in recent years, when producing a liquid crystal alignment film in a retardation film, the following optical alignment method is used: the polarizing or non-polarizing radiation is irradiated to the organic thin film that is radiation-sensitive and formed on the substrate surface to give the liquid crystal alignment ability; And proposed a variety of A liquid crystal alignment agent for a retardation film of a liquid crystal alignment film is produced by the above method (for example, refer to Patent Document 2)

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3365563

[Patent Document 2] Japanese Patent Laid-Open No. 2012-37868

The present inventors have conducted research and found that the liquid crystal alignment film formed of the liquid crystal alignment film described in Patent Document 1 has insufficient alignment restraining force of liquid crystal molecules. For example, the liquid crystal alignment film is applied to transverse electric fields such as the IPS method and the FFS method In the case of a liquid crystal display device of the conventional method, an afterimage or burn-in is likely to occur. In addition, when the liquid crystal alignment ability is provided to the coating film by rubbing treatment, in order to increase the alignment restricting force of the liquid crystal molecules, it is required to be stable against friction, that is, to have high friction resistance. On the other hand, if a rigid structure is introduced into the polymer in order to improve the abrasion resistance, the applicability (printability) of the liquid crystal alignment agent may be reduced.

This invention is made in view of the said subject, and one of the objective of this invention is to provide the liquid crystal aligning agent which can be excellent in coating property to a board | substrate, the abrasion resistance of a coating film, and the afterimage characteristic of a liquid crystal display element. Another object is to provide a liquid crystal alignment agent capable of obtaining a retardation film having good liquid crystal alignment.

The present inventors have made intensive studies in order to solve the problems of the prior art as described above, and as a result, they have found that the problem can be solved by including the polymer component of the liquid crystal alignment agent with a polymer having a specific structure, thereby completing the problem. This invention. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal display element, retardation film and manufacturing method thereof, polymer and compound.

One aspect of the present invention is to provide a liquid crystal alignment agent containing a polymer (P) having a partial structure represented by the following formula (1) in a main chain.

(In formula (1), W ¹ and W ² are each independently a divalent cyclic group having a benzene ring, a cyclohexane ring, a cyclopentane ring, or a pyridine ring as a ring skeleton; X ¹ is a single bond,- O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁰ CO- or * -CONR ^12- (where R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, "*" Represents a bonding bond with W ¹ ); X ² is -O-, * -COO-, * -OCO-, -CO-, * -NR ¹¹ CO- or * -CONR ^11- (wherein R ¹¹ is a hydrogen atom Or an alkyl group with 1 to 3 carbon atoms, "*" represents a bonding bond with W ² ); R ¹ is a single bond, an alkyldiyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, and carbon number 1 to 20 alkanediyl or 2 to 20 carbon diene dihydric partially substituted hydrogen atoms with a substituent, a divalent group, or 1 to 20 carbon dialkyl or 2 to 20 carbon diene A divalent group in which a part of the methylene group is substituted with -O- or -S-; R ² is a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹² CO-, * -CONR ^12- (wherein R ¹² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, "*" represents a bonding bond with W ¹ ), an alkyldiyl group having 1 to 5 carbon atoms, and carbon Part of the hydrogen atoms of the alkenyl group having 2 to 5 carbon atoms, the alkenyl group having 1 to 5 carbon atoms, or the alkenyl group having 2 to 5 carbon atoms is substituted with a substituent. A bivalent group formed by substitution of a part of the methylene group of an alkylene group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms by -O- or -S-; p represents 0 An integer of ~ 2; wherein, when p = 0, W ¹ is a divalent cyclic group having a cyclohexane ring, a cyclopentane ring or a pyridine ring as a ring skeleton; W ¹ and W ² are substituted or (In the case of unsubstituted phenylene, R ^{1 is} not a single bond.) One aspect of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent. In addition, a liquid crystal display element including the liquid crystal alignment film and a retardation film including the liquid crystal alignment film are provided. In addition, another aspect is to provide a method for manufacturing a retardation film, the manufacturing method comprising: a step of applying a coating film on the substrate to form a coating film; a step of irradiating the coating film with light; and A step of applying a polymerizable liquid crystal to the coating film after the light irradiation to harden the polymerizable liquid crystal.

One aspect of the present invention is to provide a polymer which is at least one polymer selected from the group consisting of polyamidic acid, polyamidate, and polyimide, and contains the following formula (d It is obtained by polymerizing the monomers of the compound represented by). In addition, a compound represented by the following formula (d) is provided.

[Chemical 2]

(In formula (d), X ³ and X ⁴ are each independently a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁴ CO-, or * -CONR ^14- ( Among them, R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with an aminophenyl group); R ³ is an alkyldiyl group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms Alkenyl diyl, phenylene, piperidinyl diyl, alkanediyl having 1 to 20 carbon atoms, or divalent radical having 2 to 20 carbon atoms substituted by a substituent, or a carbon number of 2 A divalent group in which a part of the methylene group of 1 to 20 alkylene or 2 to 20 carbon diene is substituted with -O- or -S-; R ⁴ and R ⁵ are each independently a halogen atom, Or an alkyl or alkoxy group having 1 to 6 carbon atoms; q is 0 or 1; m and n are each independently an integer of 0 to 4; when there are multiple R ⁴ and R ⁵ , multiple R ⁴ And R ⁵ may be the same or different, respectively; W ¹ , W ² , X ¹ , X ² , R ¹ , R ^2, and p are respectively synonymous with the formula (1))

By using the liquid crystal alignment agent of the present invention, it is possible to achieve good applicability to a substrate, friction resistance of a coating film, and afterimage characteristics of a liquid crystal display element. In addition, the liquid crystal alignment agent of the present invention can obtain a retardation film with good liquid crystal alignment.

10‧‧‧ Liquid crystal display element

11a, 11b‧‧‧ glass substrate

12‧‧‧LCD alignment film

13‧‧‧up electrode

14‧‧‧ Insulation

15‧‧‧ bottom electrode

16‧‧‧LCD layer

C1‧‧‧ part enclosed by dotted line

d1‧‧‧ electrode line width

d2‧‧‧Distance between electrodes

FIG. 1 is a schematic configuration diagram of an FFS-type liquid crystal display element.

2 (a) to 2 (b) are schematic plan views of an upper electrode used in the manufacture of a liquid crystal display element for friction alignment. FIG. 2 (a) is a top view of the upper electrode, and FIG. 2 (b) is a partially enlarged view of the upper electrode.

FIG. 3 is a diagram showing driving electrodes of the four systems.

4 (a) to 4 (b) are schematic plan views of an upper electrode used in the manufacture of a liquid crystal display element for photoalignment. FIG. 4 (a) is a plan view of the upper electrode, and FIG. 4 (b) is a partially enlarged view of the upper electrode.

Hereinafter, each component contained in the liquid crystal aligning agent of this invention, and other components arbitrarily mix | blended as needed are demonstrated.

<Polymer (P)>

The liquid crystal alignment agent of this invention contains the polymer (P) which has a partial structure represented by said Formula (1) in a main chain as a polymer component.

W ¹ and W ² in the formula (1) are a divalent cyclic group having a benzene ring, a cyclohexane ring, a cyclopentane ring, or a pyridine ring as a ring skeleton. The "n-valent cyclic group" in the present invention is an n-valent group obtained by removing n hydrogen atoms from the atoms constituting the ring (carbon atoms in the case of W ¹ and W ² ), and may be The ring portion has a substituent.

Specific examples of W ¹ and W ² include 1,4-phenylene, 1,3-phenylene, 1,4-cyclohexyl, 1,3-cyclohexyl, and 1,3-cyclohexyl. A pentyl group, a pyridine-2,5-diyl group, a divalent group obtained by introducing a substituent into a ring portion of each of the groups, and the like. Examples of the substituent that the cyclic skeleton of W ¹ and W ² may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Alkoxy, etc. W ¹ and W ² may be the same as or different from each other.

Among them, in terms of a high reduction effect of alternating current (AC) afterimages, it is preferable that W ¹ and W ^{2 have} at least the ring skeleton of W ¹ be a cyclohexane ring, and the ease of synthesis and cost , it is preferably a ring skeleton of W ¹ and W ² is set to a benzene ring.

When W ¹ and W ² are cyclohexyl, the divalent organic group bonded to the cyclohexane ring may be any of a cis stereo configuration or a trans stereo configuration, but in terms of AC afterimage characteristics In terms of a high improvement effect, the trans stereo configuration is preferred, and the trans-1,4-hexyl group is more preferred.

X ¹ is a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁰ CO- or * -CONR ^10- (where R ¹⁰ is a hydrogen atom or a carbon number of 1 to 3 alkyl, "*" denotes a bond and W is ^1). Preferably it is a single bond, -O-, * -COO-, * -OCO-, * -NHCO-, * -N (CH ₃ ) CO-, * -CONH- or * -CON (CH ₃ )-, more preferably It is a single bond, -O-, * -COO-, or * -OCO-. X ² is -O-, * -COO-, * -OCO-, -CO-, * -NR ¹¹ CO- or * -CONR ^11- (wherein R ¹¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms , "*" Indicates a bond with W ² ). -O-, * -COO-, * -OCO-, * -NHCO-, * -N (CH ³ ) CO-, * -CONH- or * -CON (CH ³ )-, more preferably -O -, * -COO- or * -OCO-.

R ¹ is a single bond, a part of hydrogen atoms of an alkyldiyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. A divalent group substituted with a substituent, or a divalent group obtained by substituting a part of methylene groups of an alkanediyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms by -O- or -S- .

Specific examples of the alkanediyl group having 1 to 20 carbon atoms include methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, and the like. Octanediyl, nonanediyl, decanediyl, dodecanediyl, tetradecanediyl, pentadecyldiyl, cetanediyl, octadecyldiyl, etc., these may be straight The chain may be branched. It is preferably linear. Specific examples of the alkenyl group having 2 to 20 carbon atoms include vinylidene, propylenediyl, butenediyl, pentenediyl, hexenediyl, heptenediyl, octenediyl, Nonene diyl, decene diyl, dodecyl diyl, tetradecenyl di, pentadecyl diyl, hexadecyl diyl, octadecyl diyl, and the like. These may be linear or branched, but are preferably linear.

Examples of the substituent that the alkanediyl group and the alkenediyl group may have include a halogen atom and an alkoxy group.

In terms of making friction resistance and solubility good, R ¹ is preferably an alkanediyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkanediyl group having 1 to 20 carbon atoms or carbon. A divalent group obtained by substituting a part of hydrogen atoms of an alkenyl group of 2 to 20 with a substituent, or an alkylene group of 1 to 20 carbon atoms or a part of the methylene group of an alkenyl group of 2 to 20 carbon atoms via- The divalent group substituted with O- or -S- is more preferably an alkanediyl group having 1 to 20 carbon atoms.

From the viewpoint of making the rubbing resistance and the display unevenness (resistance to frame unevenness) of the display unevenness around the sealant in the liquid crystal display element favorable, the carbon of R ¹ when R ^{1 is} not a single bond is good. The number is preferably 2 or more. Moreover, in order to make the solubility of a polymer favorable, the carbon number is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.

R ² is a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹² CO-, * -CONR ^12- (where R ¹² is a hydrogen atom or a carbon number of 1 to 3 "*" Represents a bonding bond with W ¹ ), an alkyldiyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkanediyl group having 1 to 5 carbon atoms or 2 to 6 carbon atoms A divalent group obtained by substituting a part of hydrogen atoms of 5 alkadiene groups with a substituent, or an alkanediyl group having 1 to 5 carbon atoms or a part of methylene groups of 2 to 5 alkyne groups via -O- or -S- substituted bivalent group. Here, specific examples of the alkanediyl group having 1 to 5 carbons include the aforementioned carbon groups of 1 to 5 in the illustration of R ¹ , and specific examples of the alkenyl group having 2 to 5 carbons may refer to the R Examples of ¹ are those having 2 to 5 carbon atoms. Examples of the substituent that the alkanediyl group and the alkenediyl group in R ² may have include a halogen atom and an alkoxy group.

It is preferable that R ² be a single bond, * -COO-, * -OCO-, * -NHCO-, * -N ( CH ₃ ) CO-, * -CONH-, * -CON (CH ₃ )-("*" represents a bond with W ¹ ) or an alkyldiyl group having 1 to 3 carbon atoms or a hydrogen atom of the alkyldiyl group The divalent group substituted with a fluorine atom is more preferably a single bond, * -COO-, or * -OCO-.

p is an integer of 0 to 2, and in terms of the solubility of the polymer, p is preferably 0 or 1.

From the viewpoint of the balance between the afterimage characteristics of the AC of the liquid crystal display element and the solubility of the polymer, the group represented by "-W ^1- (R ² -W ² ) p-" is preferably a cyclohexyl group or a stretched ring Hexyl, "-Ar ¹ -Ar ^2- " (Ar ¹ is phenylene and Ar ² is cyclohexyl), or "-Ar ³ -COO-Ar ^4- " (Ar ³ and Ar ⁴ are each independently Phenyl or cyclohexyl).

In the formula (1), when p = 0, W ¹ is a divalent cyclic group having a cyclohexane ring, a cyclopentane ring, or a pyridine ring in a ring skeleton.

In the case where W ¹ and W ² are both substituted or unsubstituted phenylene, R ^{1 is} not a single bond, that is, an alkyldiyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. 1, a divalent group having 1 to 20 carbon alkanediyl groups or a 2 to 20 carbon diene group having a hydrogen atom substituted by a substituent, or an alkanediyl group having 1 to 20 carbon atoms or 2 to 2 carbon atoms A divalent group in which a part of the methylene group of the 20 diene group is substituted with -O- or -S-. When the ring skeleton of W ¹ and W ² is a benzene ring, it is preferable to introduce a spacer structure into the main chain of the polymer to improve the coating effect, friction resistance, and afterimage characteristics.

When R ¹ is a single bond, p is preferably 1 or 2. In this case, it is preferable that the obtained liquid crystal display element has a high effect of improving frame unevenness resistance and afterimage characteristics.

Specific examples of the partial structure represented by the formula (1) include, for example, structures represented by the following formulae (1-1) to (1-30).

[Chemical 3]

[Chemical 5]

In the partial structures represented by the formulas (1-1) to (1-6), (1-10) to (1-23), and (1-27) to (1-30), The stereo configuration of the divalent organic group bonded to the cyclohexane ring may be any of trans and cis. In addition, the polymer (P) may have both trans and cis as the formulae (1-1) to (1-6), (1-10) to (1-23), and Partial structures represented by formulas (1-27) to (1-30). Regarding the three-dimensional configuration, with respect to the formula (1-1) to formula (1-6), formula (1-10) to formula (1-23), and formula having 1 molecule of the polymer (P) (1-27) to the total of the partial structures represented by the formula (1-30), the ratio of the trans form is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more. .

Examples of the main chain (main skeleton) of the polymer (P) include a skeleton including polyamic acid, polyimide, polyamic acid ester, polyester, and polyamine. In the present invention, the "main chain" of a polymer means a structure formed by repeating the bonding of monomers. The polymer (P) can be used by appropriately selecting one or two or more kinds of polymers selected from these depending on the application of the liquid crystal alignment agent and the like. This aggregation The substance (P) can be obtained by polymerization using a compound having a structure represented by the formula (1) in a monomer.

Among them, the polymer (P) is preferably at least one selected from the group consisting of polyamidic acid, polyamidoimide, and polyamidate.

[Polyamic acid (P)]

When the polymer (P) is polyamidic acid (hereinafter, also referred to as "polyamidic acid (P)"), the poly (amino acid) (P) can be obtained by, for example, using a tetracarboxylic acid It is obtained by reacting a dianhydride with a diamine. Specifically, it can be obtained, for example, by (i) using a tetracarboxylic dianhydride (hereinafter, also referred to as a "specific tetracarboxylic dianhydride") having a structure represented by the formula (1). A method of polymerizing a monomer; (ii) a method of polymerizing a diamine (hereinafter, also referred to as a "specific diamine") having a structure represented by the formula (1) to the monomer; iii) A method of polymerizing the specific tetracarboxylic dianhydride and the specific diamine using monomers.

(Specific tetracarboxylic dianhydride)

Examples of the specific tetracarboxylic dianhydride used in the method (i) and the method (iii) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Preferred specific examples include, for example, a compound represented by the following formula (t).

(In formula (t), A ¹¹ and A ¹² are each independently a benzene ring or a cyclohexane ring; X ¹³ and X ¹⁴ are each independently a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁵ CO- or * -CONR ^15- (wherein R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with a benzene ring having an acid anhydride group); R ¹³ is a single bond, a part of hydrogen atoms of an alkyldiyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. A divalent group substituted with a substituent, or a divalent group obtained by substituting a part of methylene groups of an alkanediyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms by -O- or -S- R is 0 or 1; wherein, when R ¹³ is a single bond, r = 0; W ¹ , W ² , X ¹ , X ² , R ¹ , R ^2, and p are synonymous with the formula (1), respectively)

X ¹³ and X ^{14 in} the formula (t) are preferably a single bond, -O-, * -COO-, or * -OCO-. Regarding specific examples of R ¹³ and preferred groups, the description of R ¹ can be applied.

Specific examples of the compound represented by the formula (t) include, for example, compounds represented by the following formulae (an-1) to (an-6).

[Chemical 7]

The compounds represented by the formulae (an-3) to (an-6) may be a compound in which the stereo configuration of the divalent organic group bonded to cyclohexane is trans, and the stereo configuration is cis. Either of the compounds may be used, or a mixture of a trans-isomer and a cis-isomer may be used.

The specific tetracarboxylic dianhydride used in the synthesis of the polyamic acid may be used singly or in combination of two or more kinds.

(Other tetracarboxylic dianhydride)

In the method (ii), a tetracarboxylic dianhydride (hereinafter, also referred to as “other tetracarboxylic dianhydride”) that does not have the structure represented by the formula (1) can be used for the monomer. Polymerized to synthesize the polyamidic acid (P). In addition, in the method (i) and the method (iii), the tetracarboxylic dianhydride used in the synthesis may be the specific tetracarboxylic dianhydride alone, but other tetracarboxylic dianhydrides may be used together with the specific tetracarboxylic dianhydride. Carboxylic dianhydride.

Examples of the other tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, and the like; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4. -Cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b- Tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b- Tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran -2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [ 5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene -2,3,5,6-Tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride), 1,3-propanediol bis (Partial Terephthalic anhydride)); Examples of the aromatic tetracarboxylic dianhydride: pyromellitic dianhydride; etc. In addition, the tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can also be used. . In addition, other tetracarboxylic dianhydrides may be used alone or in combination of two or more of them.

It is preferable that the other tetracarboxylic dianhydride used in the synthesis of the poly (amino acid) (P) is contained in a group selected from the group consisting of bicyclic [2.2.1] heptane from the viewpoint of making liquid crystal alignment and solubility in a solvent good. Ethane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxy ring Amylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione , 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione , Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, cyclohexanetetracarboxylic dianhydride and pyromellitic dianhydride At least one compound in the group.

The use ratio of the specific tetracarboxylic dianhydride in the case of the method (i) is preferably 3 mol% relative to the total amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid (P). The above is more preferably 5 mol% or more, and particularly preferably 10 mol% or more. The upper limit of the use ratio is not particularly limited, and can be arbitrarily set within a range of 100 mol% or less.

In addition, the use ratio of the specific tetracarboxylic dianhydride in the case of the method (iii) can be appropriately set according to the use ratio of the specific diamine. The total amount of the acid dianhydride can be, for example, 0.5 mol% or more, preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more.

(Specific diamine)

Specific examples of the specific diamine used in the synthesis of the polyamic acid (P) include an aliphatic diamine, an alicyclic diamine, and an aromatic diamine. Among them, an aromatic diamine is preferable, and specifically, a compound represented by the following formula (d) is preferable.

(In formula (d), X ³ and X ⁴ are each independently a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁴ CO-, or * -CONR ^14- ( Among them, R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with an aminophenyl group); R ³ is an alkyldiyl group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms Alkenyl diyl, phenylene, piperidinyl diyl, alkanediyl having 1 to 20 carbon atoms, or divalent radical having 2 to 20 carbon atoms substituted by a substituent, or a carbon number of 2 A divalent group in which a part of the methylene group of 1 to 20 alkylene or 2 to 20 carbon diene is substituted with -O- or -S-; R ⁴ and R ⁵ are each independently a halogen atom, Or an alkyl or alkoxy group having 1 to 6 carbon atoms; q is 0 or 1; m and n are each independently an integer of 0 to 4; when there are multiple R ⁴ and R ⁵ , multiple R ⁴ And R ⁵ may be the same or different, respectively; W ¹ , W ² , X ¹ , X ² , R ¹ , R ^2, and p are respectively synonymous with the formula (1))

X ³ and X ^{4 in} the formula (d) are preferably a single bond, -O-, * -COO-, or * -OCO-. Among them, when R ¹ is a single bond, X ³ and X ^{4 are} particularly preferably a single bond. Regarding specific examples of R ³ and preferred groups, the description of R ¹ can be applied. m and n are preferably 0.

Specific examples of the compound represented by the formula (d) include, for example, compounds represented by the following formulae (D-1) to (D-36).

[Chemical 10]

[Chemical 11]

[Chemical 12]

Formula (D-1) to Formula (D-3), Formula (D-5), Formula (D-7), Formula (D-8), Formula (D-10) to Formula (D-24) And the compounds represented by the formulae (D-29) to (D-35) can use compounds in which the divalent organic group bonded to the cyclohexane ring is a trans compound and the stereo configuration is cis Either of the compounds or a mixture of a trans-isomer and a cis-isomer may be used. When using the formulas (D-1) to (D-3), (D-5), (D-7), (D-8), (D-10) to (D- 24) In the case of compounds represented by formulae (D-29) to (D-35), it is preferable to set the ratio of trans isomers (the total amount when two or more compounds are used). 50 Mo Ear mole% or more, more preferably 70 mole% or more, and particularly preferably 90 mole% or more. The specific diamine used in the synthesis of the polyamic acid may be used alone or in combination of two or more of these compounds.

In addition, among the compounds represented by the formulas (D-1) to (D-36), the compounds represented by the formulas (D-5) and (D-10) to (D-17) are equivalent, respectively. A diamine having a partial structure in which R ¹ in the formula (1) is a single bond and p is 1 or 2.

(Other diamines)

In the method (i), the polyfluorene is synthesized by polymerization of a monomer using a diamine (hereinafter, also referred to as “other diamine”) that does not have the structure represented by the formula (1). Amino acid (P). In addition, in the method (ii) and the method (iii), the diamine used in the synthesis may use the specific diamine alone, but other diamines may be used together with the specific diamine.

Examples of the other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine organosiloxanes. As specific examples of these diamines, examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexyl. Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl Thioether, 4,4'-diaminodiphenylamine, 1,7-bis (4-aminophenoxy) heptane, 2,2'-dimethyl-4,4'-diamine Biphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane , 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) ) Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, N, N'-bis (4-aminophenyl) -benzidine, 3, 5-diaminobenzoic acid, dodecyloxy-2,4-diamine Benzene, dodecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3 Cholesteryl 5,5-diaminobenzoate, 3,6-bis (4-aminobenzyloxy) cholestane, 4- (4'-trifluoromethoxybenzyloxy) Group) cyclohexyl-3,5-diaminobenzoate, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 1- (2,4- Diaminophenyl) piperazine-4-carboxylic acid, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, 1- (4-aminophenyl) -2,3 -Dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl- 1H-indene-6-amine, 4-aminophenyl-4'-aminobenzoate, 4,4 '-[4,4'-propane-1,3-diylbis (piperidine-1 , 4-diyl)] diphenylamine, a compound represented by the following formula (D-1a), and the like;

(In the formula (D-1a), X ^I and X ^II are each independently a single bond, -O-, -COO-, or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single Bond or alkanediyl having 1 to 3 carbon atoms; a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1; wherein a and b will not be 0 at the same time )

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilazane; etc. In addition, Japanese Patent Application Laid-Open No. 2010-97188 can be used. Documented diamine.

The divalent group represented by "-X ^I- (R ^I -X ^II ) _d- " in the formula (D-1a) is preferably an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OC ₂ H ₄ -O- (wherein the bond marked with "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _{2c + 1} " include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, N-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecane Group, n-eicosyl, etc. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1a) include, for example, compounds represented by the following formulae (D-1-1) to (D-1-4).

In addition, other diamines used in the synthesis of the polyamidic acid may be used alone One kind of compound or two or more kinds are suitably selected and used.

The use ratio of the specific diamine in the case of the method (ii) is preferably 3 mol% or more with respect to the total amount of diamines used in the synthesis of polyamic acid (P), and more preferably It is 5 mol% or more, Especially preferably, it is 10 mol% or more. The upper limit of the use ratio is not particularly limited, and can be arbitrarily set within a range of 100 mol% or less. When an improvement effect (for example, a voltage holding ratio, liquid crystal alignment, etc.) by addition of another diamine is calculated | required, it is preferable to set the usage ratio of the said specific diamine to 95 mol% or less.

In addition, the use ratio of the specific diamine in the case of the method (iii) can be appropriately set according to the use ratio of the specific tetracarboxylic dianhydride. The total amount can be, for example, 0.5 mol% or more, preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 4 mol% or more.

When the liquid crystal alignment agent of the present invention is used in the production of a TN-type, STN-type, or vertical alignment-type liquid crystal display element, at least a part of the polymer (P) contained in the liquid crystal alignment agent may be as follows A polymer having a group (hereinafter, also referred to as a "pre-tilt developing group") capable of imparting a pre-tilt developing ability to a coating film. Examples of the pretilt developing group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, and a group having a steroid skeleton. Polycyclic structure and so on.

For example, in order to obtain a polyamidic acid (P) having a pretilt-developing group, in terms of ease of introduction of the pretilt-developing group, it is preferable to use a monomer composition Polymerization is carried out by containing a diamine having a pretilt developing group. Specifically, it can synthesize | combine by using the diamine which has the said pretilt developing group as another diamine.

In the case of using a diamine having a pretilt-angle-developing group, from the viewpoint of showing sufficiently high pretilt-angle characteristics, the use amount thereof is preferably 3 mol% or more with respect to all the diamines used in the synthesis. It is more preferably set to 5 mol% to 70 mol%.

When a liquid crystal alignment ability is imparted to a coating film produced using the liquid crystal alignment agent of the present invention by a photo-alignment method, at least a part of the polymer (P) contained in the liquid crystal alignment agent may be provided with photo-alignment. Structure of the polymer. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposition-type photo-alignment unit. Specifically, as the photo-alignment structure, a group exhibiting photo-alignment by photo isomerization, photo-dimerization, photo-decomposition, or the like can be used, and examples include a coupling group containing azobenzene or a derivative thereof as a basic skeleton. A nitrogen benzene group, a cinnamic acid structure group containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone group containing a chalcone or a derivative thereof as a basic skeleton, a benzophenone or a derivative thereof Benzophenone-containing group as a basic skeleton, coumarin-containing group as a basic skeleton, coumarin-containing group as a basic skeleton, polyfluorene-imide as a basic skeleton Structure.

In the case where the polyamic acid (P) has a photo-alignment structure, the photo-alignment structure is preferably a decomposition-type photo-alignment part, and specifically, it is preferable to have a bicyclic [2.2.2] octene skeleton or a ring Butane backbone polymer. Polyamic acid (P) having a bicyclic [2.2.2] octene skeleton or a cyclobutane skeleton can be obtained by using a bicyclic [2.2.2] oct-7-ene At least any one of -2,3,5,6-tetracarboxylic dianhydride and cyclobutane tetracarboxylic dianhydride is obtained as another tetracarboxylic dianhydride.

[Synthesis of the compound represented by the formula (1)]

The compound represented by the formula (1) can be synthesized by appropriately combining ordinary methods of organic chemistry. An example thereof is a method of synthesizing a dinitro intermediate having a nitro group instead of the primary amine group in the formula (d) with respect to the specific diamine, and then using a suitable reduction system to convert the obtained dinitro group The intermediate nitro group is aminated.

The method for synthesizing the dinitro intermediate can be appropriately selected depending on the intended compound. For example, it can be synthesized by using one of the following methods alone or combining two or more methods as appropriate: a hydroxyl-containing compound having a group represented by "-W ^1- (R ² -W ² ) p-" A method of reacting with a carboxylic acid having a group represented by "-X ³ -R ^1- " and a nitrophenyl group; and having a group represented by "-W ^1- (R ² -W ² ) p-" Method for reacting a hydroxyl group-containing compound with a carboxylic acid having a group represented by "-(R ³ -X ⁴ ) q-" and a nitrophenyl group; and having "-W ^1- (R ² -W ² ) p A method of reacting a carboxylic acid having a group represented by "-" with a hydroxyl-containing compound having a group represented by "-X ³ -R ^1- " and a nitrophenyl group; and allowing "-W ^1- (R ^2- W ² ) a method in which a carboxylic acid of the group represented by "p-" is reacted with a hydroxyl-containing compound having a group represented by "-(R ³ -X ⁴ ) q-" and a nitrophenyl group; Method for reacting a carboxylic acid having a group represented by R ¹ -X ¹ -W ^1- (R ² -W ² ) p- "with a nitrophenol or a derivative thereof; and having" -R ¹ -X ¹ -W ^{1 - (R 2 -W 2)} p- " method group or a halide with a nitrophenol derivative represented by the reaction; Having a ^{"-W 1 - (R 2 -W} 2) pX 2 -R 3 -" Method and a carboxylic acid group or a nitrophenol derivative represented by the reaction; so having "-W ¹ - (R ² -W ² ) A method in which a halide of the group represented by pX ² -R ^3- "is reacted with nitrophenol or a derivative thereof; and a group represented by" -X ³ -R ^1- "and a nitrobenzene Method for reacting a halide of a group with a hydroxyl-containing compound having a group represented by "-W ^1- (R ² -W ² ) p-"; and having a group represented by "-X ⁴ -R ^3- " and halide having ^{"-W 1 - (R 2 2} -W) p-" nitrophenyl group-containing hydroxyl compound represented by reacting; contacting with "-R ¹ -W ¹ - ( Method for reacting a hydroxyl-containing compound having a group represented by R ² -W ² ) p- "with nitrobenzidine chloride; and having" -R ¹ -W ^1- (R ² -W ² ) p- " A method for reacting a primary amine of a group represented by nitrobenzidine with a ratio of fluorenyl chloride having a group represented by "-R ¹ -W ^1- (R ² -W ² ) p-" with 4- A method of reacting nitroaniline or a derivative thereof, and the like.

The reaction to obtain the dinitro intermediate is preferably performed in an organic solvent. The organic solvent here may be any solvent that does not affect the reaction, and examples thereof include methanol, ethanol, tetrahydrofuran, toluene, dichloromethane, dimethylmethylene, dimethylformamide, and dimethylacetamide. , N-methyl-2-pyrrolidone and the like. In addition, the reaction may be performed in the presence of a catalyst, if necessary.

The reduction reaction of the dinitro intermediate is preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, or nickel. Examples of the organic solvent used herein include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis order of a specific diamine is not limited to the said method.

[Synthesis of Polyamic Acid (P)]

It is preferable that the use ratio of the tetracarboxylic dianhydride and diamine supplied to the synthesis reaction of a polyamic acid (P) is 1 equivalent with respect to the amine group of a diamine, and the anhydride group of a tetracarboxylic dianhydride becomes The ratio of 0.2 to 2 equivalents is more preferably a ratio of 0.3 to 1.2 equivalents.

In the synthesis of the polyamic acid (P), a terminally modified polymer can be synthesized by using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and diamine as described above. By synthesizing the terminal-modified polymer, the coatability (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of molecular weight regulators include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, phenyl isocyanate, and isocyanate Monoisocyanate compounds such as naphthyl esters and the like. The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used.

The synthesis reaction of the polyamic acid is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, it is preferred to use one or more members selected from the group consisting of aprotic polar solvents and phenol-based solvents (organic solvents of the first group), or organic solvents selected from the first group. A mixture of one or more of the above and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). In the latter case, the use ratio of the organic solvent in the second group is preferably 50% by weight or less, and more preferably 40% by weight, relative to the total amount of the organic solvent in the first group and the organic solvent in the second group. % Or less, and particularly preferably 30% by weight or less.

It is particularly preferable to use a member selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, γ-butyrolactone, Methylurea, hexa One or more solvents selected from the group consisting of methylphosphonium triamine, m-cresol, xylenol and halogenated phenol, or it is preferable to use one or more of these solvents with other organic compounds in the range of the ratio. A mixture of solvents.

It is preferable that the usage-amount (a) of an organic solvent is 0.1 weight%-50 weight% with respect to the total amount (a + b) of a reaction solution, and the total amount (b) of a tetracarboxylic dianhydride and a diamine. The reaction temperature of the synthesis reaction of the polyamic acid is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours.

As described above, a reaction solution obtained by dissolving polyamic acid (P) was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamic acid (P) contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamine can also be provided. The acid (P) is purified and then provided to the preparation of the liquid crystal alignment agent. In the case of dehydration and ring closure of polyamidic acid (P) to produce polyimide, the reaction solution may be directly provided to the dehydration ring closure reaction, or the polyamidic acid ( P) After separation, it is provided to the dehydration ring closure reaction. Alternatively, the separated polyamidic acid (P) may be purified and then provided to the dehydration ring closure reaction. Isolation and purification of polyamic acid can be performed according to a known method.

[Polyurethane (P)]

The polyamidate (hereinafter, also referred to as polyamidate (P)) as the polymer (P) can be obtained, for example, by the following method: [I] by allowing the synthesis reaction to A method for reacting the obtained polyamic acid (P) with an esterifying agent such as a hydroxyl-containing compound, an acetal-based compound, a halide, or an epoxy-containing compound; [II] tetracarboxylic acid di A method of reacting an ester with a diamine; [III] A method of reacting a dicarboxylic acid diester dihalide with a diamine, and the like.

Here, as specific examples of the esterifying agent used in the method [I], examples of the hydroxyl-containing compound include alcohols such as methanol, ethanol, and propanol; phenols such as phenol and cresol; and acetal compounds such as Examples include N, N-dimethylformamide diethyl acetal and N, N-diethylformamide diethyl acetal. Examples of the halide include bromomethane, bromoethane, and bromine. Octadecane, methyl chloride, octadecyl chloride, 1,1,1-trifluoro-2-iodoethane, and the like; examples of the epoxy group-containing compound include propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can be obtained by ring-opening a tetracarboxylic dianhydride using the alcohol. The tetracarboxylic acid diester dihalide used in the method [III] can be reacted with an appropriate chlorinating agent such as thionyl chloride by using the tetracarboxylic acid diester obtained as described above. And get. The diamine used in the method [II] and the method [III] preferably includes the specific diamine, and the other diamine may be used as necessary. In addition, the polyamidate (P) may have only the monoamidate structure, or may be a partial esterified product in which the pseudoamidate structure and the pseudoamidate structure coexist.

[Polyimide (P)]

The polyimide (hereinafter also referred to as polyimide (P)) as the polymer (P) can be dehydrated and ring-closed by, for example, synthesizing the polyimide (P) synthesized as described above, and Obtained by imidization.

The polyfluorene imine (P) may be a complete fluorinated imide obtained by dehydrating and closing all the fluorinated amino acids in the polyfluorinated acid (P) as a precursor thereof, or may be a fluorinated compound only Dehydration and ring closure of a part of the amino acid structure make the amino acid structure Part of the fluorene imide coexisting with the fluorene imine ring structure. The polyimide content of the polyimide contained in the liquid crystal alignment agent of the present invention is preferably 30% or more, more preferably 40% to 99%, and particularly preferably 50% to 99%. The said fluorene imidization ratio expresses the ratio of the number of fluorene imine ring structures with respect to the sum of the number of fluorene acid structures and the number of fluorene imine ring structures with respect to a polyfluorene imide, and shows it as a percentage. Here, a part of the fluorene imine ring may be an isofluorene ring.

The dehydration ring closure of the polyamic acid is preferably performed by a method of heating the polyamic acid, or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closing catalyst to the solution, depending on A method of heating is required. Among these, the latter method is preferably used.

In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The used amount of the dehydrating agent is preferably 0.01 mol to 20 mol with respect to 1 mol of the sulfamic acid structure of the polyamic acid. Examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. The used amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 mols with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as the organic solvent for synthesizing polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, and more preferably 10 ° C to 150 ° C. The reaction time is preferably 1.0 to 120 hours, and more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyfluoreneimine (P) was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or it can be removed from the reaction solution. The dehydrating agent and the dehydration ring-closing catalyst are then provided to the preparation of the liquid crystal alignment agent. The polyfluorene imide may also be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyfluorene imide may be purified and then provided to Preparation of liquid crystal alignment agent. These purification operations can be performed according to a known method. In addition, polyfluorene imine (P) can be obtained by fluoramidation of polyfluorene ester (P).

The polyamidic acid (P), polyamidate (P), and polyimide (P) obtained in this manner preferably have 20 mPa when they are made into a solution having a concentration of 15% by weight. s ~ 1,800mPa. The solution viscosity of s is more preferably 50 mPa. s ~ 1,500mPa. Solution viscosity of s. In addition, the solution viscosity (mPa.s) of the polymer is 15% by weight for a good solvent prepared using the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) The value of the polymer solution measured at 25 ° C using an E-type viscometer.

A polystyrene-equivalent weight average of the polyamidic acid (P), polyamidate (P), and polyimide (P) measured by Gel Permeation Chromatography (GPC) The molecular weight (Mw) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, and more preferably 10 or less. By being in such a molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

<Other ingredients>

The liquid crystal alignment agent of this invention contains the said polymer (P), but may contain other components as needed. Examples of other components that can be added to the liquid crystal alignment agent include Polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy-containing compounds"), functional silane compounds, metal chelate compounds, hardened Accelerators, surfactants, etc.

[Other polymers]

The other polymers may be used for improving solution characteristics or electrical characteristics. The other polymer is a polymer that does not have a partial structure represented by the formula (1) in the main chain, and the main skeleton is not particularly limited. Specific examples include derivatives derived from polyamic acid, polyimide, polyamidate, polyorganosiloxane, polyester, polyamine, cellulose derivatives, polyacetal, and polystyrene. Polymers such as polymers, poly (styrene-phenylcis butene diamidine) derivatives, poly (meth) acrylates, and the like are used as the main skeleton. Among them, at least one polymer selected from the group consisting of polyamidic acid, polyamidate, polyimide, and polyorganosiloxane is preferred. Other polymers can be synthesized by a conventionally known method. In addition, when a liquid crystal alignment ability is imparted to a coating film formed using the liquid crystal alignment agent of the present invention by a photo-alignment method, a polymer having the photo-alignment structure may be used as the other polymer.

When other polymers are added to the liquid crystal alignment agent, the blending ratio of the other polymers is preferably 50 parts by weight or less with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. It is preferably 0.1 to 40 parts by weight, and particularly preferably 0.1 to 30 parts by weight.

[Epoxy-containing compound]

The epoxy group-containing compound can be used in order to improve the adhesiveness or electrical characteristics of the liquid crystal alignment film to the substrate surface. Examples of such epoxy group-containing compounds include: Glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanedione Glycidyl ether, Glycerol diglycidyl ether, Trimethylolpropane triglycidyl ether, 2,2-Dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'-Tetraglycidyl ether -M-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4' -Diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexyl Amine and the like are preferred compounds. Other examples of the epoxy group-containing compound include an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598.

When these epoxy compounds are added to the liquid crystal alignment agent, the blending ratio of the epoxy compound is preferably 40 parts by weight or less with respect to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent. It is more preferably set to 0.1 to 30 parts by weight.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printability of a liquid crystal alignment agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyl Triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxy Silylpropyltriethylene triamine, 10-trimethyl Oxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6- Methyl diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidyloxymethyltrimethoxysilane , 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like.

When these functional silane compounds are added to a liquid crystal alignment agent, it is preferable that the blending ratio of the functional silane compound is 2 parts by weight based on 100 parts by weight of the total polymer contained in the liquid crystal alignment agent. Hereinafter, it is more preferably set to 0.02 to 0.2 parts by weight.

[Metal chelate compound]

When the polymer component of the liquid crystal alignment agent has an epoxy structure, the metal chelate compound is contained in the liquid crystal alignment agent (especially the phase) for the purpose of ensuring the mechanical strength of the film formed by low-temperature treatment. Liquid crystal alignment agent for differential films). The metal chelate compound is preferably an acetoacetone complex or an acetoacetate complex using a metal selected from aluminum, titanium, and zirconium. Specifically, for example, aluminum diisopropoxyethylacetate, aluminum tris (ethylpyruvate), aluminum tris (ethylacetylate), and diisopropyloxybis (ethylethyl) Rhenium acetate) titanium, titanium diisopropoxy bis (ethylidenepyruvate) titanium, zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and the like. When the metal chelate compound is added, the use ratio of the metal chelate compound is preferably 50 parts by weight or less with respect to 100 parts by weight of the total of the constituent components including the epoxy structure, and more preferably 0.1 part by weight. Parts to 40 parts by weight, particularly preferably 1 to 30 parts by weight.

[Hardening accelerator]

The hardening accelerator is contained in the liquid crystal alignment agent in order to ensure the mechanical strength of the formed liquid crystal alignment film and the stability of the liquid crystal alignment over time when the polymer component in the liquid crystal alignment agent has an epoxy structure ( Especially in the liquid crystal alignment agent for retardation films). As the hardening accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphate group, a sulfonic acid group, a carboxyl group, a carboxylic acid anhydride group, or the like can be used. Among them, a compound having a phenol group or a silanol group is preferred. Specific examples of the compound having a phenol group include cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, and 4-benzylphenol; and compounds having a silanol group Examples include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disilaxanediol, and 1,4-bis (hydroxydimethylsilane). Group) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, and the like. When a hardening accelerator is added, the use ratio of the hardening accelerator is preferably 50 parts by weight or less, and more preferably 0.1 to 40 parts by weight, with respect to 100 parts by weight of the total of the constituent components including the epoxy structure. It is particularly preferably 1 to 30 parts by weight.

[Surfactant]

The surfactant may be contained in a liquid crystal alignment agent (particularly, a liquid crystal alignment agent for a retardation film) for the purpose of improving the coatability of the liquid crystal alignment agent to a substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. . The use ratio of the surfactant is preferably set to 10 parts by weight or more with respect to 100 parts by weight of the total amount of the liquid crystal alignment agent. Below, it is more preferably 1 part by weight or less.

In addition, other components besides the above-mentioned components include a compound having at least one oxetanyl group in the molecule, an antioxidant, and the like.

<Solvent>

The liquid crystal alignment agent of the present invention is preferably prepared as a liquid composition in which the polymer (P) and other components used as necessary are dispersed or dissolved in a suitable solvent.

Examples of the organic solvent used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, and N, N-dimethylethyl Phenylamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol Alcohol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether Acid esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These solvents can be used alone or in combination of two or more.

The solid content concentration (the ratio of the total weight of components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) in the liquid crystal alignment agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. The range is 1% to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of a substrate by a method described later, and it is preferable to heat it to form a coating film or a liquid crystal alignment film. It is a coating film of a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coating property tends to decrease. .

A particularly preferred range of the solid content concentration varies depending on the application of the liquid crystal alignment agent or the method used when the liquid crystal alignment agent is applied to the substrate. For example, when a liquid crystal alignment agent for a liquid crystal alignment film is coated on a substrate by a spinner method, the solid content concentration (the total weight of all components other than the solvent in the liquid crystal alignment agent is included in the total weight of the liquid crystal alignment agent). The proportion) is particularly preferably in a range of 1.5% to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% to 9% by weight, and thereby set the solution viscosity to 12 mPa. s ~ 50mPa. The range of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% to 5% by weight, and thereby set the solution viscosity to 3 mPa. s ~ 15mPa. The range of s. The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C. Moreover, about the liquid crystal aligning agent for retardation films, it is preferable that the solid content concentration of a liquid crystal aligning agent is 0.2 to 10 weight% from a viewpoint of making the coating property of a liquid crystal aligning agent and the film thickness of the coating film moderate. The range of% is more preferably in the range of 3% to 10% by weight.

<Liquid crystal display element and retardation film>

Liquid crystal alignment can be produced by using the liquid crystal alignment agent of the present invention described above membrane. The liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention can be preferably applied to a liquid crystal alignment film for a liquid crystal display element (for a liquid crystal cell) and a liquid crystal alignment film for a retardation film. Hereinafter, a liquid crystal display element and a retardation film of the present invention will be described.

[Liquid crystal display element]

A liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited. For example, it can be applied to TN type, STN type, and VA type (including Vertical Alignment-Multidomain Vertical Alignment (VA-MVA) type, vertical Alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), IPS type, FFS type, optically compensated bend (OCB) type and other action modes.

The liquid crystal display element of the present invention can be produced by, for example, a step including the following steps (1-1) to (1-3). Step (1-1) uses different substrates depending on the required operation mode. Steps (1-2) and (1-3) are common to each operation mode.

[Step (1-1): Formation of Coating Film]

First, a liquid crystal alignment agent of the present invention is coated on a substrate, and then a coating surface is heated to form a coating film on the substrate.

(1-1A) When manufacturing, for example, a TN-type, STN-type, or VA-type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are used as a pair, and the transparent conductive films are provided on each of the two substrates. The formation surface is preferably coated with the liquid crystal alignment agent of the present invention by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. For the substrate, for example, glass such as float glass and soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, and poly (alicyclic olefin) can be used. Transparent substrate. The transparent conductive film provided on one side of the substrate can be oxidized with a NESA film (registered trademark of the United States PPG) containing tin oxide (SnO ₂ ), and an oxide containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Indium tin oxide (ITO) film and the like. In order to obtain a patterned transparent conductive film, for example, the following methods may be used: a method of forming a pattern by photoetching after forming a patternless transparent conductive film; a method of using a mask having a desired pattern when forming a transparent conductive film Wait. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface on which the coating film is formed may be coated with a functional silane compound or a functional titanium compound in advance. Before processing.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing the applied liquid crystal alignment agent from sagging or the like. The pre-baking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, a firing (post-baking) step is performed for the purpose of completely removing the solvent and thermally imidizing the amido acid structure present in the polymer as necessary. The firing temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the film formed as described above is preferably 0.001 μm to 1 In m, it is more preferably 0.005 μm to 0.5 μm.

(1-1B) In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, an electrode formation surface of a substrate provided with an electrode including a transparent conductive film or a metal film patterned in a comb-tooth shape is provided, and The liquid crystal alignment agent of the present invention is coated on one side of the opposing substrate on which the electrodes are provided, and then each coated surface is heated to form a coating film. Regarding the material, coating method, heating conditions after coating, the method of patterning the transparent conductive film or metal film, the substrate pretreatment, and the preferred film thickness of the formed coating film, the substrate and the transparent conductive film used at this time, and The (1-1A) is the same. As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the cases (1-1A) and (1-1B), after the liquid crystal alignment agent is coated on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, by further heating after the coating film is formed, the dehydration ring-closing reaction of the polyamic acid, the polyamic acid ester, and the polyfluorene imide prepared in the liquid crystal alignment agent of the present invention proceeds, thereby producing Further imidized coating.

[Step (1-2): Alignment Capability Provisioning Process]

In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a process of imparting liquid crystal alignment ability to the coating film formed in the step (1-1) is performed. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the alignment ability imparting process include a rubbing treatment in which a coating film is rubbed in a certain direction using a roller wound with a cloth containing fibers such as nylon, rayon, and cotton, and the coating film is irradiated with polarized or non-polarized radiation. Alignment processing, etc. The other side On the other hand, in the case of manufacturing a VA-type liquid crystal display element, the coating film formed in the step (1-1) may be directly used as a liquid crystal alignment film, and the coating film may be subjected to an alignment ability providing process. In addition, since the coating film obtained by using the liquid crystal alignment agent of the present invention has good friction resistance, it is possible to impart a high alignment restraining force to the coating film by rubbing treatment.

In the photo-alignment treatment, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used as radiation for irradiating the coating film. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized or partially polarized, the substrate surface may be irradiated from a vertical direction, or may be irradiated from an oblique direction, or a combination of these irradiations may be performed. When irradiating non-polarized light, the irradiation direction is set to an oblique direction.

The light source used can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like. Ultraviolet rays in a preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, and the like. The radiation exposure is preferably ^{100J / cm 2 ~ 50,000J / cm} 2, more preferably ^{300J / cm 2 ~ 20,000J / cm} 2. In addition, in order to improve the reactivity, the coating film may be subjected to light irradiation while being heated. The temperature during heating is usually 30 ° C to 250 ° C, preferably 40 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C.

In addition, the following treatment may be further performed on the liquid crystal alignment film after the rubbing treatment, so that the liquid crystal alignment film has different liquid crystal alignment capabilities in each region: a part of the liquid crystal alignment film is irradiated with ultraviolet rays to a part of the liquid crystal alignment film. Treatment of changing the pretilt angle; or forming a part of the surface of the liquid crystal alignment film After the etchant film, a rubbing treatment is performed in a direction different from the rubbing treatment just before, and then the resist film is removed. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be applied to a polymer sustained alignment (PSA) type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell]

A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed in the above-mentioned manner, and arranging liquid crystal between the two substrates disposed opposite to each other. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged to face each other across a gap (cell gap) with their respective liquid crystal alignment films facing each other, and the peripheral portions of the two substrates are bonded using a sealant, and are divided by the substrate surface and the sealant. After filling and filling the liquid crystal into the cell gap, the injection hole is sealed, so that a liquid crystal cell can be manufactured. The second method is a method called a liquid crystal drip (ODF) method. A predetermined position on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, a UV-curable sealant, and the liquid crystal is dripped at predetermined positions on the liquid crystal alignment film surface. The alignment film is bonded to another substrate, and the liquid crystal is spread on the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using any method, it is desirable to remove the liquid crystal cell manufactured as described above and further heat the liquid crystal used to a temperature at which the isotropic phase becomes an isotropic phase, and then cool it to room temperature to remove it. Flow alignment during liquid crystal filling.

As the sealant, an adhesive generally used as an adhesive for liquid crystals can be used, and for example, an epoxy resin containing a hardener can be used. As the sealant, an epoxy resin or the like which further contains alumina balls as a spacer can be used.

Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferred. For example, a Schiff base liquid crystal and azoxy can be used. Based liquid crystal, biphenyl based liquid crystal, phenylcyclohexane based liquid crystal, ester based liquid crystal, terphenyl based liquid crystal, biphenyl cyclohexane based liquid crystal, pyrimidine based liquid crystal, dioxane based liquid crystal, bicyclooctane based liquid crystal Liquid crystal, cubic liquid crystal, and the like. In addition, these liquid crystals may be used by adding the following substances: cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate ); Chiral agent sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxymethylene-p-amino-2 -Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate.

Furthermore, a liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called an “H film” with a protective film of cellulose acetate or a polarizing plate including the H film itself. A "membrane" is a film formed by absorbing iodine while extending the orientation of polyvinyl alcohol.

[Phase Difference Film]

Next, a method for manufacturing a retardation film using the liquid crystal alignment agent of the present invention will be described. When the retardation film of the present invention is manufactured, not only the generation of dust or static electricity can be suppressed in the step, but also a uniform liquid crystal alignment film can be formed, and by using an appropriate photomask during radiation irradiation, In terms of arbitrarily forming a plurality of regions having different liquid crystal alignment directions on the substrate, it is preferable to use a light alignment method. Specifically, manufacturing can be performed through the following steps (2-1) to (2-3).

[Step (2-1): Formation of Coating Film Using Liquid Crystal Alignment Agent]

First, a liquid crystal alignment agent of the present invention is applied on a substrate to form a coating film. Examples of the substrate used here include triacetin cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polyamine, polyimide, polyimide Transparent substrate of synthetic resins such as methyl methacrylate and polycarbonate. Among these substrates, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. In addition, in terms of low hygroscopicity of the solvent, good optical characteristics, and low cost, polymethyl methacrylate can be preferably used as a substrate for a retardation film. In addition, to the substrate for applying the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the coating film, a conventionally known pretreatment may be performed on the surface on the substrate surface where the coating film is formed.

In most cases, a retardation film is used in combination with a polarizing film. At this time, in order to exhibit the required optical characteristics, it is necessary to precisely control the angle with respect to the polarization axis of the polarizing film to a specific direction to attach the retardation film. Therefore, here, by A liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle is formed on a substrate such as a TAC film or polymethyl methacrylate, and a step of bonding a retardation film to a polarizing film while controlling the angle thereof can be omitted. In addition, this can contribute to improving the productivity of the liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle, it is preferable to perform the photo alignment method using the liquid crystal alignment agent of the present invention.

The liquid crystal alignment agent may be applied on the substrate by a suitable coating method. For example, a roll coater method, a spinner method, a printing method, an inkjet method, a rod coater method, or an extrusion die method may be used. Direct gravure coater method, chamber doctor coater method, offset gravure coater method, single roll kiss coater method, using small Diameter gravure roll reverse kiss coater method, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air knife coater method, The positive rotation roll coater method, the blade coater method, the knife coater method, the impregnating coater method, the MB coater method, the MB trans coater method, and the like.

After coating, the coating surface is heated (baking) to form a coating film. The heating temperature at this time is preferably set to 40 ° C to 150 ° C, and more preferably set to 80 ° C to 140 ° C. The heating time is preferably 0.1 minutes to 15 minutes, and more preferably 1 minute to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 nm to 1,000 nm, and more preferably 5 nm to 500 nm.

[Step (2-2): Light irradiation step]

Then, the coating film formed on the substrate in the manner described above is irradiated with light to give the coating film a liquid crystal alignment capability, thereby forming a liquid crystal alignment film. Here, the irradiated light includes, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm. Among these lights, ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferred. The irradiation light may be polarized light or non-polarized light. The polarized light is preferably light including linearly polarized light.

When the light used is polarized light, the substrate surface may be irradiated with light from a vertical direction, or may be irradiated with light from an oblique direction, or these irradiations may be performed in combination. When non-polarized light is irradiated, the substrate surface must be irradiated from the oblique direction.

Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps (Hg-Xe lamps), and the like. Polarized light can be obtained by a method in which these light sources are used in combination with, for example, a filter and a diffraction grating.

The light irradiation amount is preferably 0.1 mJ / cm ² or more and less than 1,000 mJ / cm ² , more preferably 1 mJ / cm ² to 500 mJ / cm ² , and particularly preferably ² mJ / cm ² to 200 mJ / cm. ² .

[Step (2-3): Formation of liquid crystal layer]

Then, a polymerizable liquid crystal is applied to the coating film after being irradiated with light in the manner described above, and is cured. Thereby, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one of heating and light irradiation. This polymerizable liquid crystal can be used The conventionally known liquid crystals include, for example, Non-Patent Document 1 ("UV-Curable Liquid Crystals and Their Application", "Liquid Crystals", Vol. 3 No. 1 (1999 ), Pages 34 to 42). In addition, it may be: a cholesteric liquid crystal; a disc-type liquid crystal; a twisted nematic alignment type liquid crystal to which a chiral agent is added; and the like. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may be a composition containing a known polymerization initiator or a suitable solvent.

When coating the polymerizable liquid crystal as described above on the formed liquid crystal alignment film, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method can be used.

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation, thereby curing the coating film to form a liquid crystal layer. It is preferable to perform these processes overlappingly, and to obtain a good alignment.

The heating temperature of a coating film can be suitably selected according to the kind of polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, heating is preferably performed at a temperature in a range of 40 ° C to 80 ° C. The heating time is preferably 0.5 minutes to 5 minutes.

As the irradiation light, non-polarized ultraviolet rays having a wavelength in a range of 200 nm to 500 nm can be preferably used. The light irradiation amount is preferably 50 mJ / cm ² to 10,000 mJ / cm ² , and more preferably 100 mJ / cm ² to 5,000 mJ / cm ² .

The thickness of the formed liquid crystal layer is appropriately set according to the required optical characteristics. For example, when manufacturing a 1/2 wavelength plate of visible light with a wavelength of 540 nm, select The retardation of the formed retardation film has a thickness of 240 nm to 300 nm. If the retardation film is a 1/4 wavelength plate, the thickness of the retardation is selected to be 120 nm to 150 nm. The thickness of the liquid crystal layer that can obtain the target retardation varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for manufacturing a quarter-wave plate is in a range of 0.6 μm to 1.5 μm.

The retardation film obtained in this manner can be preferably used as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film manufactured using the liquid crystal alignment agent of the present invention is applied is not limited in its operation mode, and can be applied to various known modes such as TN type, STN type, IPS type, FFS type, and VA type. . The retardation film is used by attaching a substrate-side surface of the retardation film to an outer surface of a polarizing plate arranged on a viewing side of a liquid crystal display element. Therefore, it is preferable that the substrate of the retardation film is made of TAC or an acrylic substrate, and the substrate of the retardation film also functions as a protective film of a polarizing film.

Here, a method for producing a retardation film on an industrial scale is a roll-to-roll method. The method is to unroll a film from a roll of a long substrate film, perform continuous steps to form a liquid crystal alignment film on the rolled film, apply polymerizable liquid crystal to the liquid crystal alignment film, and A method of performing a hardening process and a process of laminating a protective film as necessary, and recovering the film after the step as a wound body. The retardation film formed using the liquid crystal alignment agent of the present invention has good adhesion to a substrate, and even when the retardation film is stored in the form of a roll, the liquid crystal alignment film and the substrate are difficult to peel off. Therefore, it is possible to suppress a decrease in product yield when manufacturing a retardation film by a roll-to-roll method, and also from the viewpoint of productivity. Preferred.

The liquid crystal display element of the present invention can be effectively applied to a variety of devices, for example, it can be used in clocks, portable game machines, word processors, note type personal computers, car navigation systems, and video cameras. Various display devices such as camcorder, personal digital assistant (PDA), digital camera, mobile phone, smartphone, various monitors, LCD televisions, and information displays.

[Example]

Hereinafter, the present invention will be further specifically described using examples, but the present invention is not limited to these examples.

In the following examples and synthesis examples, the following methods were used to measure the weight average molecular weight Mw of the polymer, the fluorene imidization rate and epoxy equivalent weight, and the solution viscosity of the polymer solution. In addition, the compound represented by Formula X may be abbreviated as "compound X" below.

[Polymer average molecular weight Mw]

Mw is a polystyrene conversion value measured by GPC under the following conditions.

Column: Made by Tosoh, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / cm ²

[Polyhydrazone imidization rate of polymer]

A solution containing polyfluorene imine was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylsulfine. Tetramethylsilane was used as a reference substance at room temperature. measured at ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR). Based on the obtained ¹ H-NMR spectrum, the hydrazone imidization ratio was determined using the following formula (1).

醯 Imination ratio (%) = (1-A ¹ / A ² × α) × 100 ... (1)

(In formula (1), A ¹ is a peak area of NH-derived protons occurring near a chemical shift of 10 ppm, A ² is a peak area of other protons, and α is a precursor of other protons relative to the polymer. (Number ratio of one proton of NH group in (Polyamic acid))

[Epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solution viscosity of polymer solution]

Using an E-type rotary viscometer, the solution viscosity (mPa.s) of the polymer solution was measured at 25 ° C.

<Synthesis of a compound having a structure represented by the formula (1)>

[Example 1-1: Synthesis of compound (DA-1)]

Compound (DA-1) was synthesized according to the following scheme 1.

[Chemical 15]

[Example 1-2: Synthesis of Compound (DA-2)]

Compound (DA-2) was synthesized according to the following scheme 2.

[Example 1-3: Synthesis of compound (DA-3)]

The compound (DA-3) was synthesized according to the following scheme 3.

[Chemical 17]

[Example 1-4: Synthesis of compound (DA-4)]

Compound (DA-4) was synthesized according to the following scheme 4.

[Example 1-5: Synthesis of compound (DA-5)]

Compound (DA-5) was synthesized according to the following scheme 5.

The 4,4'-dihydroxydicyclohexyl group used in the reaction was synthesized using a mixture of structural isomers of the cis-isomer and the trans-isomer.

[Example 1-6: Synthesis of compound (DA-6)]

Compound (DA-6) was synthesized according to the following scheme 6.

[Example 1-7: Synthesis of compound (AN-4)]

Compound (AN-4) was synthesized according to the following scheme 7.

[Example 1-8: Synthesis of compound (DA-14)]

The compound (DA-14) was synthesized according to the following scheme 8.

[Example 1-9: Synthesis of compound (DA-15)]

The compound (DA-15) was synthesized according to the following scheme 9.

<Synthesis of Polymer>

[Example 2-1: Synthesis of Polymer (PA-1)]

9.62 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride (93 mol parts based on 100 mol parts of the total amount of diamine used in the synthesis), and 12.83 g of a compound (DA-1) as a diamine (50 mol parts based on 100 mol parts of the total amount of diamine used in the synthesis), and 1,5-bis (4-aminophenoxy) 7.55 g of pentanone (50 mol parts relative to 100 mol parts of the total amount of diamine used in the synthesis) was dissolved in 85 g of N-methyl-2-pyrrolidone (NMP) and γ -A mixed solvent of 85 g of butyrolactone (γ-butyrolactone (GBL)) was reacted at 30 ° C. for 6 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. After the recovered precipitate was washed with methanol, it was dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining a polyamic acid (hereinafter referred to as a polymer Compound (PA-1)) 28.3 g. The obtained polymer (PA-1) was prepared with a solvent composition of NMP: GBL = 50: 50 to 15% by weight, and the viscosity of the solution was measured. As a result, it was 561 mPa. s. In addition, when the polymer solution was left to stand at 20 ° C for 3 days, gelation did not occur, and storage stability was good.

[Examples 2-2 to 2-11 and Synthesis Example 1: Synthesis of Polyamic Acid]

In Example 2-1, except that the type and amount of the tetracarboxylic dianhydride and diamine used in the reaction were changed to those described in Table 1 below, a polymer was obtained in the same manner as in Example 2-1. Amino acid. In addition, regarding the tetracarboxylic dianhydride, the numerical value in Table 1 shows the usage ratio (mol%) with respect to the whole amount of the tetracarboxylic dianhydride used in the reaction, and regarding the diamine, the numerical value in Table 1 represents The proportion (mole%) of the total amount of diamine used in the reaction. The polymer solutions obtained in the examples were left to stand at 20 ° C. for 3 days, and as a result, no gelation occurred, and the storage stability was good.

The abbreviations of tetracarboxylic dianhydride and diamine in Table 1 are as follows.

(Tetracarboxylic dianhydride)

AN-1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

AN-2: pyromellitic dianhydride

AN-3: 2,3,5-tricarboxycyclopentylacetic dianhydride

AN-5: 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3 -Dione

AN-6: Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride

AN-7: 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione

(Diamine)

DA-7: 4,4'-bis (4-aminophenoxy) biphenyl

DA-8: 4,4'-diaminodiphenylmethane

DA-9: 1,5-bis (4-aminophenoxy) pentane

DA-10: 4,4'-diaminodiphenylamine

DA-11: 3,5-diaminobenzoic acid

DA-12: Cholesteryl 3,5-diaminobenzoate

DA-13: 4- (tetradecyloxy) benzene-1,3-diamine

In addition, the polymer (PA-9) is particularly suitable for a TN type liquid crystal display element, and the polymer (PA-10) is suitable for a VA type (vertical alignment type) liquid crystal display element.

[Example 2-12: Synthesis of polymer (PI-1)]

16.43 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride (98 mol parts based on 100 mol parts of the total amount of diamine used in the synthesis), and 18.21 g of amine compound (DA-1) (50 mol parts relative to 100 mol parts of the total amount of diamine used in synthesis) and 15.36 g (compared to the diamine used in synthesis) 100 mol parts (50 mol parts in total) was dissolved in 200 g of NMP, and the reaction was performed at room temperature for 6 hours. Then, add 250 g of NMP, 11.6 g of pyridine and 14.97 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 80 ° C for 5 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining polyfluorene imine (PI-1) having a fluorinated imidization ratio of about 68%. The obtained polyfluorene imine (PI-1) was prepared to 15% by weight using NMP. When the viscosity of this solution was measured, it was 893 mPa. s.

[Synthesis Example 2: Synthesis of Polyorganosiloxane (S-1)]

In a reaction vessel including a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and triethyl 10.0 g of amine was mixed at room temperature. Into this, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to form a thick transparent liquid. A polyorganosiloxane having an oxetanyl group is obtained. When ¹ H-NMR analysis was performed on the polyorganosiloxane having an oxetanyl group, it was found that a peak based on the oxetanyl group was obtained at a chemical shift (δ) = 3.2 ppm as a theoretical intensity. No side reactions of the oxetanyl group were generated. The epoxy equivalent of this oxetanyl-containing polyorganosiloxane was measured and found to be 186 g / equivalent.

Then, in a 100 mL three-necked flask, 9.3 g of the obtained polyorganosiloxane having oxetanyl group, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid, and UCAT 18X (commercial product) were introduced. First name, made by San-Apro (share) 0.10 g, and reacted for 12 hours while stirring at 80 ° C. After completion of the reaction, the reaction mixture was poured into methanol, and the resulting precipitate was recovered. The precipitate was dissolved in ethyl acetate to prepare a solution. After the solution was washed three times with water, the solvent was distilled off to remove As a white powder, 6.3 g of polyorganosiloxane (S-1) having an oxetanyl group and a cinnamic acid structure was obtained. About this polyorganosiloxane (S-1), the polystyrene-equivalent weight average molecular weight Mw measured by the gel permeation chromatography was 3,500.

<Preparation and Evaluation of Liquid Crystal Alignment Agent>

[Example 3-1: Friction alignment FFS liquid crystal display element]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-1) obtained in Example 2-1 as a polymer was dissolved in a mixed solvent containing γ-butyrolactone (GBL), NMP, and a butyl cellosolve (BC) ( In GBL: NMP: BC = 40: 40: 20 (weight ratio)), a solution having a solid content concentration of 3.5% by weight was prepared. This solution was filtered with a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-1).

(2) Evaluation of coating properties

The prepared liquid crystal alignment agent (R-1) was coated on a glass substrate using a spinner, and pre-baked on a hot plate at 80 ° C for 1 minute, and then a 200 ° C oven in which nitrogen was replaced in the library. After heating for 1 hour (post-baking), a coating film having an average film thickness of 1,000 Å was formed. This coating film was observed with a microscope with a magnification of 100 times and 10 times, and the film thickness unevenness and the presence or absence of pinholes were investigated. The evaluation was performed in such a manner that the film thickness was not observed even when observed with a microscope 100 times. Both coatings and pinholes were evaluated as "good", and at least any of film thickness unevenness and pinholes were observed with a 100x microscope, but film thickness was not observed with a 10x microscope Both the unevenness and the pinholes were evaluated as "applicable", and the case where at least any one of the film thickness unevenness and pinholes were clearly observed with a microscope at 10 times was evaluated as the "poor" coatingability. In this example, even if the film thickness unevenness and pinholes were not observed even with a microscope 100 times, the coating property was "good".

(3) Evaluation of friction resistance

The obtained coating film was subjected to 7 rubbing treatments using a friction machine having a cotton-rolled roll, at a roll rotation speed of 1000 rpm, a table moving speed of 20 cm / sec, and a gross press-in length of 0.4 mm. The foreign matter (fragment of the coating film) on the obtained substrate by friction removal was observed with an optical microscope, and the number of foreign matter in a region of 500 μm × 500 μm was calculated and measured. The evaluation is performed as follows: the case where the number of foreign objects is 3 or less is evaluated as abrasion resistance “good”, the case where 4 or more and 7 or less is evaluated as abrasion resistance “may”, and the case 8 or more It was evaluated as "bad" in abrasion resistance. As a result, the abrasion resistance of this coating film was "good".

(4) Manufacturing of FFS-type liquid crystal display elements using friction treatment

An FFS-type liquid crystal display element 10 shown in FIG. 1 was produced. First, a pair of a glass substrate 11a having an electrode pair on one side and a counter glass substrate 11b not provided with an electrode are formed as a pair, and the electrode pair is sequentially formed with a bottom electrode 15 without a pattern, and nitrided as an insulating layer 14. A silicon film, and an upper electrode 13 patterned into a comb-tooth shape, and then on the surface of the glass substrate 11a having a transparent electrode and the side facing the glass substrate 11b Above, the spinner was used to coat the liquid crystal alignment agent (R-1) prepared in (1), respectively, to form a coating film. Next, the coating film was pre-baked on a hot plate at 80 ° C for 1 minute, and then heated (post-baked) at 230 ° C for 15 minutes in an oven replaced with nitrogen in the storehouse to form an average film thickness of 1,000Å coating film. A schematic plan view of the upper electrode 13 used here is shown in FIGS. 2 (a) to 2 (b). 2 (a) is a plan view of the upper electrode 13, and FIG. 2 (b) is an enlarged view of a portion C1 surrounded by a dotted line in FIG. 2 (a). In this embodiment, the line width d1 of the electrodes is set to 4 μm, and the distance d2 between the electrodes is set to 6 μm. The structure of the driving electrode used is shown in FIG. In this case, the bottom electrode 15 operates as a common electrode and acts on the driving electrodes of all four systems, and the areas of the driving electrodes of the four systems become pixel regions, respectively.

Then, each surface of the coating film formed on the glass substrate 11 a and the glass substrate 11 b was subjected to a rubbing treatment using cotton to prepare a liquid crystal alignment film 12. In FIG. 2 (b), the direction in which the coating film formed on the glass substrate 11a is rubbed is indicated by an arrow. Next, one of a pair of substrates was coated with "XN-21-S" (trade name) (manufactured by Mitsui Chemicals Co., Ltd.) (manufactured by Mitsui Chemicals Co., Ltd.) as an outer edge of a surface having a liquid crystal alignment film on one of the substrates. The substrate 11a and the substrate 11b are bonded to each other with anti-parallel directions via a spacer having a diameter of 3.5 μm, and the sealant is hardened. Then, a liquid crystal MLC-6221 (manufactured by Merck) is injected between the pair of substrates from the liquid crystal injection port to form a liquid crystal layer 16. Furthermore, a polarizing plate (not shown in the figure) is attached to both outer surfaces of the substrate 11 a and the substrate 11 b so that the polarization directions of the two polarizing plates are orthogonal to each other, thereby producing a liquid crystal display element 10.

(5) Evaluation of liquid crystal alignment

For the manufactured FFS-type liquid crystal display element, a microscope was used to observe when turned on at a magnification of 50 times. ON (OFF) (apply. Release) the presence or absence of an abnormal region during a change in light and shade when the voltage is 5V. The evaluation was performed as follows: the case where no abnormal region was observed was evaluated as "good" in liquid crystal alignment, and the case where abnormal region was observed was evaluated as "poor" in liquid crystal alignment. In this liquid crystal display element, the liquid crystal alignment was "good".

(6) Evaluation of voltage holding ratio

For the FFS liquid crystal display device manufactured as described above, a voltage of 5 V was applied at 23 ° C for an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate after 167 milliseconds after the release was applied was measured ( VHR), with a result of 99.6%. In addition, VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(7) Uneven resistance around the sealant (resistance to frame unevenness)

The FFS liquid crystal display device manufactured as described above was stored at 25 ° C and 50% RH for 30 days, and then driven at an AC voltage of 5V to observe the lighting state. The evaluation was performed as follows: If no difference in brightness (blacker or whiter) was observed around the sealant, the evaluation of the frame unevenness resistance was "good". Although the difference in brightness was recognized, it was within 10 minutes after lighting. The disappearance of the brightness difference was evaluated as "OK", and the case where the brightness difference was visually recognized even after 10 minutes was evaluated as "Defective". As a result, the difference in brightness of the liquid crystal display element was not recognized, and the frame unevenness resistance was judged to be “good”.

(8) Pre-tilt angle characteristics

For the FFS liquid crystal display device manufactured as described above, the angle of inclination of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using He-Ne laser light, and this value was used as the pretilt angle θ. The crystal rotation method is based on Non-Patent Document 2 (TJ Cheffer et al., Journal of Applied Physics, J. Appl. Phys., Vol. 48, p. 1783 (1977)) and Non-Patent Document 3 (F. Nakano et al., "Japanese Journal of Applied Physics (JPN. J. Appl. Phys.)", Vol. 19, p. 2013 (1980)) Perform the method described.

A case where the pretilt angle θ was less than 1.0 ° was evaluated as a good pretilt angle evaluation, and a case where 1.0 ° or more was evaluated as a prefailure angle evaluation “bad”. As a result, the pretilt angle of the liquid crystal display element was 0.5 °, which was judged as a pretilt angle The characteristic is "good".

(9) Evaluation of contrast after driving stress (evaluation of AC afterimage characteristics)

The same operations as in (4) were performed except that the polarizing plates were not bonded to the outer surfaces of the substrate, and an FFS-type liquid crystal cell was produced. This FFS-type liquid crystal cell was driven by an AC voltage of 10V for 30 hours, and then a device having a polarizer and an analyzer disposed between the light source and the light amount detector was used to measure the minimum relative value represented by the following formula (2) Transmission (%).

Minimum relative transmittance (%) = (β-B ⁰ ) / (B ¹⁰⁰ -B ⁰ ) × 100 ... (2)

(In Equation (2), B ⁰ is the amount of light transmitted through a blank Nicol prism with a blank; B ¹⁰⁰ is the amount of light transmitted through a parallel Nicol prism with a blank; β is orthogonal (With a Nicols prism, the liquid crystal display element is sandwiched between the polarizer and the analyzer to minimize the amount of light transmitted)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. In the FFS liquid crystal display element, the smaller the black level in the dark state, the better the contrast. Those with a minimum relative transmittance of less than 1.0% were evaluated as "good" AC afterimage characteristics, those with 1.0% or more and less than 1.5% were evaluated as "good", and those with 1.5% or more were evaluated as "bad". As a result, the minimum relative transmittance of this liquid crystal display element was 0.2%, and the AC afterimage characteristics were judged to be “good”.

[Examples 3-2 to 3-8 and Comparative Example 1]

In Example 3-1, a liquid crystal alignment agent was prepared in the same manner as in Example 3-1 except that components of the kinds shown in Table 2 below were used as polymers, respectively, and an FFS-type liquid crystal display element was manufactured. For various evaluations. The evaluation results are shown in Table 2 below. In addition, in Table 2, the numerical value of the polymer amount represents a blending ratio (parts by weight) of each polymer to 100 parts by weight of the entire polymer component in the liquid crystal alignment agent.

As shown in Table 2, in Examples 3-1 to 3-8, the coating properties of the liquid crystal alignment agent, the abrasion resistance of the coating film, the liquid crystal alignment property, the voltage holding ratio, the unevenness resistance around the sealant, Both the pre-tilt angle characteristics and the AC afterimage characteristics are "good" or "possible" results, and various characteristics are balanced. In contrast, in the liquid crystal display element of Comparative Example 1, although the applicability and the abrasion resistance were evaluated as “allowable”, the voltage retention rate, unevenness resistance around the sealant, pretilt characteristics, and AC afterimage characteristics were all Worse results than the examples.

In addition, in the examples using the polymer (P) having a partial structure represented by the formula (1), the reason why the frame unevenness resistance becomes "good" or "possible" is not determined, but one reason is presumed. This is because the spacer structure (-R ^1- ) and the mesogenic structure (-W ^1- (R ² -W ² ) p-) in the polymer (P) are used to improve the hydrophobicity and decrease the water absorption rate, thereby The hydrolysis resistance is improved, and as a result, unevenness can be suppressed.

[Example 4-1: Photo-alignment FFS type liquid crystal display element]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-2) obtained in Example 2-2 as a polymer was dissolved in γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), and butyl cellosolve. In a mixed solvent (GBL: NMP: BC = 40: 40: 20 (weight ratio)), a solution having a solid content concentration of 3.5% by weight was prepared. This solution was filtered with a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-9).

(2) Evaluation of surface unevenness of coating film

The prepared liquid crystal alignment agent (R-9) was coated on a glass substrate using a spinner, pre-baked on a hot plate at 80 ° C for 1 minute, and then a 200 ° C oven with nitrogen replacement in the library was used. Medium heating (post-baking) for 1 hour, thereby forming a coating film having an average film thickness of 1,000 Å. The coating film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. The evaluation was performed as follows: a case with a surface roughness of less than 2.0 nm was evaluated as "good", a case with a size of 2.0 nm or more and less than 5.0 nm was evaluated as "good", and a case with 5.0 nm or more was evaluated as "bad". In this example, Ra is 0.9 nm, and the surface unevenness is "good".

(3) Evaluation of alignment

The obtained coating film was irradiated with polarized ultraviolet light of 300 J / cm ² including a bright line of 313 nm from a substrate normal direction using a Hg-Xe lamp and a Glan-Taylor prism, and subjected to an alignment treatment. The refractive index anisotropy (nm) of the substrate with the alignment film was measured using a liquid crystal alignment film inspection device (LayScan) manufactured by MORITEX. The evaluation was performed as follows: a case of 0.020 nm or more was evaluated as "good", a case of less than 0.020 nm and 0.010 nm or more was evaluated as "good", and a case of less than 0.010 nm was evaluated as "bad". As a result, this substrate was 0.036 nm, which was "good".

(4) Manufacturing of FFS-type liquid crystal display element using photo-alignment method

First, in the same manner as in (4) of Example 3-1, the liquid crystal alignment agent (R-9) prepared in (1) was applied to each surface of the pair of glass substrates 11a and 11b by a spinner, respectively. ) To form a coating film. Next, the coating film was pre-baked on a hot plate at 80 ° C. for 1 minute, and then heated (post-baked) at 230 ° C. for 15 minutes in an oven in which nitrogen was replaced in the warehouse to form an average film thickness of 1,000. Å coating film. Here, a schematic plan view of the upper electrode 13 used is shown in FIGS. 4 (a) to 4 (b). 4 (a) is a plan view of the upper electrode 13, and FIG. 4 (b) is an enlarged view of a portion C1 surrounded by a dotted line in FIG. 4 (a). In this embodiment, a substrate having an upper electrode with a line width d1 of the electrodes of 4 μm and a distance d2 between the electrodes of 6 μm is used. In addition, the upper electrode 13 uses the driving electrodes of the four systems of the electrode A, the electrode B, the electrode C, and the electrode D in the same manner as (4) of the embodiment 3-1 (see FIG. 3).

Then, on each surface of the coating film, a Hg-Xe lamp and a Glan Taylor prism were irradiated with polarized ultraviolet light 300 J / cm ² including a bright line of 313 nm from the substrate normal direction, thereby obtaining a pair of substrates having a liquid crystal alignment film. . At this time, the direction of the line segment from which the polarized ultraviolet rays are irradiated is set from the normal direction of the substrate and the polarized surface of the polarized ultraviolet rays is projected onto the substrate becomes the two-way arrows in FIGS. 4 (a) to 4 (b). The direction of the polarizing plane is set as the direction of the light, and then the light irradiation process is performed.

Then, an epoxy adhesive with an alumina ball having a diameter of 5.5 μm was added by screen printing on the outer periphery of the surface of one of the substrates having the liquid crystal alignment film, and then a pair of substrates The liquid crystal alignment film is face-to-face, and the substrates are superimposed and pressure-bonded so that the direction in which the polarized light polarized by the polarized ultraviolet rays is projected onto the substrate, and the adhesive is thermally hardened at 150 ° C. for 1 hour. Then, the substrate gap was filled with the liquid crystal "MLC-6221" manufactured by Merck from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Thereafter, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C. and then slowly cooled to room temperature.

Next, FPS liquid crystal display elements were manufactured by laminating polarizing plates on both surfaces of the substrate. At this time, one of the polarizing plates is attached in such a manner that its polarizing direction is parallel to the projection direction of the polarized ultraviolet rays of the liquid crystal alignment film facing the substrate, and the other polarizing plate is based on its polarizing direction and the previous polarizing plate. Attach the polarized light in an orthogonal manner.

(5) Evaluation of liquid crystal alignment

About the manufactured photo-alignment FFS-type liquid crystal display element, it carried out similarly to (5) of the said Example 3-1, and evaluated the liquid-crystal orientation. As a result, the liquid crystal alignment property was "good" in this liquid crystal display element.

(6) Evaluation of voltage holding ratio

With respect to the manufactured photo-alignment FFS-type liquid crystal display element, the voltage retention ratio (VHR) was measured in the same manner as in (6) of Example 3-1, and the voltage retention ratio was evaluated. As a result, the VHR was 99.4%.

(7) Resistance to frame unevenness

About the manufactured photo-alignment FFS-type liquid crystal display element, it carried out similarly to (7) of said Example 3-1, and evaluated the frame unevenness tolerance. As a result, no difference in brightness was recognized in this liquid crystal display element, and the resistance to frame unevenness was judged to be “good”.

(8) AC residual image evaluation

The AC afterimage evaluation was performed in the same manner as in (9) of Example 3-1. In the AC afterimage evaluation, the evaluation was performed using a liquid crystal cell without a polarizing plate in the same manner as in (9) of Example 3-1. As a result, the minimum relative transmittance was 0.1%, and the contrast characteristic was judged to be “good”.

[Example 4-2 and Example 4-3]

In Example 4-1, a liquid crystal alignment agent was prepared in the same manner as in Example 4-1 except that components of the kinds shown in Table 3 below were used as polymers, respectively, and an FFS-type liquid crystal display element was manufactured. For various evaluations. The evaluation results are shown in Table 3 below. In addition, in Table 3, the numerical value of the polymer amount represents a blending ratio (parts by weight) of each polymer to 100 parts by weight of the entire polymer component in the liquid crystal alignment agent.

[Example 5-1: retardation film]

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-2) obtained in Example 2-2 and 5 parts by weight of the polyorganosiloxane (S-1) obtained in Synthesis Example 2 were dissolved in a mixed solvent containing NMP and BC ( In NMP: BC = 50: 50 (weight ratio)), a solution having a solid content concentration of 5.5% by weight was prepared. This solution was filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-10).

(2) Manufacturing of retardation film

On one side of the TAC film as a substrate, the prepared liquid crystal alignment agent (R-10) was applied using a bar coater, and baked in an oven at 120 ° C. for 2 minutes to form a coating film having a film thickness of 100 nm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 10 mJ / cm ² including a bright line of 313 nm vertically from a substrate normal line using a Hg-Xe lamp and a Glan Taylor prism. Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered with a filter having a pore size of 0.2 μm, and then the polymerizable liquid crystal was coated on a coating film after light irradiation using a rod coater, so that A coating film of a polymerizable liquid crystal is formed. After baking in an oven whose temperature was adjusted to 50 ° C for 1 minute, the coating film surface was irradiated with a non-polarized ultraviolet light including 365 nm of bright light at a vertical direction of 1,000 mJ / cm ² using a Hg-Xe lamp to make it polymerizable. The liquid crystal is hardened to form a liquid crystal layer, thereby producing a retardation film.

(3) Evaluation of liquid crystal alignment

The retardation film produced in the above (2) was evaluated for the liquid crystal alignment by observing the presence or absence of an abnormal region using a visual inspection under a crossed Nicols prism and a polarizing microscope (magnification of 2.5 times). The evaluation is performed as follows: the case where the alignment is good under visual observation and no abnormal region is observed under a polarizing microscope is evaluated as the liquid crystal alignment "good"; the abnormal region is not observed under visual inspection, but under a polarizing microscope The case where the abnormal region was observed below was evaluated as "acceptable" for the liquid crystal alignment; the case where the abnormal region was observed under both the visual observation and the polarizing microscope was evaluated as "poor" for the liquid crystal alignment. As a result, this retardation film was evaluated as "good" in liquid crystal alignment.

(4) Adhesiveness

Using the retardation film produced in the above (2), the adhesion between the coating film formed of the liquid crystal alignment agent and the substrate was evaluated. First, using spacers with guides at equal intervals, using a cutter, a cut was made from the surface of the liquid crystal layer side of the retardation film to form 10 × 10 lattice patterns in a range of 1 cm × 1 cm. The depth of each cut is from the surface of the liquid crystal layer to the vicinity of the midpoint of the thickness of the substrate. Then, after the cellophane tape was adhered so as to cover the entire surface of the lattice pattern, the cellophane tape was peeled off. band. The cut portion of the grid pattern after peeling was observed by visual observation under a crossed Nicols prism, and adhesiveness was evaluated. The evaluation was performed as follows: The case where peeling was not confirmed at the portion along the cut-in line and the intersection portion of the lattice pattern was evaluated as "good" adhesion; the number of the lattice pattern was observed in the portion with respect to the entire lattice pattern. When the number of peeled grids is less than 15%, the adhesiveness is evaluated as “acceptable”; when the number of peeled grids in the part is 15% or more with respect to the total number of the grid patterns, the adhesion is evaluated as close adhesion. Sexual "bad". As a result, the retardation film was "good" in adhesion.

Claims (12)

A liquid crystal alignment agent comprising a polymer (P) having a partial structure represented by the following formula (1) in a main chain, In formula (1), W ¹ is a substituted or unsubstituted cyclohexyl group; W ² is a divalent cyclic group having a benzene ring, a cyclohexane ring, a cyclopentane ring or a pyridine ring as a ring skeleton; X ¹ is a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁰ CO- or * -CONR ^10- , where R ¹⁰ is a hydrogen atom or a carbon number of 1 to 3 "*" Represents a bonding bond with W ¹ ; X ² is -O-, * -COO-, * -OCO-, -CO-, * -NR ¹¹ CO- or * -CONR ^11- , where , R ¹¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with W ² ; R ¹ is a single bond, an alkanediyl group having 1 to 20 carbon atoms, and an olefin having 2 to 20 carbon atoms Diradical, alkanediyl group having 1 to 20 carbon atoms, or divalent group substituted with a part of hydrogen atoms of a part of hydrogen atoms of alkenediyl group having 2 to 20 carbon atoms, or alkanediyl group or carbon number having 1 to 20 carbon atoms A divalent group in which a part of the methylene group of 2 to 20 is substituted with -O- or -S-; R ² is a single bond, -O-, * -COO-, * -OCO-, -CO -, * -NR ¹² CO-, * -CONR ^12- , alkanediyl with 1 to 5 carbons, alkenediyl with 2 to 5 carbons, alkanediyl with 1 to 5 carbons or 2 to 5 carbons A divalent group in which a part of hydrogen atoms of the alkenyl group is substituted with a substituent, or an alkanediyl group having 1 to 5 carbon atoms or a carbon number of 2 to 5 A divalent group in which a part of the methylene group of 5 is substituted by -O- or -S-, wherein R ¹² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents the same as W ¹ A bonding bond; p is 1 or 2, the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamidate, and polyimide, and the polymer ( P) is a polymer obtained by polymerizing a monomer containing a compound represented by the following formula (d), In formula (d), X ³ and X ⁴ are each independently a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁴ CO- or * -CONR ^14- , where , R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with an aminophenyl group; R ³ is an alkyldiyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms Group, a phenyl group, a piperidine diyl group, an alkanediyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, a divalent group substituted with a substituent, or a carbon group having 1 to 2 carbon atoms A divalent group in which an alkylene group of 20 or an alkenyl group having 2 to 20 carbon atoms is substituted with -O- or -S-; R ⁴ and R ⁵ are each independently a halogen atom or carbon An alkyl or alkoxy group of 1 to 6; q is 0 or 1; m and n are each independently an integer of 0 to 4; when there are multiple R ⁴ and R ⁵ , multiple R ⁴ and R ⁵ may be the same or different, respectively; W ¹ , W ² , X ¹ , X ² , R ¹ , R ² and p are respectively synonymous with the formula (1). The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein R ¹ is an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, and an alkanediyl group having 1 to 20 carbon atoms. Or a divalent group in which a part of hydrogen atoms of 2 to 20 carbon diene groups are substituted with a substituent, or an alkylene group of 1 to 20 carbon atoms or a part of methylene group of 2 to 20 carbon atoms A divalent group substituted with -O- or -S-. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the polymer (P) is a polymer obtained by polymerizing a monomer containing a tetracarboxylic dianhydride, and contains a polymer selected from the group consisting of bicyclic [2.2.1 ] Heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tris Carboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3- Dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione , Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, cyclohexanetetracarboxylic dianhydride and pyromellitic dianhydride At least one of the group serves as the tetracarboxylic dianhydride. A liquid crystal alignment film is formed by using the liquid crystal alignment agent according to any one of claims 1 to 3 of the scope of patent application. A liquid crystal alignment film is obtained by applying a liquid crystal alignment agent as described in any one of claims 1 to 3 on a substrate to form a coating film, and irradiating the coating film with light. . A liquid crystal alignment film is obtained by coating the substrate with the liquid crystal alignment agent according to any one of claims 1 to 3 of the patent application scope and then performing a rubbing treatment. A method for manufacturing a liquid crystal alignment film, comprising: applying a liquid crystal alignment agent according to any one of claims 1 to 3 on a substrate to form a coating film; and performing a coating film on the substrate; A step of imparting alignment ability to the liquid crystal by light irradiation. A liquid crystal display element includes the liquid crystal alignment film according to any one of items 4 to 6 of the scope of patent application. A retardation film includes the liquid crystal alignment film according to item 4 or item 5 of the patent application scope. A method for manufacturing a retardation film, comprising: coating a substrate with a liquid crystal alignment agent according to any one of claims 1 to 3 to form a coating film; and applying light to the coating film. A step of irradiating; and a step of hardening a polymerizable liquid crystal on the coating film after light irradiation. A polymer comprising at least one polymer selected from the group consisting of polyamidic acid, polyamidate, and polyimide, and containing a compound represented by the following formula (d) Obtained by polymerizing monomers, In formula (d), W ¹ is a substituted or unsubstituted cyclohexyl group; W ² is a divalent cyclic group having a benzene ring, a cyclohexane ring, a cyclopentane ring or a pyridine ring as a ring skeleton; X ¹ , X ³ , and X ⁴ are each independently a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁰ CO-, or * -CONR ^10- , where R ¹⁰ Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, "*" represents a bonding bond with W ¹ or an aminophenyl group; X ² is -O-, * -COO-, * -OCO-, -CO-, * -NR ¹¹ CO- or * -CONR ^11- , wherein R ¹¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with W ² ; R ¹ is a single bond and carbon number 1 Alkyl di-20 to 20, alkenyl 2 to 20 carbon, alkyl 1 to 20 carbon or alkenyl 2 to 20 carbon atom Or a divalent group in which a part of the methylene group of an alkanediyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is substituted with -O- or -S-; R ² is a single bond, -O -, * -COO-, * -OCO-, -CO-, * -NR ¹² CO-, * -CONR ^12- , alkanediyl with 1 to 5 carbons, alkenediyl with 2 to 5 carbons, carbon A divalent alkadiyl group having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms which is partially substituted with a substituent Group, or a divalent group obtained by substituting a part of methylene groups of an alkylenediyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms by -O- or -S-, wherein R ¹² is a hydrogen atom Or an alkyl group having 1 to 3 carbon atoms, "*" represents a bonding bond with W ¹ ; R ³ is an alkyldiyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, phenylene, and piperidine Diradical, alkanediyl group having 1 to 20 carbon atoms, or divalent group substituted with a part of hydrogen atoms of a part of hydrogen atoms of alkenediyl group having 2 to 20 carbon atoms, or alkanediyl group or carbon number having 1 to 20 carbon atoms A divalent group in which part of the methylene group of 2 to 20 is substituted with -O- or -S-; R ⁴ and R ⁵ are each independently a halogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxy group; p is 1 or 2; q is 0 or 1; m and n are each independently an integer of 0 to 4; at ^4, a plurality of R ⁵ where R, R & lt plurality of ^4, R ⁵ may be They may be the same or different. A compound represented by the following formula (d), In formula (d), W ¹ is a substituted or unsubstituted cyclohexyl group; W ² is a divalent cyclic group having a benzene ring, a cyclohexane ring, a cyclopentane ring or a pyridine ring as a ring skeleton; X ¹ , X ³ , and X ⁴ are each independently a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NR ¹⁰ CO-, or * -CONR ^10- , where R ¹⁰ Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, "*" represents a bonding bond with W ¹ or an aminophenyl group; X ² is -O-, * -COO-, * -OCO-, -CO-, * -NR ¹¹ CO- or * -CONR ^11- , wherein R ¹¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and "*" represents a bonding bond with W ² ; R ¹ is a single bond and carbon number 1 Alkyl di-20 to 20, alkenyl 2 to 20 carbon, alkyl 1 to 20 carbon or alkenyl 2 to 20 carbon atom Or a divalent group in which a part of the methylene group of an alkanediyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is substituted with -O- or -S-; R ² is a single bond, -O -, * -COO-, * -OCO-, -CO-, * -NR ¹² CO-, * -CONR ^12- , alkanediyl with 1 to 5 carbons, alkenediyl with 2 to 5 carbons, carbon A divalent alkadiyl group having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms which is partially substituted with a substituent Group, or a divalent group obtained by substituting a part of methylene groups of an alkylenediyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms by -O- or -S-, wherein R ¹² is a hydrogen atom Or an alkyl group having 1 to 3 carbon atoms, "*" represents a bonding bond with W ¹ ; R ³ is an alkyldiyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, phenylene, and piperidine Diradical, alkanediyl group having 1 to 20 carbon atoms, or divalent group substituted with a part of hydrogen atoms of a part of hydrogen atoms of alkenediyl group having 2 to 20 carbon atoms, or alkanediyl group or carbon number having 1 to 20 carbon atoms A divalent group in which part of the methylene group of 2 to 20 is substituted with -O- or -S-; R ⁴ and R ⁵ are each independently a halogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxy group; p is 1 or 2; q is 0 or 1; m and n are each independently an integer of 0 to 4; at ^4, a plurality of R ⁵ where R, R & lt plurality of ^4, R ⁵ may be They may be the same or different.