KR20190137712A - Liquid crystal alignment agent for photo alignment, liquid crystal alignment film and liquid crystal display device using the same - Google Patents

Abstract

When applied to a liquid crystal display element with high stability with respect to light, the liquid crystal aligning film which implements higher contrast, and the liquid crystal aligning agent which can form such a liquid crystal aligning film are provided.
A liquid crystal aligning agent for photoalignment containing a polymer component having a structural unit containing a photoreactive structure, wherein the polymer component consists of a polymer obtained by polymerizing a monomer composition containing at least a first monomer and a second monomer, or a derivative thereof. The first monomer includes a photoreactive structure in a portion forming the structural unit of the polymer, and the portion forming the structural unit of the polymer causes a chemical reaction by heating, and the second monomer is a structure of the polymer. The part which forms a unit contains a photoreactive structure, and the part which forms the structural unit of a polymer does not produce the chemical reaction by heating.

Description

Liquid crystal aligning agent for photo-alignment, a liquid crystal aligning film, and a liquid crystal display element using the same TECHNICAL FIELD TECHNICAL FIELD

This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and the liquid crystal display element using the same. In detail, the liquid crystal aligning agent for forming the liquid crystal aligning film of a photo-alignment system (henceforth abbreviated as a photo-alignment film), the liquid crystal aligning film of the photo-alignment system formed using this liquid crystal aligning agent, and this liquid crystal aligning film It relates to a liquid crystal display device having a.

Liquid crystal display device, TN (Twisted Nematic) mode, Super Twisted Nematic (STN) mode, In-Plane Switching (IPS) mode, FFS (Fringe Field Switching) mode, Multi-domain Vertical Alignment (VA) mode Various drive systems are known. These liquid crystal display elements are applied to the image display apparatus of various electronic apparatuses, such as a television and a mobile telephone, and the development is progressing aiming at the further improvement of the display quality. Specifically, the improvement of the performance of the liquid crystal display element is achieved not only by the drive system and the improvement of the element structure but also by the constituent members used for the element. And among the structural members used for a liquid crystal display element, especially a liquid crystal aligning film is one of the important members regarding display quality, and in order to respond to the demand of the high quality of a liquid crystal display element, this liquid crystal aligning film is actively researched.

Here, a liquid crystal aligning film is provided in contact with the liquid crystal layer on a pair of board | substrates provided in the both sides of the liquid crystal layer of a liquid crystal display element, and orients the liquid crystal molecule which comprises a liquid crystal layer with a fixed regularity with respect to a board | substrate. It has a function to make. By using the liquid crystal aligning film with high liquid crystal aligning property, the liquid crystal display element with high contrast and the afterimage characteristic improved can be implement | achieved (for example, refer patent document 1 and 2).

In forming such a liquid crystal aligning film, the solution (varnish) which melt | dissolved polyamic acid, soluble polyimide, or polyamic acid ester in the organic solvent is mainly used now. In order to form a liquid crystal aligning film by these varnishes, after apply | coating a varnish to a board | substrate, a coating film is solidified by heating etc. and the polyimide-type liquid crystal aligning film is formed, and the orientation process suitable for the display mode mentioned above is performed as needed. As an orientation processing method, the rubbing method which rubs the surface of an alignment film with a cloth etc., and adjusts the direction of a polymer molecule, and irradiates an alignment film with ultraviolet-ray of linearly polarized light produces photochemical changes, such as photoisomerization and dimerization, and anisotropy to a film | membrane. The photo-alignment method for imparting is known. Among them, the photo-alignment method has a higher uniformity in orientation than the rubbing method and is a non-contact alignment treatment method, so that the film does not have scratches, or oscillation or static electricity. There exists an advantage of being able to reduce the cause which causes display defects of liquid crystal display elements, such as these.

As a liquid crystal aligning film using such a photo-alignment method, Patent Documents 1-5, for example, describe that a photo-alignment film having a large anchoring energy and a good liquid crystal alignment property is obtained by applying a technique of photoisomerization.

Japanese Unexamined Patent Publication No. 2010-197999 International Publication No. 2013/157463 Japanese Laid-Open Patent Publication 2005-275364 Japanese Unexamined Patent Publication No. 2007-248637 Japanese Unexamined Patent Publication No. 2009-069493 Japanese Patent Laid-Open No. 11-249142 International Publication No. 2013/161569 Japanese Laid-Open Patent Publication No. 2015-135464 International Publication No. 2017/119376

As mentioned above, the polyimide-type liquid crystal aligning film which gave the anisotropy by performing the orientation process by the photo-alignment method is known. However, the polyimide liquid crystal aligning film by the photo-alignment method is generally inferior in electrical characteristics compared with the polyimide liquid crystal aligning film by a rubbing process, and especially in the use situation where light from a backlight is irradiated for a long time, There exists a tendency which tends to inhibit the display quality of a display element. This is because a specific site (photoreactive group) introduced into the liquid crystal aligning film to generate a photochemical reaction, and in particular, an azo group easily absorbs light and generates radicals, thus the voltage retention of the liquid crystal display element (hereinafter referred to as VHR). Flagship) is considered to be reduced.

About this, the study which suppresses the fall of the voltage retention of a liquid crystal display element is studied by studying a layer structure etc., using the polyimide liquid crystal aligning film by a conventional optical orientation method (for example, patent documents 6- 9). However, even if such a configuration is employed in the liquid crystal alignment film, as long as the liquid crystal alignment film has a photoreactive group, a decrease in voltage retention due to the photodeterioration cannot be avoided, thereby realizing display quality that satisfies the recent demand. Things are difficult.

Therefore, the present inventors have found that when applied to a liquid crystal display element, it is difficult to cause a drop in voltage retention due to light irradiation, and to discover a configuration of a new liquid crystal alignment layer that realizes high contrast and clear contrast display in response to recent demands. The review was conducted. As a result, about the problem of voltage retention deterioration, it introduce | transduces the substituent which chemically reacts with a photoreactive group to the polymer of a liquid crystal aligning film, and reacts a photoreactive group with a substituent by heating, and converts it into the structure with high photostability by light irradiation, It has been found that the deterioration of the electrical characteristics due to this is significantly suppressed.

In Patent Documents 6 to 9, in order to suppress a decrease in the voltage retention of the liquid crystal display element, research has been carried out by paying attention to the configuration of the liquid crystal alignment film, but a structure which chemically reacts with a photoreactive group to the polymer of the liquid crystal alignment film is introduced and heated. There is no description of converting the photoreactive group into a structure stable to light by a chemical reaction by, and from these documents, the reduction of the voltage retention of the liquid crystal display element is suppressed by introducing such a structure. Cannot be predicted.

Under such circumstances, the inventors of the present invention provide a liquid crystal aligning film capable of forming a liquid crystal aligning film that has high stability to light and, when applied to a liquid crystal display element, realizes higher contrast, and such a liquid crystal aligning film. For the purpose of doing so, a polite review was conducted. Moreover, earnestly examined for the purpose of providing the liquid crystal display element which has high contrast and high contrast display, while maintaining a high voltage retention even if it exposes to the light from a backlight etc. for a long time.

As a result of earnestly examining in order to solve the said subject, the present inventors have a 1st monomer which has a photoreactive structure and a chemical reaction by heating, and has a photoreactive structure, and does not produce a chemical reaction by heating. By forming the liquid crystal aligning film using the polymer component synthesize | combined using the 2nd monomer which does not use for a liquid crystal aligning agent, in the liquid crystal display element to which the liquid crystal aligning film was applied, the fall of the voltage retention by light irradiation is suppressed remarkably, and contrast Was found to be high and a clear contrast display was realized. The present invention has been proposed based on these findings, and specifically has the following constitution.

[1] A liquid crystal aligning agent for photoalignment containing a polymer component having a structural unit containing a photoreactive structure, wherein the polymer component is a polymer obtained by polymerizing a monomer composition containing at least a first monomer and a second monomer; A derivative thereof, wherein the first monomer includes a photoreactive structure in a portion forming the structural unit of the polymer, and a portion in which the structural portion of the polymer forms a chemical reaction by heating. The second monomer has a photoreactive structure in a portion forming the structural unit of the polymer, and the portion forming the structural unit of the polymer does not cause a chemical reaction by heating. Liquid crystal aligning agent.

[2] The liquid crystal aligning agent for photoalignment according to [1], wherein the chemical reaction in the first monomer is a cyclization reaction.

[3] To [1] or [2], in which the first monomer includes a photoreactive structure having at least one of a structure represented by the following formula (a-1) and a structure represented by the following formula (a-2). The liquid crystal aligning agent for photoalignments described.

[Formula 1]

[In Formula (a-1), R ^<a> is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl carbon. Represents a niyl group;

In formula (a-2), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or Unsubstituted arylcarbonyl group;

In formulas (a-1) and (a-2), * represents a bonding position with a photoreactive group.]

[4] The liquid crystal aligning agent for photoalignment according to any one of [1] to [3], in which the first monomer includes a photoreactive structure having a photoisomerization structure or an optical freeze potential structure.

[5] The liquid crystal aligning agent for photoalignment according to any one of [1] to [4], in which the first monomer includes a photoreactive structure having a structure represented by the following Formula (1).

[Formula 2]

[In Formula (1), R <^1> and R <^2> respectively independently represents the group represented by a hydrogen atom, following formula (1-1), or following formula (1-2), At least one of R <^1> and R <^2> is , A group represented by the following formula (1-1) or the following formula (1-2);

* Represents a bonding position in the benzene ring, and is either one of a position capable of substituting with a hydrogen atom in one benzene ring or one of positions capable of being substituted with a hydrogen atom of the other benzene ring;

The hydrogen atom of the benzene ring may be substituted with a substituent.]

[Formula 3]

[In Formula (1-1) and Formula (1-2), R <^4> and R <^5> is respectively independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane oil group, a substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group;

* Represents a bonding position to the benzene ring in formula (1).]

[6] The polymer or derivative thereof obtained by polymerizing the monomer composition is at least one selected from polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer and polyamideimide,

The liquid crystal aligning agent for photoalignment in any one of [1]-[5] whose said 1st monomer is diamine represented by following formula (2).

[Formula 4]

[In Formula (2), R <^1> and R <^2> respectively independently represents the group represented by a hydrogen atom, a formula (1-1), or a formula (1-2), At least ^{1 of} R <^1> and R <^2> is a formula Group represented by (1-1) or formula (1-2);

R ⁶ and R ⁸ are each independently a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) -Or represent a single bond, and in R ⁶ and R ⁸ , one of -CH ₂ -or two non-adjacent groups of the linear alkylene group may be substituted with -O-;

R ⁷ and R ⁹ each independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond;

The bonding position of H ₂ NR ⁷ -R ⁶ -is any one of positions replaceable with a hydrogen atom in one benzene ring, and the bonding position of H ₂ NR ⁹ -R ⁸ -is bonded to the other benzene ring. Any of hydrogen atom and a position which can be substituted;

The hydrogen atom in the benzene ring may be substituted with a substituent.]

[Formula 5]

[In Formula (1-1) and Formula (1-2), R <^4> and R <^5> is respectively independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane oil group, a substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group;

* Represents a bonding position to the benzene ring in formula (2).]

[7] The liquid crystal aligning agent for photoalignment according to [5] or [6], wherein R ¹ is a group represented by Formula (1-1) and R ² is a hydrogen atom.

[8] The liquid crystal aligning agent for photoalignment according to [7], wherein R ⁴ is a hydrogen atom or a substituted or unsubstituted alkyl group.

[9] The liquid crystal aligning agent for photoalignment according to [6], wherein the diamine represented by the formula (2) is a diamine represented by any one of the following formulas (3) to (6).

[Formula 6]

[In formula (3)-(6), R <^4> is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or substituted or unsubstituted independently A substituted arylcarbonyl group;

The hydrogen atom of the benzene ring may be substituted with a substituent;

In formulas (5) and (6), R ⁵ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted group. Substituted arylcarbonyl group is shown.]

[10] The diamine represented by the formula (2) is represented by the following formulas (3-1) to (3-9), formulas (4-1) to (4-9), formulas (5-1), The liquid crystal aligning agent for photoalignment as described in [6] or [9] which is a diamine represented by any of Formula (5-2), Formula (6-1), and Formula (6-2).

[Formula 7]

[Formula 8]

[Wherein Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, ⁱ Pr represents an isopropyl group, Bu represents a butyl group, and ^t Bu represents a t-butyl group, respectively.]

[11] The liquid crystal aligning agent for photoalignment according to any one of [1] to [10], in which the second monomer includes a photoreactive structure having a photoisomerization structure or a photodimerization structure.

[12] The liquid crystal aligning agent for photoalignment according to [11], in which the second monomer contains a photoreactive structure having a photoisomerization structure.

[13] The liquid crystal aligning agent for photoalignment according to any one of [6] to [12], wherein the second monomer is a diamine.

[14] The liquid crystal aligning agent for photoalignment according to any one of [6] to [13], in which the monomer composition contains tetracarboxylic dianhydride.

[15] The compound according to any one of [1] to [14], wherein a compounding amount of the first monomer in the monomer composition is 15 to 85 mol% based on the total moles of the first monomer and the second monomer. Liquid crystal aligning agent for photoalignment.

[16] the liquid crystal aligning agent further contains a second polymer component,

The liquid crystal aligning agent for photoalignment according to any one of [1] to [15], wherein the second polymer component is composed of a polymer obtained by polymerizing a monomer composition comprising a monomer not containing a photoreactive structure or a derivative thereof.

[17] The polymer or derivative thereof obtained by polymerizing the monomer composition is at least one member selected from polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer and polyamideimide. ] Liquid crystal aligning agent for photoalignments.

[18] The liquid crystal aligning agent for photoalignment according to any one of [1] to [17], which is used for formation of a liquid crystal alignment film of a transverse electric field type liquid crystal display element.

[19] A liquid crystal alignment film formed of the liquid crystal aligning agent for photoalignment according to any one of [1] to [18].

[20] A liquid crystal display device having the liquid crystal alignment film as described in [19].

[21] An alignment step of irradiating polarized light to the film made of the liquid crystal aligning agent for photoalignment according to any one of [1] to [18] to impart anisotropy, and a heating and baking step of heating and baking the film provided with anisotropy. The formation method of the liquid crystal aligning film which has a cyclization reaction in the photoreactive structure of the polymer component which the said liquid crystal aligning agent for photo-alignment contains, and reduces a photoreactive group at the time of the said heating baking process.

[22] The method for forming a liquid crystal alignment film according to [21], wherein the heating and firing step is performed in a step of two or more steps by changing the heating temperature.

[23] A method for producing a liquid crystal display element, wherein the liquid crystal alignment film is formed using the method for forming a liquid crystal alignment film according to [21] or [22].

[24] The method for producing a liquid crystal display element according to [23], wherein the liquid crystal display element to be manufactured is a transverse electric field type liquid crystal display element.

[25] A polyamic acid or derivative thereof formed by polymerizing a monomer composition containing a first monomer, a second monomer, and a non-photoreactive tetracarboxylic dianhydride,

The first monomer is a diamine represented by the following formula (2),

The second monomer is formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula ( IV-3), formula (V-1), formula (V-2), formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1), formula (VIII -1) and said polyamic acid or its derivative which is a compound represented by either of formula (VIII-2).

[Formula 9]

[In Formula (2), R <^1> and R <^2> respectively independently represents the group represented by a hydrogen atom, a formula (1-1), or a formula (1-2), At least ^{1 of} R <^1> and R <^2> is a formula Group represented by (1-1) or formula (1-2);

R ⁶ and R ⁸ are each independently a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) -Or represent a single bond, and in R ⁶ and R ⁸ , one of -CH ₂ -or two non-adjacent groups of the linear alkylene group may be substituted with -O-;

R ⁷ and R ⁹ each independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond;

The bonding position of H ₂ NR ⁷ -R ⁶ -is any one of positions replaceable with a hydrogen atom in one benzene ring, and the bonding position of H ₂ NR ⁹ -R ⁸ -is bonded to the other benzene ring. Any of hydrogen atom and a position which can be substituted;

The hydrogen atom in the benzene ring may be substituted with a substituent.]

[Formula 10]

[In Formula (1-1) and Formula (1-2), R <^4> and R <^5> is respectively independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane oil group, a substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group;

* Represents a bonding position to the benzene ring in formula (2).]

[Formula 11]

[Formula 12]

(Formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (IV-3), Formula (V-1), Formula (V-2), Formula (V-3), Formula (VI-1), Formula (VI-2), Formula (VII-1), Formula (VIII-1), and In formula (VIII-2), the group in which the bond position is not fixed to any one of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary, and in formula (IV-3), r is an integer from 1 to 10, in the formula (V-2), r ⁶ independently represent the _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently 0 to 2 an integer, formula according to (V-3), ring a and ring B is at least one is each independently selected from the just recalled cyclic hydrocarbon, a condensed polycyclic hydrocarbon, and clothing, R ¹¹ is 1 to 20 carbon atoms straight chain alkylene, -COO-, -OCO-, -NHCO-, -CONH- , -N (CH 3) CO-, or -CON (CH ₃₎ - represents the, R ¹² are, of 1 to 20 carbon atoms Straight chain alkylene, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, Or -CON (CH ₃ )-, and in R ¹¹ and R ¹² , one or two of -CH ₂ -of the linear alkylene may be substituted with -O-, and R ⁷ to R ¹⁰ are each -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH are independently represented, b to e are each independently an integer of 0 to 4, and in formula (VII-1), R ⁴ and R ⁶ is independently C1-C20 linear alkylene, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ )-, or in the shown, R ⁴ and R ⁶ bond, -CH ₂ of the linear alkylene-two not one of or adjacent are optionally substituted by -O-, R ⁵ and R ⁷ is a monocyclic hydrocarbon independently Hydrogen, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond.)

[26] The second monomer may be represented by the following Formula (V-2-1), Formula (V-3-2), Formula (VI-2-1), Formula (VII-1-1) and Formula (VII-1). The polyamic acid or its derivative as described in [25] which is a compound represented by any of -2).

[Formula 13]

[27] The polyamic acid according to [25] or [26], comprising at least one selected from polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide derivative.

By using the liquid crystal aligning film formed with the liquid crystal aligning agent for photoalignment of this invention, the fall of the voltage retention with light irradiation is suppressed, and a contrast is high and a liquid crystal display element with a clear contrast display can be implement | achieved.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail. Although description of the element | module described below may be made | formed based on typical embodiment and a specific example, this invention is not limited to such embodiment. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

Liquid crystal aligning agent for photo-alignment

When the film | membrane is formed on the board | substrate, "the liquid crystal aligning agent for optical orientation" in this invention means the liquid crystal aligning agent which can provide anisotropy by irradiating a polarization, and is simply a "liquid crystal aligning agent" in this specification. May be called. The liquid crystal aligning agent (liquid crystal aligning agent) for photoalignment of this invention is used for formation of a liquid crystal aligning film.

The liquid crystal aligning agent for photoalignments of this invention is a liquid crystal aligning agent for photoalignments containing the polymer component which has a structural unit containing a photoreactive structure, Comprising: The polymer component contains a 1st monomer and a 2nd monomer at least. It consists of a polymer obtained by superposing | polymerizing a monomer composition or its derivative (s). Of the monomers contained in the monomer composition, the first monomer includes a photoreactive structure in a portion that forms the structural unit of the polymer, and a portion in which the portion that forms the structural unit of the polymer causes a chemical reaction by heating. The second monomer includes a photoreactive structure in a portion forming the structural unit of the polymer, and a portion in which the structural unit of the polymer does not cause a chemical reaction by heating.

The "photoreactive structure" in this invention means the atomic group whose structure changes by irradiation of light. Such photoreactive structure usually has a specific site (photoreactive group) which absorbs light and causes chemical change, and the structure changes due to chemical change of the photoreactive group. In the following description, the change in photoreactive structure by such light irradiation is called photochemical change. As a specific example of photochemical change, photoisomerization, an optical freeze potential, etc. are mentioned. Although the wavelength of the light which produces a structural change in a photoreactive structure is not specifically limited, It is preferable that it is 150-800 nm, It is more preferable that it is 200-400 nm, It is more preferable that it is 300-400 nm. Moreover, it is preferable that the light irradiation intensity | strength required for generating a structural change in a photoreactive structure is 0.05-20 J / cm <^2> .

The "first monomer" in this invention is a molecule | numerator of the compound which superposes | polymerizes with the other molecule | numerator contained in a monomer composition, and forms a polymer, and contains the photoreactive structure in the part which forms the structural unit of a polymer, and the polymer The part which forms the structural unit of will generate a chemical reaction by heating. In addition, the "second monomer" in this invention is a molecule | numerator of the compound which superposes | polymerizes with the other molecule | numerator contained in a monomer composition, and forms a polymer, and includes the photoreactive structure in the part which forms the structural unit of a polymer, and The part which forms the structural unit of the polymer does not cause a chemical reaction by heating.

Here, the "part which forms the structural unit of a polymer" in a 1st monomer and a 2nd monomer is a polymerizable group (it reacts with the polymerizable group of another molecule at the time of polymerization, and forms a bond in the molecule | numerator which comprises a monomer). A group of atoms except for (end group), in other words, remains after the polymerization, and means a part constituting the structural unit of the polymer. In the following description, "the part which forms the structural unit of a polymer" may be called "structural unit formation part."

Moreover, in this invention, when the film | membrane which consists of a polymer of this monomer is left still at 200 degreeC for 10 minutes among the monomer containing a photoreactive structure in a structural unit formation part, the maximum in the range of 200 nm-900 nm of the said photoreactive structure. The monomer in which the transmittance at the absorption wavelength changes by 20% or more from the transmittance before standing is assumed to correspond to a monomer, ie, a "first monomer", in which the structural unit forming portion causes a chemical reaction by heating, and the change in transmittance due to such heating Monomer which does not represent "a second monomer" shall be assumed.

Although the chemical reaction which arises by heating in a 1st monomer is not specifically limited, It is preferable that it is a reaction which converts the photoreactive group of a photoreactive structure into the structure which does not have photoreactivity, and a photoreactive group and the molecule | numerator of the said monomer are It is especially preferable that it is a cyclization reaction with another group which has. Thereby, the linearity of a polymer becomes high and a liquid crystal aligning film with higher orientation can be obtained.

The "polymer component" in the present invention is composed of a polymer obtained by polymerizing a monomer composition containing at least a first monomer and a second monomer or a derivative thereof, usually a molecule of a plurality of polymers or a molecule of a plurality of derivatives. It is an aggregate consisting of. The "polymer" which comprises a polymer component contains the structural unit derived from a 1st monomer, and the structural unit derived from a 2nd monomer because the monomer composition which is a raw material contains a 1st monomer and a 2nd monomer. However, one part of the polymer which comprises a polymer component may contain only one of the structural unit derived from a 1st monomer, and the structural unit derived from a 2nd monomer. In the following description, the structural unit derived from a 1st monomer is called "a 1st structural unit" among the structural units which comprise a polymer, and the structural unit derived from a 2nd monomer is called "2nd structural unit."

The "derivative" of the polymer in the present invention means that a part of the polymer obtained by polymerizing the monomer composition is substituted with another atom or atomic group. It is preferable that derivative | guide_body is substituted by another atom or the atomic group in parts other than the 1st structural unit and the 2nd structural unit of a polymer.

In the polymer obtained by polymerizing a monomer composition or its derivative, the structural unit (first structural unit) derived from a 1st monomer contains the "photoreactive structure" which the structural unit formation part of the 1st monomer contained, and It is a structural unit which causes a chemical reaction by heating, and the structural unit (2nd structural unit) derived from a 2nd monomer contains the "photoreactive structure" which the structural unit formation part of the 2nd monomer contained, It is a structural unit which does not produce a chemical reaction. That is, the "polymer component" contained in the liquid crystal aligning agent of the present invention includes a photoreactive structure, further includes a first structural unit and a photoreactive structure that cause a chemical reaction by heating, and further perform a chemical reaction by heating. It can also be called aggregate of the polymer containing the 2nd structural unit which does not produce | generate, or its derivative (s).

The liquid crystal aligning agent (liquid crystal aligning agent) for photoalignment of this invention is used for formation of a liquid crystal aligning film. In order to form a liquid crystal aligning film by the liquid crystal aligning agent of this invention, after apply | coating a liquid crystal aligning agent to a board | substrate, for example, forming a film | membrane, the polarization for photo-alignment is irradiated. Thus, in the polymer main chain (the main chain of the polymer constituting the polymer component or derivative thereof) substantially parallel to the polarization direction, the photoreactive structures of the first structural unit and the second structural unit selectively cause a photochemical reaction to have a structure Is changed, and the component in the polymer backbone that is directed in a particular direction (the result of the structural change) becomes dominant. That is, the polymer main chain which comprises a film | membrane orients in a specific direction, and it will be in the state to which anisotropy was provided. Thereafter, this photo-aligned film is heated and baked to form a solid liquid crystal alignment film. In this heat firing, in the present invention, the first structural unit of the polymer or its derivatives undergoes a chemical reaction, and the photoreactive group is lost, and the number of photoreactive groups decreases or the photoreactive group does not exist in the entire film. . For this reason, the formed liquid crystal aligning film hardly generate | occur | produces a radical even when exposed to strong light, and shows high stability with respect to light. In addition, at this time, since the second structural unit maintains the structure immediately after the photoalignment treatment without causing a chemical reaction, the structure effectively contributes to the anisotropy of the polymer main chain. Thereby, the formed liquid crystal aligning film exhibits favorable liquid crystal alignability in addition to having high stability with respect to light. For this reason, in the liquid crystal display element in which the liquid crystal aligning film was formed by this liquid crystal aligning agent, while maintaining high voltage retention even if it exposes to the light from a backlight for a long time, contrast is high and clear contrast display can be performed.

Below, the polymer component which the liquid crystal aligning agent of this invention contains, the monomer composition used as the raw material of this polymer component, the polymer which polymerizes this monomer composition, or its derivative (s) is demonstrated in detail.

<Polymer component>

The liquid crystal aligning agent of this invention contains the polymer component which has a structural unit containing a photoreactive structure. When a photo-alignment process is given to the film | membrane of a liquid crystal aligning agent, a polymer component orientates the polymer main chain in a specific direction and expresses anisotropy. In the following description, the "polymer component which has a structural unit containing a photoreactive structure" may be called "photoreactive polymer component."

The photoreactive polymer component is composed of a polymer obtained by polymerizing a monomer composition containing at least a first monomer and a second monomer or a derivative thereof, and the structural unit containing the photoreactive structure is a first monomer contained in the monomer composition. And a second monomer.

The liquid crystal aligning agent may include one type of polymer component obtained from a single monomer composition, or may include two or more types of polymer components having different compositions of the monomer composition. Moreover, the liquid crystal aligning agent may contain both the polymer component which consists of a polymer which superposes | polymerizes a monomer composition, and the polymer component which consists of derivatives of this polymer.

Hereinafter, the monomer composition used as a raw material of a polymer component is demonstrated.

Monomer Composition

The monomer composition used by this invention is a composition containing at least a 1st monomer and a 2nd monomer, may be comprised only by a 1st monomer and a 2nd monomer, and may contain the other monomer.

[First monomer]

A 1st monomer is a compound which includes a photoreactive structure in the part (structural unit formation part) which forms the structural unit of a polymer, and the part which forms the structural unit of the polymer produces a chemical reaction by heating. In this invention, the structural unit formation part of this 1st monomer is introduce | transduced into a polymer, and includes the photoreactive structure, and forms the 1st structural unit which produces a chemical reaction by heating. The first monomer contained in the monomer composition may be only one kind or two or more kinds.

In addition, in the following description, the monomer "expresses a photoreactive structure in a structural unit formation part" may be expressed as "photoreactive", for example, the monomer containing a photoreactive structure in a "structural unit formation part". "May be called" photoreactive monomer. " Moreover, the characteristic which a structural unit formation part raises a chemical reaction by heating may be called "thermal reactivity".

The structural unit formation part of a 1st monomer may consist only of a photoreactive structure, and may contain another structure. The number of photoreactive structures which a structural unit formation part contains may be one, or two or more may be sufficient as it. When a structural unit formation part contains two or more photoreactive structure, these photoreactive structures may mutually be same or different.

It is preferable that the structural unit formation part of a 1st monomer has a photoreactive structure containing at least one of the structure represented by a following formula (a-1), and the structure represented by a following formula (a-2). Thereby, the polymer which comprises at least one of the structure represented by a formula (a-1) and the structure represented by a formula (a-2) as a polymer formed by superposing | polymerizing a monomer composition can be obtained. In the liquid crystal aligning agent containing such a polymer or its derivative as a polymer component, when the coating film of this liquid crystal aligning agent is heated, the substituent and the photoreactive group of the benzene ring in each formula cyclize, and the photoreactive group is lost, and the whole film | membrane is lost. The number of photoreactive groups decreases or no photoreactive group is present. As a result, the liquid crystal aligning film stable with respect to light can be formed.

Here, the structural unit formation part may include only the structure represented by Formula (a-1), may include only the structure represented by Formula (a-2), and the structure and formula ( Both of the structures shown by a-2) may be included. Moreover, the number of structures represented by Formula (a-1) and the number of structures represented by Formula (a-2) which a structural unit formation part contains may respectively be one, or two or more may be sufficient as it. When the structural unit formation part contains two or more structures represented by Formula (a-1), those structures may mutually be same or different, and the structural unit formation part contains two or more structures represented by Formula (a-2). When doing this, these structures may mutually be same or different.

[Formula 14]

In formula (a-1), R ^a represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. In formula (a-2), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or Unsubstituted arylcarbonyl group is shown. R ^b and R ^c may be the same as or different from each other. In Formula (a-1) and Formula (a-2), * is a coupling | bonding position with a photoreactive group. * May be directly bonded to the photoreactive group, or may be connected to the photoreactive group via a divalent group.

In the formula (a-1), the alkyl group of the R is ^a straight-chain, and is may be either branched, cyclic. Preferable carbon number of an alkyl group is 1-10, More preferably, it is 1-6, More preferably, it is 1-4, More preferably, it is 1-3. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 1-ethylbutyl group, etc. can be illustrated.

Alkanoyl group in R ^a, straight chain, and may be either branched, cyclic. Preferable carbon number of an alkanoyl group is 1-10, More preferably, it is 1-6, More preferably, it is 1-2, More preferably, it is 1. Specific examples of the alkane oil group include a methane oil group, an ethane oil group, a propane oil group, an isopropane oil group, a butan oil group, an isobutan oil group, a sec-butan oil group, a tert-butan oil group, a pentane oil group, Isopentane oil group, neopentane oil group, tert-pentane oil group, 1-methyl butane oil group, 1-ethyl propane oil group, hexane oil group, isohexane oil group, 1-methyl pentane oil group, 1-ethyl view Tan oil group etc. can be illustrated.

Alkoxycarbonyl group, a straight chain, and may be either branched, cyclic in the R ^a. Preferable carbon number of an alkoxycarbonyl group is 1-10, More preferably, it is 1-6, More preferably, it is 1-3, More preferably, it is 2. Specific examples of the alkoxycarbonyl group include methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyl Oxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, tert-pentyloxycarbonyl group, 1-methylbutyloxycarbonyl group, 1-ethylpropyloxycarbonyl group, hexyloxycarbonyl group, iso Hexyloxycarbonyl group, 1-methylpentyloxycarbonyl group, 1-ethyl butyloxycarbonyl group, etc. can be illustrated.

The aryl group of the arylcarbonyl group in R ^a may be monocyclic or may be a condensed ring. Preferable carbon number of an aryl group is 6-22, More preferably, it is 6-14, More preferably, it is 6-10. As a specific example of an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, etc. can be illustrated. As a specific example of an arylcarbonyl group, a phenylcarbonyl group, a 1-naphthylcarbonyl group, etc. can be illustrated.

The alkyl group, the alkanoyl group, the alkoxycarbonyl group, and the arylcarbonyl group in R ^a may each be substituted with a substituent. As a substituent, a hydroxyl group, an amino group, a halogeno group, etc. are mentioned.

Among these, from the point which can improve the performance of the liquid crystal aligning film finally manufactured, it is preferable that R ^<a> is a methyl group, an ethyl group, a propyl group, a hydrogen atom, a methanoyl group, and a phenyl group.

In Formula (a-2), description of the alkyl group, the alkanoyl group, the alkoxycarbonyl group, the arylcarbonyl group, and the substituent which can be substituted by these groups in R <^b> and R <^c> is mentioned above. The description of the alkyl group, the alkanoyl group, the alkoxycarbonyl group, the arylcarbonyl group, and the substituent which can be substituted by these groups in R ^<a> of Formula (a-1) can be referred to.

In formula (a-1) and formula (a-2), although the photoreactive group couple | bonded with * is not specifically limited, Azo group, a 1,2-ethenediyl group, a 1, 2- ethanediyl group, an imino group , A carbonyl group, an oxycarbonyl group, and the like.

The hydrogen atom of each benzene ring in Formula (a-1) and Formula (a-2) may be substituted by the substituent. About the preferable range and specific example of a substituent, in the following formula (1), the preferable range and specific example of the substituent which can be substituted by a benzene ring can be referred.

It is preferable that the photoreactive structure which has at least one of the structure represented by Formula (a-1) and the structure represented by Formula (a-2) comprises the azobenzene structure, and it is more preferable that it is a structure represented by following formula (1). Do. When ultraviolet rays are irradiated to the structure represented by the following formula (1), trans-cis isomerization of azo groups occurs and the direction of the polymer main chain changes. Thereby, the liquid crystal aligning film which the polymer main chain oriented in the specific direction is obtained.

[Formula 15]

In Formula (1), R <^1> and R <^2> respectively independently represents group represented by a hydrogen atom, Formula (1-1), or Formula (1-2), At least one of R <^1> and R <^2> is a formula ( 1-1) or group represented by Formula (1-2). One of R ¹ and R ² may be sufficient as the group represented by Formula (1-1) or Formula (1-2) in R ¹ and R ² . When both R ¹ and R ² are groups represented by formula (1-1) or formula (1-2), those groups may be the same as or different from each other.

* Represents the bonding position with respect to the structure of both sides of the structure represented by Formula (1), and the hydrogen atom in any one of the position and the position which can be substituted by the hydrogen atom in the one benzene ring, or the other benzene ring And one of the positions which can be substituted.

[Formula 16]

In formula (1-1), R <^4> is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl. Group. In formula (a-2), R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or Unsubstituted arylcarbonyl group is shown. R <^4> and R <^5> may mutually be same or different. In Formula (1-1) and Formula (1-2), * represents a bonding position with respect to each benzene ring in Formula (1). Description of the alkyl group, the alkanoyl group, the alkoxycarbonyl group, the arylcarbonyl group in R <^4> and R <^5> , the substituent which can be substituted by these groups, a preferable range, and a specific example are R of said Formula (a-1) ^The description, preferable ranges, and specific examples of the alkyl group, alkanoyl group, alkoxycarbonyl group, arylcarbonyl group and substituents which may be substituted with these groups in a can be referred to.

The hydrogen atom of the benzene ring in Formula (1) may be substituted by the substituent. Preferred examples of the substituent include an alkyl group, an alkoxy group, a halogenated alkyl group, a halogeno group, and a carboxyalkyl group. The alkyl group may be any of linear, branched or cyclic. Preferable carbon number of an alkyl group is 1-4, More preferably, it is 1-2. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Preferable carbon number of an alkoxy group is 1-4, More preferably, it is 1-2. As a specific example of an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- butoxy group, etc. can be illustrated. As a specific example of a halogenated alkyl group, a trifluoromethyl group etc. can be illustrated. As a specific example of a halo geno group, a fluoro group, a chloro group, a bromo group, an iodo group, etc. can be illustrated. As a specific example of a carboxyalkyl group, a carboxy methyl group, a carboxyethyl group, etc. can be illustrated.

The photoreactive structure introduced into the structural unit formation part of a 1st monomer can mention photoisomerization structures, such as a stilbene structure and an acylhydrazone structure, optical freeze potential structures, such as a phenyl ester structure, in addition to said azobenzene structure. have. The photoreactive structure contained in the structural unit formation part of a 1st monomer becomes like this. Preferably, it is a photoisomerization structure, such as an azobenzene structure, a stilbene structure, an acylhydrazone structure, Especially, it is especially preferable that it is an azobenzene structure.

(Chemical reaction by heating of structural unit having photoreactive structure)

The structural unit formation part of the 1st monomer used by this invention has a photoreactive structure, and produces a chemical reaction by heating. As a result, in the polymer or derivative thereof in which the structural unit forming unit is introduced as the first structural unit, the anisotropy is imparted by the photoalignment method (after generating the structural change in the photoreactive structure by light irradiation), and then heating is performed. The photoreactive structure can be converted into a structure stable to light.

The chemical reaction by heating to the structure which has a photoreactive structure and introduce | transduces a substituent at the specific position of an azobenzene structure, an acylhydrazone structure, or a phenyl ester structure as an example of a structure which has a photoreactive structure below and also produces a chemical reaction by heating The mechanism by which the photoreactive group is lost by the reaction will be described. The structure represented by following formula (A-1) is contained in the structure represented by Formula (1), and is more preferable as a photoreactive structure introduce | transduced into a 1st monomer. Moreover, the structure represented by following formula (B-1), (C-1), or (D-1) can also be used suitably as a photoreactive structure introduce | transduced into a 1st monomer.

(A) Cyclic Reaction of Azobenzene Structure: 5-membered Ring Formation

In the first structural unit having an azobenzene structure represented by the azobenzene structure, that is, the formula (A-1) having an R ^1A substituent on the ortho to the benzene ring azo group on one side, as shown in the following reaction formula, by heating, azo group Reacts with substituent R ^1A of the benzene ring to form an indazole ring, and the azo group is lost. For details of this reaction, see New J. chem., 1999, 23, 1223-1230.

[Formula 17]

In Formula (A-1), R ^1A represents a group represented by Formula (A-1-1) or Formula (A-1-2). In formula (A-1-1) and formula (A-1-2), R ^4A and R ^5A each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, and a substituent. Or an unsubstituted alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group. R ^4A and for a description of the preferred range, specific examples of R ^5A, in the alkyl group in R ^a in the formula (a-1) above, alkanoyl, alkoxycarbonyl group, aryl carbonyl group, and groups thereof may be substituted See description, preferred ranges, and embodiments of the substituents.

(B) Cyclic Reaction of Azobenzene Structure: 6-membered Ring Formation

In the first structural unit having an azobenzene structure represented by the azobenzene structure, that is, the formula (B-1) having a substituent group (-CH ₂ COOR ^1B) on the benzene ring ortho to the azo group in one side, as shown in the following scheme By heating, an azo group reacts with the substituent of the benzene ring (-CH ₂ COOR ^1B ) to form a cyclic structure, and the azo group is lost.

[Formula 18]

In Formula (B-1), R ^1B represents a hydrogen atom or a substituted or unsubstituted alkyl group. For descriptions, preferred ranges, and specific examples of the alkyl group and the substituents that may be substituted with the alkyl group, refer to the descriptions, the preferred ranges, and the specific examples of the alkyl group and the substituents in R ^a in the formula (a-1). Can be.

(C) Cyclic Reaction of Acylhydrazone Structure: 5-membered Ring Formation

In the first structural unit having an acyl hydrazone structure already shown by acyl hydrazone structure, i.e., formula (C-1) having a R ^1C substituents on ortho to the group of the benzene ring, as shown in the following scheme. Similarly, by heating, the imino group (= NR) reacts with the substituent R ^1C of the benzene ring to form a cyclic structure, and the imino group is lost.

[Formula 19]

In Formula (C-1), R ^1C represents a group represented by Formula (C-1-1) or Formula (C-1-2). In formula (C-1), formula (C-1-1) and formula (C-1-2), R ^2C , R ^4C and R ^5C are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, A substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group. For the description, preferred ranges, and specific examples of the substituents which may be substituted with alkyl groups, alkanoyl groups, alkoxycarbonyl groups, arylcarbonyl groups, and these groups in R ^2C , R ^4C, and R ^5C , the above formulas (a-1) ) can refer to an alkyl, alkanoyl, alkoxycarbonyl group, aryl carbonyl group, and described with a preferred range of the substituent that may be substituted with these, specific examples of R in the ^a.

(D) Cyclic Reaction After Freeze Potential: 5-membered Ring Formation

The phenyl ester structure having a substituent (-CH ₂ NHR ^1D ) on the ortho to the ester linkage site of the benzene ring, that is, the phenyl ester structure represented by the following formula (D-1), is subjected to a freeze potential, as shown in the following reaction formula, The carbonyl group reacts with the substituent of the benzene ring (-CH ₂ NHR ^1D ) to form a cyclic structure, and the carbonyl group is lost.

[Formula 20]

In Formula (D-1), R ^1D represents a substituted or unsubstituted alkyl group. For descriptions, preferred ranges, and specific examples of the alkyl group and the substituents that may be substituted with the alkyl group, refer to the descriptions, the preferred ranges, and the specific examples of the alkyl group and the substituents in R ^a in the formula (a-1). Can be.

Whether the first structural unit containing the photoreactive structure caused a chemical reaction can be confirmed by an ultraviolet visible absorption spectrum (transmittance), nuclear magnetic resonance (NMR) spectrum, and infrared spectroscopy (IR) spectrum. For example, when the photoreactive structure comprises the azobenzene structure, it can be confirmed that the above cyclization reaction has occurred by increasing the transmittance at 365 nm which is the absorption wavelength of the azobenzene. Here, in the liquid crystal aligning agent using the 1st monomer containing an azobenzene structure as a photoreactive structure, it is preferable that the transmittance | permeability of 365 nm rises 10% or more by the chemical reaction by heating. When the film | membrane which consists of this liquid crystal aligning agent heats and heats at 230 degreeC for 30 minutes specifically, it is preferable that the transmittance | permeability in 365 nm of the film rises 10% or more from the transmittance | permeability in 365 nm of the film before heat baking. In such a liquid crystal aligning agent, after performing a photo-alignment process on the film, the photoreactivity of an azobenzene structure can be reliably reduced by heating. Thereby, the liquid crystal aligning film which is high in light stability and shows favorable liquid-crystal orientation can be formed.

(Compound Example of First Monomer)

As a preferable example of a 1st monomer, the diamine represented by Formula (2) is mentioned.

The diamine represented by Formula (2) has the azobenzene structure common to the structure represented by Formula (1). For this reason, as a polymer formed by superposing | polymerizing a monomer composition by using this diamine as a 1st monomer, for example, using a tetracarboxylic dianhydride or its derivative as a 2nd monomer and other monomers, it is represented by Formula (1). Polyamic acid, a polyamic acid ester, a polyamic acid polyamide copolymer, etc. which have the structure shown to the structural unit of a principal chain can be obtained. Moreover, derivatives, such as a polyimide, partial polyimide, and a polyamic acid ester, can be produced from this polyamic acid, and derivatives, such as polyamideimide, can be produced from a polyamic acid-polyamide copolymer. Thereby, various derivatives which include the structure represented by Formula (1) in the structural unit of a main chain can be obtained. For the detailed description of the polymer or derivative obtained by polymerizing the monomer composition, reference may be made to the descriptions in the columns of [Polymer or derivative thereof polymerized by monomer composition] and (Synthesis method of polymer from monomer composition).

[Formula 21]

In Formula (2), R <^1> and R <^2> respectively independently represents group represented by a hydrogen atom, Formula (1-1), or Formula (1-2), At least one of R <^1> and R <^2> is a formula ( 1-1) or group represented by Formula (1-2). For description of R ¹ and R ² in formula (2), reference may be made to the description of R ¹ and R ² in formula (1).

R ⁶ and R ⁸ are each independently a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) -Or a single bond. In R ⁶ and R ⁸ , one of —CH ₂ — of the linear alkylene group or two not adjacent to each other may be substituted with —O—. R <^6> and R <^8> may mutually be same or different. R ⁷ and R ⁹ each independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond. R ⁷ and R ⁹ may be the same as or different from each other.

The monocyclic hydrocarbon in R ⁷ and R ⁹ may be an alicyclic ring or an aromatic ring. It is preferable that carbon number of monocyclic hydrocarbon is 6-12, It is more preferable that it is 6-10, It is more preferable that it is 6-8. As a specific example of a monocyclic hydrocarbon, a benzene ring, a cyclohexane ring, and a cyclohexene ring can be mentioned.

It is preferable that carbon number of the condensed polycyclic hydrocarbon in R <^7> and R <^9> is 10-26, It is more preferable that it is 10-18, It is more preferable that it is 10-14. As a specific example of a condensed polycyclic hydrocarbon, a naphthalene ring, anthracene ring, and phenanthrene ring are mentioned.

The heterocycle in R ⁷ and R ⁹ may be an alicyclic ring or an aromatic ring. It is preferable that it is 1-26, as for carbon number of a heterocycle, it is more preferable that it is 3-14, and it is more preferable that it is 3-8. As a hetero atom which a heterocyclic ring contains as a reduction, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned. As a specific example of a heterocyclic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indole ring, and an oxazole ring can be mentioned.

In Formula (2), -R ⁶ -R ⁷ -NH ₂ is bonded to one benzene ring in Formula (2), and the bonding position is a position capable of substituting with a hydrogen atom in the benzene ring. Which is either. -R ⁸ -R ⁹ -NH ₂ is bonded to the other benzene ring in Formula (2), and the bonding position is any one of a hydrogen atom and a substitutable position in the benzene ring. The remaining substitutable position of the benzene ring may be unsubstituted or may be substituted with a substituent. About the preferable range and specific example of a substituent, in the said Formula (1), the preferable range and specific example of the substituent which can be substituted by a benzene ring can be referred.

[Formula 22]

In formula (1-1), R <^4> is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl. Group. In formula (1-2), R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or Unsubstituted arylcarbonyl group is shown. In Formulas (1-1) and (1-2), * represents a bonding position to the benzene ring in Formula (2). Description of R <^4> , R <^5> , * in Formula (1-1) and (1-2) is R <^4> of Formula (1-1) and (1-2) in Formula (1). See the description of R ⁵ , *.

It is preferable that the diamine represented by Formula (2) is a diamine represented by either of following formula (3)-(6) from the ease of synthesis | combination, the ease of a raw material acquisition, and the height of liquid crystal alignability.

[Formula 23]

In Formula (3)-(6), R <^4> and R <^5> is synonymous with R <^4> and R <^5> in Formula (1-1) and Formula (1-2) of Formula (2). It is preferable that R <^4> and R <^5> are a hydrogen atom, a C1-C10 alkyl group, or a C1-C10 alkanyl group each independently. Formula (3) R ⁴ in each other, the formula (5) R ⁴ together, R ⁵ together and R ⁴ and R ^5, R ⁴ and R ⁵ in the formula (6), but each may be the same or different from each other, the same is desirable.

As a preferable specific example of the diamine represented by any of Formula (3)-(6), Formula (3-1)-(3-9), Formula (4-1)-(4-9), Formula (5-1) ), A diamine represented by any one of Formula (5-2), Formula (6-1), and Formula (6-2). The polymer component which synthesize | combined these diamine as a 1st monomer tends to show high liquid crystal alignability. In each formula, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, ⁱ Pr represents an isopropyl group, Bu represents a butyl group, and ^t Bu represents a t-butyl group, respectively.

[Formula 24]

[Formula 25]

Synthesis of Diamine

The diamine represented by any one of said Formula (3)-(6) can be synthesize | combined as follows.

In order to synthesize the diamine represented by Formula (3), after commercially available 5-nitroanthranilic acid is reduced to obtain 2-amino-5-nitrophenylmethanol, the oxidation reaction of the aromatic amine in the benzene ring Azobenzene having a hydroxymethyl group on the ortho of the azo group and a nitro group on parawi is obtained. Subsequently, a hydroxyl group is used as a trifluoro methanesulfonic acid ester, and it is set as an alkoxy group by a nucleophilic substitution reaction. Finally, the diamine of interest is obtained by reducing the nitro group.

In order to synthesize the diamine represented by Formula (4), 1-alkoxymethyl-3-nitrobenzene was obtained from a commercially available 1-bromomethyl-3-nitrobenzene by a nucleophilic substitution reaction, and then the nitro group was reduced. Obtain 3-alkoxymethylaniline. Subsequently, azobenzene is synthesize | combined by the diazo coupling with 4-nitroaniline, and the target diamine is obtained by reducing a nitro group.

In order to synthesize the diamine represented by Formula (5), after commercially available 5-nitroanthranilic acid is reduced to obtain 2-amino-5-nitrophenylmethanol, the oxidation reaction of the aromatic amine in the benzene ring Azobenzene having a hydroxymethyl group on the ortho of the azo group and a nitro group on parawi is obtained. Subsequently, a hydroxyl group is used as a trifluoromethanesulfonic acid ester, and it is set as N, N'- dialkylamino group by a nucleophilic substitution reaction. Finally, the diamine of interest is obtained by reducing the nitro group.

In order to synthesize the diamine represented by Formula (6), N, N'-dialkyl-1- (3-nitrophenyl) methane by commercial nucleophilic substitution reaction is carried out from commercially available 1-bromomethyl-3-nitrobenzene. After obtaining the amine, the nitro group is reduced to give dialkylaminomethyl-3-nitrobenzene. Subsequently, azobenzene is synthesize | combined by the diazo coupling with 4-nitroaniline, and the target diamine is obtained by reducing a nitro group.

These diamines may be purified by recrystallization or column chromatography.

In order to provide the liquid crystal aligning agent which can become a liquid crystal aligning film with higher liquid crystal aligning property, among these compounds, Formula (4-1), Formula (4-2), Formula (4-3), Formula (4-4) , It is preferable to use at least one of diamine represented by any one of Formula (4-5) and Formula (6-1) as a 1st monomer.

[Second monomer]

A 2nd monomer is a compound which contains a photoreactive structure in the part (structural unit formation part) which forms the structural unit of a polymer, and the part which forms the structural unit of the polymer does not produce the chemical reaction by heating. In this invention, the structural unit formation part of this 2nd monomer is introduce | transduced into a polymer, and forms the 2nd structural unit which contains a photoreactive structure and does not produce the chemical reaction by heating. When the liquid crystal aligning agent contains the polymer which has such a 2nd structural unit as a polymer component, and heat-calculates after performing the photo-alignment process on the film | membrane, in the 2nd structural unit, the orientation state immediately after the photo-alignment process will be Retained, effectively contributing to the anisotropy of the polymer backbone. For this reason, the obtained liquid crystal aligning film shows the outstanding liquid crystal aligning property. Here, one type may be sufficient as the 2nd monomer which a monomer composition contains, or two or more types may be sufficient as it.

The structural unit formation part of a 2nd monomer may consist only of a photoreactive structure, and may contain another structure. The number of photoreactive structures which a structural unit formation part contains may be one, or two or more may be sufficient as it. When a structural unit formation part contains two or more photoreactive structure, these photoreactive structures may mutually be same or different.

It is preferable that it is a photoisomerization structure or a photodimerization structure, and, as for the photoreaction structure introduced into the structural unit formation part of a 2nd monomer, it is more preferable that it is a photoisomerization structure. As a photoisomerization structure, an azobenzene structure, a stilbene structure, an acylhydrazone structure, etc. are mentioned, As a photodimerization structure, a coumarin structure, a cinnamate structure, a chalcone structure, a tolan structure, etc. are mentioned.

(Compound Example of Second Monomer)

As a 2nd monomer, following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula ( IV-3), formula (V-1), formula (V-2), formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1), formula (VIII -1) and the compound represented by any one of formula (VIII-2) can be used.

[Formula 26]

[Formula 27]

In each said formula, the group in which the bond position is not fixed to any one carbon atom which comprises a ring shows that the bond position in the ring is arbitrary. In formula (IV-3), r is an integer of 1-10. In the formula (V-2), R ⁶ independently represent the _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently an integer from 0 to 2. In Formula (V-3), ring A and ring B each independently represent at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocycles. R ¹¹ is 1 to 20 carbon atoms in the straight-chain alkylene group, -COO-, -OCO-, -NHCO-, -CONH- , -N (CH 3) CO-, or -CON (CH ₃₎ - represents the, R ¹² represents straight-chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, or -CON (CH ₃ )-, and R ¹¹ And in R ¹² , one or two of -CH ₂ -of linear alkylene may be substituted with -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , denotes -CF _3, or -OH, and, b ~ e are each independently an integer of 0-4. In the formula (VII-1), R ⁴ and R ⁶ is a straight chain of 1 to 20 carbon atoms independently alkylene, -COO-, -OCO-, -NHCO-, -CONH- , -N (CH 3) CO -, -CON (CH ₃ )-or a single bond, and in R ⁴ and R ⁶ , one or two non-adjacent of -CH ₂ -of the linear alkylene may be substituted with -O-, R ⁵ and R ⁷ independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond.

Ring A and ring B of Formula (V-3) and monocyclic hydrocarbon in R <^5> and R <^7> of Formula (VII-1) may be alicyclic or an aromatic ring may be sufficient as them. It is preferable that carbon number of monocyclic hydrocarbon is 6-12, It is more preferable that it is 6-10, It is more preferable that it is 6-8. As a specific example of a monocyclic hydrocarbon, a benzene ring, a cyclohexane ring, and a cyclohexene ring can be mentioned.

It is preferable that carbon number of the condensed polycyclic hydrocarbon in ring A and ring B of Formula (V-3), and R <^5> and R <^7> of formula (VII-1) is 10-26, and it is 10-18. More preferably, it is more preferable that it is 10-14. As a specific example of a condensed polycyclic hydrocarbon, a naphthalene ring, anthracene ring, and phenanthrene ring are mentioned.

The ring A and the ring B of the formula (V-3) and the heterocycle in R ⁵ and R ⁷ of the formula (VII-1) may be alicyclic or aromatic rings. It is preferable that it is 1-26, as for carbon number of a heterocycle, it is more preferable that it is 3-14, and it is more preferable that it is 3-8. As a hetero atom which a heterocyclic ring contains as a reduction, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned. As a specific example of a heterocyclic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indole ring, and an oxazole ring can be mentioned.

Using the diamine represented by Formula (2) as a 1st monomer, Formula (II-1), Formula (III-1), Formula (IV-1), Formula (IV-3), Formula (2) as a 2nd monomer The structure represented by Formula (1) as a polymer formed by superposing | polymerizing a monomer composition by using the compound (tetracarboxylic dianhydride) represented by any one of V-1) and Formula (VI-1), and Formula (II-1) , Except for -CO-O-CO- in formula (III-1), formula (IV-1), formula (IV-3), formula (V-1), or formula (VI-1). The polyamic acid which has a structure and the carbonyl group and carboxyl group converted from -CO-O-CO- in the structural unit of a principal chain can be obtained. Using the diamine represented by Formula (2) as a 1st monomer, As a 2nd monomer, Formula (II-2), Formula (III-2), Formula (IV-2), Formula (V-2), Formula ( When using the compound (diamine) represented by any one of V-3), Formula (VI-2), Formula (VII-1), Formula (VIII-1), and Formula (VIII-2), another monomer As a polymer formed by polymerizing a monomer composition by using tetracarboxylic dianhydride or a derivative thereof, the structure represented by formula (1), formula (II-2), formula (III-2), formula (IV-2), formula (V-2), formula (V-3), formula (VI-2), formula (VII-1), formula (VIII-1), or a group represented by the formula -NH _2, except in (VIII-2) the structure of the portion, and a polyamic acid or polyamic acid ester, polyamic acid having a conversion from -NH- -NH ₂ in the structural unit of the main chain - can be obtained, such as polyamide copolymer. In addition, derivatives such as polyimide, partial polyimide and polyamic acid ester can be produced from polyamic acid, and derivatives such as polyamideimide can be produced from polyamic acid-polyamide copolymer. Thereby, the structure represented by Formula (1), Formula (II-1), Formula (II-2), Formula (III-1), Formula (III-2), Formula (IV-1), Formula (IV-) 2), formula (IV-3), formula (V-1), formula (V-2), formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1 ), Formula (VIII-1), or various derivatives having a structure of the main chain constituting unit except for -CO-O-CO- and -NH ₂ in formula (VIII-2).

For the detailed description of the polymer or derivative obtained by polymerizing the monomer composition, reference may be made to the descriptions in the columns of [Polymer or derivative thereof polymerized by monomer composition] and (Synthesis method of polymer from monomer composition).

As a 2nd monomer, in said, Formula (II-1), Formula (II-2), Formula (III-1), Formula (III-2), Formula (IV-1), Formula (IV-2), Any one of formula (IV-3), formula (V-1), formula (V-2), formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1) Preferred are compounds represented by one. Moreover, the compound represented by said Formula (V-1), Formula (V-2), Formula (VI-1), Formula (VI-2), and Formula (VII-1) is more preferable at the point of the photosensitivity. . In Formula (V-2) and Formula (VI-2), the compound in which the binding position of two amino groups is all para is especially preferable. In addition, in Formula (V-2), the compound of a = 0 can be used more suitably from the point of the orientation.

As a more preferred embodiment of the second monomer, the following formula (V-2-1), formula (V-3-2), formula (VI-2-1), formula (VII-1-1) and formula (VII) The compound represented by -1-2) is mentioned.

[Formula 28]

[The compounding quantity of the 1st monomer and the 2nd monomer in a monomer composition]

It is preferable that it is 15-85 mol% with respect to the total mole number of a 1st monomer and a 2nd monomer, and, as for the compounding quantity of the 2nd monomer in a monomer composition, it is more preferable that it is 15-40 mol%, 20-30 mol% Is more preferred.

It is preferable that it is 5-45 mol% with respect to the total mole number of all the monomer components which comprise a monomer composition, and, as for the compounding quantity of the 1st monomer in a monomer composition, it is more preferable that it is 25-45 mol%, 25-40 mol More preferably%.

It is preferable that it is 5-40 mol% with respect to the total mole number of all the monomer components which comprise a monomer composition, and, as for the compounding quantity of the 2nd monomer in a monomer composition, it is more preferable that it is 10-30 mol%, 10-25 mol More preferably%.

When the polymer obtained from the monomer composition is a polyamic acid or a derivative thereof, and the first monomer is a diamine, the compounding amount of the diamine in the monomer composition is 15 to 80 mol% based on the total amount of the diamine contained in the monomer composition. Preferably, 50-80 mol% is more preferable.

When the polymer obtained from the monomer composition is a polyamic acid or a derivative thereof, and the second monomer is a diamine, the compounding amount of the diamine in the monomer composition is 15 to 80 mol% based on the total amount of the diamine contained in the monomer composition. Preferably, 20-50 mol% is more preferable.

[Other monomers]

The monomer composition may contain monomers other than a 1st monomer and a 2nd monomer, ie, the monomer which does not contain a photoreactive structure in the part (structural unit formation part) which forms a structural unit.

In addition, in the following description, a monomer may express "non-photoreactive" that "the photoreactive structure is not included in a structural unit formation part", for example, does not include a photoreactive structure in a "structural unit formation part. Monomer "is sometimes referred to as a" non-photoreactive monomer ".

For example, the diamine represented by Formula (2) is used as a 1st monomer, and Formula (II-1), Formula (II-2), Formula (III-1), Formula (III-2) are used as a 2nd monomer. ), Formula (IV-1), formula (IV-2), formula (IV-3), formula (V-1), formula (V-2), formula (V-3), formula (VI-1) , A compound represented by any one of formula (VI-2), formula (VII-1), formula (VIII-1), and formula (VIII-2), in particular formula (II-2), formula (III-2), In formula (IV-2), formula (V-2), formula (V-3), formula (VI-2), formula (VII-1), formula (VIII-1), and formula (VIII-2) When using the compound (diamine) which is represented by either, by using non-photoreactive tetracarboxylic dianhydride as another monomer, polyamic acid can be obtained as a polymer which superposes | polymerizes a monomer composition, and it is non-reactive as another monomer. A polyamic acid ester or a polyamic acid polyamar as a polymer which polymerizes a monomer composition by using the derivative of tetracarboxylic dianhydride of Derivatives of polyamic acid, such as an id copolymer, can be obtained. For the detailed description of the polymer or derivative obtained by polymerizing the monomer composition, reference may be made to the descriptions in the columns of [Polymer or derivative thereof polymerized by monomer composition] and (Synthesis method of polymer from monomer composition).

(Non-photoreactive tetracarboxylic dianhydride)

The tetracarboxylic dianhydride as the non-photoreactive monomer can be selected without limitation from known tetracarboxylic dianhydrides. Such tetracarboxylic dianhydride includes an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and an aliphatic system (heterocyclic system in which a dicarboxylic acid anhydride is not directly bonded to an aromatic ring). May belong to any group).

Suitable examples of such tetracarboxylic dianhydrides include tetracarboxylic dianhydrides represented by any one of the following formulas (AN-I) to (AN-V) in terms of ease of obtaining raw materials, ease of polymer production, and electrical properties of the membrane. Can be.

[Formula 29]

In formula (AN-I), formula (AN-IV) and formula (AN-V), each X independently represents a single bond or -CH _2- . In formula (AN-II), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or a divalent group represented by the following Formula (G13-1) is represented, and -CH ₂ -may be substituted with -O-, -CO-, or -NH-.

[Formula 30]

In Formula (G13-1), G ^13a and G ^13b each independently represent a single bond or a divalent group selected from -O-, -CONH- or -NHCO-. It is preferable that a phenylene group is a 1, 4- phenylene group or a 1, 3- phenylene group.

In Formulas (AN-II) to (AN-IV), Y independently represents one selected from the group of the following trivalent group. Each combination of the trivalent group is a hand, and is connected to any one of the carbonyl carbon atom constituting ring group or a position a hydrogen atom and the substitution of A ¹⁰ in the respective formula. At least one hydrogen atom of this trivalent group may be substituted by the methyl group, the ethyl group, or the phenyl group.

[Formula 31]

In formulas (AN-III) to (AN-V), ring A ¹⁰ independently represents a cyclic group obtained by removing hydrogen atoms by the number of bonds from a monocyclic hydrocarbon having 3 to 10 carbon atoms, or a condensate having 6 to 30 carbon atoms. The cyclic group which removed the hydrogen atom by the number of the bond hands from polycyclic hydrocarbon is shown. At least one hydrogen atom in each cyclic group may be substituted by the methyl group, the ethyl group, or the phenyl group. In addition, the bond which is hung on each ring is connected to any carbon constituting the ring, and two bonds may be bonded to the same carbon atom.

Moreover, what is represented by either of the following formula (AN-1)-a formula (AN-16-15) is mentioned as tetracarboxylic dianhydride.

Tetracarboxylic dianhydride represented by formula (AN-1):

[Formula 32]

In Formula (AN-1), G ¹¹ represents a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group, or a 1,4-cyclohexylene group. X ¹¹ independently represents a single bond or —CH ₂ —. G ¹² independently represents any of the following trivalent groups.

[Formula 33]

When G < ¹² >is> CH-, the hydrogen atom of> CH- may be substituted by the methyl group. When G ¹² is> N-, G ¹¹ is not a single bond and -CH ₂ -and X ¹¹ is not a single bond. R ¹¹ represents a hydrogen atom or a methyl group.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-1), the compound represented by a following formula is mentioned.

[Formula 34]

In formula (AN-1-2) and (AN-1-14), m is an integer of 1-12 each independently.

Tetracarboxylic dianhydride represented by formula (AN-2):

[Formula 35]

In formula (AN-2), R ⁶¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-2), the compound represented by a following formula is mentioned.

[Formula 36]

Tetracarboxylic dianhydride represented by formula (AN-3):

[Formula 37]

In Formula (AN-3), ring A ¹¹ represents a cyclohexane ring or a benzene ring.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-3), the compound represented by a following formula is mentioned.

[Formula 38]

Tetracarboxylic dianhydride represented by formula (AN-4):

[Formula 39]

In formula (AN-4), G ¹³ is a single bond,-(CH ₂ ) _m- , -O-, -S-, -C (CH ₃ ) _2- , -SO _2- , -CO-,- C (CF ₃ ) ₂ — or a divalent group represented by the following Formula (G13-1) is represented, and m is an integer of 1 to 12. Ring A ¹¹ represents a cyclohexane ring or a benzene ring each independently. G ¹³ may be bonded to any one of positions substituted with a hydrogen atom of ring A ¹¹ .

[Formula 40]

In Formula (G13-1), G ^13a and G ^13b each independently represent a divalent group represented by a single bond, -O-, -CONH-, or -NHCO-. It is preferable that a phenylene group is a 1, 4- phenylene group or a 1, 3- phenylene group.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-4), the compound represented by a following formula is mentioned.

[Formula 41]

[Formula 42]

In Formula (AN-4-17), m is an integer of 1-12.

[Formula 43]

[Formula 44]

Tetracarboxylic dianhydride represented by formula (AN-5):

[Formula 45]

In formula (AN-5), R ¹¹ independently represents a hydrogen atom or a methyl group. In the second of the benzene ring of R ¹¹ R ¹¹ it can be bonded to any one of the benzene ring substitutable positions.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-5), the compound represented by a following formula is mentioned.

[Formula 46]

Tetracarboxylic dianhydride represented by formula (AN-6):

[Formula 47]

In formula (AN-6), X ¹¹ independently represents a single bond or -CH _2- . X ¹² represents —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—. n is 1 or 2. When n is 2, two X <^12> may mutually be same or different.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-6), the compound represented by a following formula is mentioned.

[Formula 48]

Tetracarboxylic dianhydride represented by formula (AN-7):

[Formula 49]

In formula (AN-7), X ¹¹ represents a single bond or -CH _2- .

As an example of the tetracarboxylic dianhydride represented by a formula (AN-7), the compound represented by a following formula is mentioned.

[Formula 50]

Tetracarboxylic dianhydride represented by formula (AN-8):

[Formula 51]

In formula (AN-8), X ¹¹ represents a single bond or -CH _2- . R ¹² represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. Ring A ¹² represents a cyclohexane ring or a cyclohexene ring.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-8), the compound represented by a following formula is mentioned.

[Formula 52]

Tetracarboxylic dianhydride represented by formula (AN-9):

[Formula 53]

In formula (AN-9), r is 0 or 1 each independently.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-9), the compound represented by a following formula is mentioned.

[Formula 54]

Tetracarboxylic dianhydride represented by formula (AN-10-1) and formula (AN-10-2):

[Formula 55]

Tetracarboxylic dianhydride represented by formula (AN-11):

[Formula 56]

In Formula (AN-11), ring A ¹¹ represents a cyclohexane ring or a benzene ring independently.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-11), the compound represented by a following formula is mentioned.

[Formula 57]

Tetracarboxylic dianhydride represented by formula (AN-12):

[Formula 58]

In Formula (AN-12), ring A ¹¹ represents a cyclohexane ring or a benzene ring each independently.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-12), the compound represented by a following formula is mentioned.

[Formula 59]

Tetracarboxylic dianhydride represented by formula (AN-15):

[Formula 60]

In Formula (AN-15), w is an integer of 1-10.

As an example of the tetracarboxylic dianhydride represented by a formula (AN-15), the compound represented by a following formula is mentioned.

[Formula 61]

The following compounds are mentioned as tetracarboxylic dianhydride of that excepting the above.

[Formula 62]

In the said tetracarboxylic dianhydride, the suitable material which improves each characteristic of the liquid crystal aligning film mentioned later is demonstrated. In the case where emphasis is placed on improving the orientation of the liquid crystal, compounds represented by the formula (AN-1), the formula (AN-3), and the formula (AN-4) are preferable, and the formula (AN-1-2) and the formula The compound represented by (AN-1-13), formula (AN-3-2), formula (AN-4-17), and formula (AN-4-29) is more preferable, and the formula (AN-1-2 ), M = 4 or 8 is preferable, in formula (AN-4-17), m = 4 or 8 is preferable and m = 8 is more preferable.

In the case of focusing on improving the transmittance of the liquid crystal display device, formula (AN-1-1), formula (AN-1-2), formula (AN-3-1), formula (AN-4-17), Expression (AN-4-30), Expression (AN-5-1), Expression (AN-7-2), Expression (AN-10-1), Expression (AN-16-3), Expression (AN-16 -4) and the compound represented by a formula (AN-2-1) are preferable, Especially, in a formula (AN-1-2), m = 4 or 8 is preferable and a formula (AN-4-17) In m, 4 or 8 is preferable, and m = 8 is more preferable.

When emphasizing improving VHR of a liquid crystal display element, Formula (AN-1-1), Formula (AN-1-2), Formula (AN-3-1), Formula (AN-4-17), Expression (AN-4-30), Expression (AN-7-2), Expression (AN-10-1), Expression (AN-16-3), Expression (AN-16-4), and Expression (AN- The compound represented by 2-1) is preferable, and m = 4 or 8 is preferable in a formula (AN-1-2), and m = 4 or 8 is preferable in a formula (AN-4-17). And m = 8 is more preferable.

By lowering the volume resistance value of the liquid crystal aligning film, improving the relaxation rate of the residual electric charge (residual DC) in the liquid crystal aligning film is effective as one of the methods of preventing sticking. When this purpose is important, Formula (AN-1-13), Formula (AN-3-2), Formula (AN-4-21), Formula (AN-4-29), and Formula (AN-11) The compound represented by -3) is preferable.

(Non-photoreactive diamine and non-photoreactive dihydrazide)

When the monomer composition is a composition for synthesizing polyamic acid or a derivative thereof, for example, a diamine represented by formula (2) is included as the first monomer, and formula (II-1) and formula (II-) are used as the second monomer. 2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (IV-3), formula (V-1), formula (V-2) ), A compound represented by any one of formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1), formula (VIII-1), and formula (VIII-2) In addition, when it contains non-photoreactive tetracarboxylic dianhydride or its derivative (s) as needed, you may contain a non-photoreactive diamine and non-photoreactive dihydrazide in a monomer composition. Thereby, the structural unit derived from a non-photoreactive diamine and the structural unit derived from a non-photoreactive dihydrazide can be introduce | transduced into the polymer obtained from a monomer composition, and the characteristic of the liquid crystal aligning film obtained can be controlled.

As diamine and dihydrazide used as a non-photoreactive monomer, it can select from well-known diamine and dihydrazide, without being restrict | limited.

Diamine can be divided into two types according to the structure. That is, when the skeleton which connects two amino groups is seen as a main chain, it is the group which branch | branches from a main chain, ie, diamine which has a side chain group, and a diamine which does not have a side chain group. In the following description, the diamine which has such a side chain group may be called a side chain type diamine. And the diamine which does not have such a side chain group may be called non-branched diamine. This side chain group is group which has an effect which enlarges a pretilt angle.

By appropriately dividing the non-branched diamine and the branched diamine, it is possible to cope with the pretilt angle required for each.

It is preferable to use side chain diamine together so that the characteristic of this invention may not be impaired. Moreover, it is preferable to select and use side chain type diamine and non-branch type diamine for the purpose of improving the vertical alignment property, VHR, adhesion characteristics, and orientation property with respect to a liquid crystal.

Known diamine and dihydrazide are shown below.

[Formula 63]

In the above-mentioned formula (DI-1), G ²⁰ is, -CH ₂ -, or represents a group represented by the formula (DI-1-a). When G ²⁰ is -CH _2- , at least one of m -CH ₂ -may be substituted with -NH-, -O-, and at least one hydrogen atom of m -CH ₂ -may be substituted with a hydroxyl group. . m is an integer of 1-12. When m in DI-1 is 2 or more, some G <^20> may mutually be same or different. However, when the date represented by the formula G ²⁰ (DI-1-a), m is 1.

[Formula 64]

In formula (DI-1-a), v is an integer of 1-6 each independently.

In formula (DI-3), formula (DI-6) and formula (DI-7), G ²¹ is independently a single bond, -NH-, -NCH _3- , -O-, -S-, -SS -, -SO _2- , -CO-, -COO-, -CONCH _3- , -CONH-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -N (CH ₃ )-(CH ₂ ) _k -N (CH ₃ )-,-(OC ₂ H ₄ ) _m -O-, -O-CH _2- C (CF ₃ ) ₂ -CH ₂ -O-, -O-CO- (CH ₂ ) _m -CO-O-, -CO-O- (CH ₂ ) _m -O-CO-,-(CH ₂ ) _m -NH- (CH ₂ ) _m- , -CO- (CH ₂ ) _k -NH- (CH ₂ ) _k -,-(NH- (CH ₂ ) _m ) _k -NH-, -CO-C ₃ H _6- (NH-C ₃ H ₆ ) _n -CO-, or -S- (CH ₂ ) _m -S-; independently, m is an integer of 1 to 12, k is an integer of 1 to 5, n is 1 or 2. In Formula (DI-4), s is an integer of 0-2 independently.

In formula (DI-5), G ³³ is a single bond, -NH-, -NCH _3- , -O-, -S-, -SS-, -SO _2- , -CO-, -COO-,- CONCH _3- , -CONH-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -N (CH ₃ )-(CH ₂ ) _k -N (CH ₃ )-,-(OC ₂ H ₄ ) _m -O-, -O-CH ₂ -C (CF ₃ ) ₂ -CH ₂ -O-, -O- CO- (CH ₂ ) _m -CO-O-, -CO-O- (CH ₂ ) _m -O-CO-,-(CH ₂ ) _m -NH- (CH ₂ ) _m- , -CO- (CH ₂ ) _k -NH- (CH ₂ ) _k -,-(NH- (CH ₂ ) _m ) _k -NH-, -CO-C ₃ H _6- (NH-C ₃ H ₆ ) _n -CO-, or -S- (CH ₂ ) _m -S-, -N (Boc)-(CH ₂ ) _e -N (Boc)-, -NH- (CH ₂ ) _e -N (Boc)-, -N (Boc) -(CH ₂ ) _e -,-(CH ₂ ) _m -N (Boc) -CONH- (CH ₂ ) _m -,-(CH ₂ ) _m -N (Boc)-(CH ₂ ) _m- , (DI-5-a) or a group represented by the following formula (DI-5-b), m is an integer of 1 to 12 independently, k is an integer of 1 to 5, e is an integer of 2 to 10, and , n is 1 or 2. Boc is a t-butoxycarbonyl group.

In formula (DI-6) and formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or an alkylene group having 1 to 10 carbon atoms.

At least one hydrogen atom of the cyclohexane ring and the benzene ring in the formulas (DI-2) to (DI-7) is -F, -Cl, an alkylene group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , —CO ₂ H, —CONH ₂ , —NHC ₆ H ₅ , a phenyl group, or a benzyl group may be substituted, and in formula (DI-4), at least one hydrogen atom of the cyclohexane ring and the benzene ring may be , May be substituted with one selected from the group of the group represented by any one of the following formula (DI-4-a) to (DI-4-i), in the formula (DI-5), when G ³³ is a single bond At least one hydrogen atom of the cyclohexane ring and the benzene ring may be substituted with NHBoc or N (Boc) ₂ .

The group whose bond position is not fixed to the carbon atom which comprises a ring shows that the bond position in the ring is arbitrary. Then, the binding position of -NH ₂ of the cyclohexane ring or a benzene ring is, G ^21, is any position other than the coupling position of G ²² or G ^33.

[Formula 65]

[Formula 66]

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ independently represents a hydrogen atom or —CH ₃ . In formula (DI-4-f) and formula (DI-4-g), m is an integer of 0-12 each independently, and Boc is a t-butoxycarbonyl group.

[Formula 67]

In Formula (DI-5-a), q is an integer of 0-6 each independently. R ⁴⁴ represents a hydrogen atom, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[Formula 68]

In formula (DI-11), r is 0 or 1. In Formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is any position.

[Formula 69]

In formula (DI-12), R ²¹ and R ²² each independently represents an alkyl group or a phenyl group having a carbon number of 1 to 3, G ²³ are independently substituted with an alkylene group, a phenylene group or an alkyl group having 1 to 6 carbon atoms A phenylene group is shown and w is an integer of 1-10.

In formula (DI-13), R <^23> represents a C1-C5 alkyl group, a C1-C5 alkoxy group, or -Cl independently, p is an integer of 0-3 independently, q is 0-4 Is an integer.

In formula (DI-14), ring B represents a monocyclic heterocyclic aromatic group, R ²⁴ represents a hydrogen atom, -F, -Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkenyl group, or an alkynyl group. and q are independently the integer of 0-4. When q is two or more, some R <^24> may mutually be same or different.

In Formula (DI-15), ring C represents a heterocyclic aromatic group or a heterocyclic aliphatic group.

In Formula (DI-16), G ²⁴ represents a single bond, an alkylene group having 2 to 6 carbon atoms, or a 1,4-phenylene group, and r is 0 or 1. And the group in which the bond position is not fixed to the carbon atom which comprises a ring shows that the bond position in the ring is arbitrary.

In formula (DI-13)-formula (DI-16), the coupling | bonding position of -NH2 _{couple |} bonded with a ring is arbitrary positions.

As a diamine which does not have a side chain of said Formula (DI-1)-(DI-16), the specific example of the following formula (DI-1-1)-formula (DI-16-1) is mentioned.

Examples of the diamine represented by the formula (DI-1) are shown below.

[Formula 70]

In formula (DI-1-7) and formula (DI-1-8), k is an integer of 1-3 each independently. In formula (DI-1-9), v is an integer of 1-6 each independently.

Examples of the diamine represented by formulas (DI-2) to (DI-3) are shown below.

[Formula 71]

Examples of the diamine represented by the formula (DI-4) are shown below.

[Formula 72]

[Formula 73]

[Formula 74]

[Formula 75]

[Formula 76]

[Formula 77]

In formula (DI-4-20) and (DI-4-21), m is an integer of 1-12 each independently.

[Formula 78]

Examples of the diamine represented by the formula (DI-5) are shown below.

[Formula 79]

In formula (DI-5-1), m is an integer of 1-12.

[Formula 80]

In formula (DI-5-12) and formula (DI-5-13), m is an integer of 1-12 each independently.

[Formula 81]

In formula (DI-5-16), v is an integer of 1-6.

[Formula 82]

In formula (DI-5-30), k is an integer of 1-5.

[Formula 83]

In formula (DI-5-35)-formula (DI-5-37), and formula (DI-5-39), m is an integer of 1-12 each independently, and is a formula (DI-5-38) And in formula (DI-5-39), k is an integer of 1-5 each independently, and in formula (DI-5-40), n is an integer of 1 or 2.

[Formula 84]

In formulas (DI-5-42) to (DI-5-44), e is an integer of 2 to 10 independently, and in formula (DI-5-45), R ⁴³ is a hydrogen atom, -NHBoc Or -N (Boc) ₂ . In Formulas (DI-5-42) to (DI-5-44), Boc is a t-butoxycarbonyl group.

[Formula 85]

[Formula 86]

Examples of the diamine represented by the formula (DI-6) are shown below.

[Formula 87]

Examples of the diamine represented by the formula (DI-7) are shown below.

[Formula 88]

In formula (DI-7-3) and formula (DI-7-4), m is an integer of 1-12 each independently, n is 1 or 2 independently.

[Formula 89]

[Formula 90]

Examples of the diamine represented by the formula (DI-8) are shown below.

[Formula 91]

Examples of the diamine represented by the formula (DI-9) are shown below.

[Formula 92]

Examples of the diamine represented by the formula (DI-10) are shown below.

[Formula 93]

Examples of the diamine represented by the formula (DI-11) are shown below.

[Formula 94]

Examples of the diamine represented by the formula (DI-12) are shown below.

[Formula 95]

Examples of the diamine represented by the formula (DI-13) are shown below.

[Formula 96]

[Formula 97]

[Formula 98]

Examples of the diamine represented by the formula (DI-14) are shown below.

[Formula 99]

Examples of the diamine represented by the formula (DI-15) are shown below.

[Formula 100]

[Formula 101]

Examples of the diamine represented by the formula (DI-16) are shown below.

[Formula 102]

As dihydrazide which does not have a known side chain, the compound represented by either of the following formula (DIH-1) (DIH-3)-is mentioned.

[Formula 103]

In formula (DIH-1), G ²⁵ is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) ₂ -is represented.

In formula (DIH-2), ring D represents a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen atom of this group may be substituted by the methyl group, the ethyl group, or the phenyl group. In formula (DIH-3), ring E each independently represents a cyclohexane ring or a benzene ring, and at least one hydrogen atom of this group may be substituted with a methyl group, an ethyl group, or a phenyl group. Some E may mutually be same or different. Y represents a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2-. . In formula (DIH-2) and formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is any position.

Examples of the compound represented by any one of formulas (DIH-1) to (DIH-3) are shown below.

[Formula 104]

In formula (DIH-1-2), m is an integer of 1-12.

[Formula 105]

[Formula 106]

Such diamine and dihydrazide have the effect of improving electrical characteristics, such as lowering the ion density of the liquid crystal display device.

A diamine suitable for the purpose of increasing the pretilt angle will be described. As a diamine which has a side chain group suitable for the purpose of enlarging a pretilt angle, the diamond represented by any of Formula (DI-31)-(DI-35) and Formula (DI-36-1)-(DI-36-8) Min can be mentioned.

[Formula 107]

In formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH _2- , -CF ₂ O -, -OCF _2- , or-(CH ₂ ) _ma -are represented, and ma is an integer of 1-12. Preferred examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and an alkylene group having 1 to 3 carbon atoms, and particularly preferred examples are a single bond, -O-, -COO -, -OCO-, -CH ₂ O-, -CH _2- , and -CH ₂ CH _2- . R ²⁵ represents a group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl group, at least one hydrogen atom may be substituted with -F, and at least one -CH ₂ -may be substituted with -O-, -CH = CH- or -C≡C-. The hydrogen atoms of the phenyl _{group, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, or may be substituted by alkoxy of 3 to 30 carbon atoms or an alkyl group having a carbon number of 3 to 30. Although the bonding position of -NH2 _{couple |} bonded with the benzene ring shows arbitrary positions in the ring, it is preferable that the bonding position is a meta position or a para position. That is, the group "R ²⁵ -G ²⁶ -" when the top 1 a bonding site, two binding positions are preferably third and fifth, or 2nd and 5th.

[Formula 108]

In Formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, which are each independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more -CH ₂ of the alkylene group. -May be substituted with -O-, -COO-, -OCO-, -CONH-, or -CH = CH-. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,3-dioxane-2,5-diyl group, Pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, naphthalene-1,5-diyl group, naphthalene-2,7-diyl group or anthracene-9,10-diyl group, and ring B ^{In 21} , ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen atom may be substituted with -F or -CH ₃ , and s, t and u are each independently an integer of 0 to 2, The sum total of these is 1-5, and when s, t, or u is 2, the two bonding groups in each parenthesis may be same or different, and two rings may be same or different. R ²⁶ is a hydrogen atom, -F, -OH, an alkoxy group having 1 to 30 alkyl group, a fluorine-substituted alkyl group of 1 to 30 carbon atoms, having a carbon number of 1 to _{30, -CN, -OCH 2 F, -OCHF} 2, or - OCF ₃ may be represented and at least one —CH ₂ — of the alkyl group having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

[Formula 109]

In formula (DI-31-b), R <^27> and R <^28> is a C1-C3 alkyl group each independently, v is an integer of 1-6. Preferred examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

[Formula 110]

In formula (DI-32) and formula (DI-33), G ³⁰ independently represents a single bond, -CO- or -CH _2- , R ²⁹ independently represents a hydrogen atom or -CH ₃ , and R ³⁰ represents a hydrogen atom, a C1-C20 alkyl group, or a C2-C20 alkenyl group independently. At least one hydrogen atom of the benzene ring in Formula (DI-33) may be substituted by a C1-C20 alkyl group or a phenyl group. And the group in which the bond position is not fixed to any carbon atom which comprises a ring shows that the bond position in the ring is arbitrary. It is preferable that one of the two groups "-phenylene-G ³⁰ -O-" in the formula (DI-32) is bonded to the third position of the steroid nucleus, and the other is bonded to the sixth position of the steroid nucleus. Equation 2 groups in (DI-33) - coupling position of the benzene ring of the "phenylene group -G ³⁰ -O-" is, for the engaged position of the steroid nucleus, it is preferred that each of the above meta or para great. In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

[Formula 111]

In formula (DI-34) and formula (DI-35), G ³¹ independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² represents a single bond or an alkylene group having 1 to 3 carbon atoms. . R ³¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, at least one -CH ₂ in the alkyl group-is, or may be substituted with -O-, -CH = CH- or -C≡C-. R ³² represents an alkyl group having 6 to 22 carbon atoms, and R ³³ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group, and r is 0 or 1. And although -NH2 _{couple |} bonded with the benzene ring shows that the coupling | bonding position in the ring is arbitrary, it is preferable that it is a meta position or a para position independently with respect to the bonding position of G <^31> .

Examples of the compound represented by formula (DI-31) are shown below.

[Formula 112]

In formula (DI-31-1)-(DI-31-11), R <^34> represents a C1-C30 alkyl group or a C1-C30 alkoxy group each independently, Preferably it is a C5-C25 alkyl group Or an alkoxy group having 5 to 25 carbon atoms. R <^35> represents a C1-C30 alkyl group or a C1-C30 alkoxy group each independently, Preferably it is a C3-C25 alkyl group or a C3-C25 alkoxy group.

[Formula 113]

In Formulas (DI-31-12) to (DI-31-17), each of R ^{36 's} independently represents an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R ³⁷ 's each independently represent an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms.

[Formula 114]

[Formula 115]

[Formula 116]

Formula 117

[Formula 118]

In Formulas (DI-31-18) to (DI-31-43), each R ³⁸ independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and preferably an alkyl group having 3 to 20 carbon atoms. Or a C3-C20 alkoxy group. R ³⁹ each independently represents a hydrogen atom, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF _3, preferably 3 carbon atoms It is an alkyl group of -25, or a C3-C25 alkoxy group. And G ³³ represents an alkylene group having 1 to 20 carbon atoms.

Formula 119

[Formula 120]

[Formula 121]

[Formula 122]

Examples of the compound represented by formula (DI-32) are shown below.

Formula 123]

Examples of the compound represented by formula (DI-33) are shown below.

[Formula 124]

[Formula 125]

Examples of the compound represented by formula (DI-34) are shown below.

[Formula 126]

[Formula 127]

[Formula 128]

[Formula 129]

In formulas (DI-34-1) to (DI-34-12), each R ⁴⁰ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. And R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Examples of the compound represented by formula (DI-35) are shown below.

[Formula 130]

In formulas (DI-35-1) to (DI-35-3), each of R ^{37 's} independently represents an alkyl group having 6 to 30 carbon atoms, and R ⁴¹ ' s each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Indicates.

The compound represented by Formula (DI-36-1)-(DI-36-8) is shown below.

[Formula 131]

In formulas (DI-36-1) to (DI-36-8), each of R ^{42 's} independently represents an alkyl group having 3 to 30 carbon atoms.

In the said diamine and dihydrazide, the suitable material which improves each characteristic of the liquid crystal aligning film mentioned later is demonstrated. In the case of focusing more on improving the orientation of the liquid crystal, formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), and formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3), and formula (DI-11 It is preferable to use the compound represented by -2). In Formula (DI-5-1), m = 2, 4 or 6 is preferable and m = 4 is more preferable. In Formula (DI-5-12), m = 2-6 are preferable and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable and m = 1 is more preferable.

In the case of focusing on improving the transmittance, formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), and formula (DI- 5-24) and the diamine represented by a formula (DI-7-3) are preferable, and the compound represented by a formula (DI-2-1) is more preferable. In Formula (DI-5-1), it is preferable that it is m = 2, 4 or 6, and m = 4 is more preferable. In formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

In the case of focusing on improving the VHR of the liquid crystal display device, the formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), Using the compound represented by a formula (DI-4-15), a formula (DI-4-22), a formula (DI-5-28), a formula (DI-5-30), and a formula (DI-13-1) It is preferable that it is preferable, and diamine represented by a formula (DI-2-1), a formula (DI-5-1), and a formula (DI-13-1) is more preferable. In formula (DI-5-1), m = 1 is preferable. In Formula (DI-5-30), k = 2 is preferable.

By lowering the volume resistance value of the liquid crystal aligning film, improving the relaxation rate of the residual electric charge (residual DC) in the liquid crystal aligning film is effective as one of the methods of preventing sticking. When this purpose is important, Formula (DI-4-1), Formula (DI-4-2), Formula (DI-4-10), Formula (DI-4-15), and Formula (DI-5- 1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-4-20), formula (DI-4-21), formula ( It is preferable to use the compound represented by DI-7-12) and a formula (DI-16-1), and a formula (DI-4-1), a formula (DI-5-1), and a formula (DI-5- The compound represented by 13) is more preferable. In Formula (DI-5-1), m = 2, 4 or 6 is preferable and m = 4 is more preferable. In Formula (DI-5-12), m = 2-6 are preferable and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable and m = 1 is more preferable. In Formula (DI-7-12), m = 3 or 4 is preferable and m = 4 is more preferable.

In each diamine, a part of diamine may be substituted by monoamine in the range whose ratio of monoamine with respect to diamine is 40 mol% or less. Such substitution can cause the termination of the polymerization reaction when producing the polyamic acid, and can suppress the further progress of the polymerization reaction. For this reason, by such substitution, the molecular weight of the polymer (polyamic acid or its derivative) obtained can be easily controlled, for example, the coating property of a liquid crystal aligning agent can be improved, without the effect of this invention being impaired. . As long as the effect of this invention is not impaired, the diamine substituted by monoamine may be 1 type, or 2 or more types may be sufficient as it. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octa Decylamine and n-eicosylamine.

(Monoisocyanate)

When the monomer composition is a composition for synthesizing polyamic acid or a derivative thereof, for example, a diamine represented by formula (2) is included as the first monomer, and formula (II-1) and formula (II-) are used as the second monomer. 2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (IV-3), formula (V-1), formula (V-2) ), A compound represented by any one of formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1), formula (VIII-1), and formula (VIII-2) In addition, if necessary, when containing non-photoreactive tetracarboxylic dianhydride or its derivative (s), you may further contain a monoisocyanate compound in a monomer composition. By containing a monoisocyanate compound in a monomer composition, the terminal of the obtained polyamic acid or its derivative is modified, and molecular weight is adjusted. By using this terminal modified polyamic acid or its derivative, the coating characteristic of a liquid crystal aligning agent can be improved, for example, without the effect of this invention being impaired. It is preferable that content of the monoisocyanate compound in a monomer is 1-10 mol% with respect to the total amount of the diamine and tetracarboxylic dianhydride in a monomer from said viewpoint. As said monoisocyanate compound, phenyl isocyanate and naphthyl isocyanate are mentioned, for example.

(Combination of monomer)

As a combination of monomers in the monomer composition,

The first monomer is a diamine represented by formula (2), and the second monomer is formula (II-1), formula (III-1), formula (IV-1), formula (IV-3), formula (V -1) and a combination which is a compound (tetracarboxylic dianhydride) represented by any one of formula (VI-1),

The first monomer is a diamine represented by formula (2), and the second monomer is formula (II-2), formula (III-2), formula (IV-2), formula (V-2), formula (V -3), a compound (diamine) represented by any one of formula (VI-2), formula (VII-1), formula (VIII-1), and formula (VIII-2), and non-photoreactive as other monomers The combination which added tetracarboxylic dianhydride or its derivative (s) is mentioned. As a derivative of tetracarboxylic dianhydride, the compound etc. which substituted a part of acid dianhydride contained in tetracarboxylic acid diester, tetracarboxylic acid diester dichloride, and tetracarboxylic dianhydride compound with organic dicarboxylic acid are mentioned. Thereby, the structure represented by Formula (1) and Formula (II-1), Formula (III-1), Formula (IV-1), Formula (IV-3), Formula (V-1), or Formula (VI) The structure of the part except -CO-O-CO- in -1), and the polyamic acid which has the carbonyl group and carboxyl group converted from -CO-O-CO- in the structural unit of a principal chain, or Formula (1) Structure shown, formula (II-2), formula (III-2), formula (IV-2), formula (V-2), formula (V-3), formula (VI-2), formula (VII- 1), polyamic acid, and having a formula (VIII-1) or formula (VIII-2) converted from the structure -NH-, and -NH ₂ in portions except for the -NH ₂ in the structural unit of the main chain Derivatives of these polyamic acids can be obtained. Moreover, you may add said non-photoreactive diamine, non-photoreactive dihydrazide, and monoisocyanate further to these combinations.

[Polymer or Derivative thereof Polymerizing Monomer Composition]

The photoreactive polymer component contained in the liquid crystal aligning agent of this invention consists of a polymer obtained by superposing | polymerizing said monomer composition, or its derivative (s). Although each polymer which comprises a polymer component has a structural unit derived from a 1st structural unit, a 2nd structural unit, and the other monomer added as needed, respectively, the number and arrangement of each structural unit are the same as each other. You may or may not be different. Moreover, each derivative which comprises a polymer component is a structure corresponding to the structural unit derived from the structural unit corresponding to a 1st structural unit, the structural unit corresponding to a 2nd structural unit, and the other monomer added as needed, respectively. Although it has a unit, the number and arrangement | positioning of each structural unit may mutually be same or different.

Preferred types of polymers or derivatives thereof obtained by polymerizing monomer compositions include polyamic acid, polyamic acid derivatives, polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, and poly (styrene-phenylmaleimide) derivatives. And poly (meth) acrylates. Examples of the polyamic acid derivatives include polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide. As a polymer formed by superposing | polymerizing a monomer composition or its derivative, it is preferable that it is a polyamic acid and a polyamic acid derivative, and it is more preferable that it is polyamic acid.

Polyamic acid is a polymer synthesize | combined by the polymerization reaction of the diamine represented by Formula (DI), and the tetracarboxylic dianhydride represented by Formula (AN), and has a repeating unit represented by Formula (PAA). By dehydrating and ring-closing polyamic acid, the polyimide liquid crystal aligning film which has a repeating unit represented by Formula (PI) can be formed. Here, the diamine represented by Formula (2) is used as a 1st monomer here, for example, Formula (II-1), Formula (III-1), Formula (IV-1), (IV-) as a 2nd monomer 3), the compound (tetracarboxylic dianhydride) represented by any one of Formula (V-1) and Formula (VI-1) is used, or the diamine represented by Formula (2) is used as a 1st monomer, 2 Monomers of formula (II-2), formula (III-2), formula (IV-2), formula (V-2), formula (V-3), formula (VI-2), formula (VII-1 ), Azobenzene represented by Formula (1) by using a compound (diamine) represented by any one of Formula (VIII-1) and Formula (VIII-2) and using a non-photoreactive tetracarboxylic dianhydride as another monomer. Structure and formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (IV-3) ), Formula (V-1), formula (V-2), formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1), formula (VIII-1) , or a group represented by the formula (VIII-2) of -CO-O-CO-, or the structure of the portion other than the -NH _2, -CO-O-CO- It can obtain a polyamic acid having a structural transformation from -NH ₂ in the structural unit of the main chain.

[Formula 132]

[Formula 133]

In Formula (AN), Formula (PAA), and Formula (PI), X ¹ represents a tetravalent organic group. In Formula (DI), Formula (PAA), and Formula (PI), X ² represents a divalent organic group. About the preferable range and specific example of the tetravalent organic group in X <^1> , Formula (II-1), Formula (III-1), Formula (IV-1), (IV-3), Formula (V-1) ), And the corresponding structures of the structure of the moiety except for -CO-O-CO- and the tetracarboxylic dianhydrides described in the fields of (tetracarboxylic dianhydride) of formula (VI-1). have. About the preferable range and specific example of the bivalent organic group in X <^2> , The preferable range and specific example of the structure represented by Formula (1), Formula (II-2), Formula (III-2), Formula (IV- 2), the corresponding structures of formula (V-2), formula (V-3), formula (VI-2), formula (VII-1), formula (VIII-1), and formula (VIII-2) The structure of portions other than -NH ₂ ).

The derivatives of polyamic acid are compounds in which a part of the polyamic acid is substituted with another atom or atomic group to modify its properties, and in particular, it is preferable to increase the solubility in a solvent used in the liquid crystal aligning agent. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, polyamic acid amides, and the like. More specifically, 1) polyimide in which all amino groups and carboxyl groups in the polyamic acid are dehydrated and closed; 2) partial polyimide that has undergone partial dehydration ring closure, 3) polyamic acid ester in which the carboxyl group of polyamic acid is converted to ester, and 4) a portion of the acid dianhydride contained in the tetracarboxylic dianhydride compound is substituted with organic dicarboxylic acid for reaction. The polyamide acid-polyamide copolymer obtained, and the polyamide imide which carried out the dehydration ring-closing reaction part 5 or part of 5) the polyamic acid polyamide copolymer are mentioned. Among these derivatives, examples of the polyimide include those having a structural unit represented by the formula (PI), and examples of the polyamic acid ester include those having a structural unit represented by the following formula (PAE).

[Formula 134]

In formula (PAE), X <^1> is a tetravalent organic group, X <^2> is a divalent organic group, and Y represents an alkyl group. X ^1, it is possible to see the description of the X ^1, X ² in the desired range for the specific example of X ^2, equation (PAA). About description, preferable range, and specific example of Y, the description about a alkyl group in R ^<a> of said Formula (a-1), ^a preferable range, and a specific example can be referred.

(Method of Synthesis of Polymer from Monomer Composition)

The polymerization of the first monomer, the second monomer, and other monomers added as necessary and the generation of the derivative from the obtained polymer can be carried out under the reaction conditions usually used.

Below, the case where a monomer composition consists of a monomer for synthesize | combining a polyamic acid or its derivative (s) is demonstrated about the polymerization reaction conditions of this monomer, and reaction conditions for producing a derivative | guide_body.

The synthesis of the polyamic acid and its derivatives from the monomer composition can be carried out in the same manner as the synthesis of the known polyamic acid or its derivatives used for forming the film of the polyimide.

For example, it is preferable that the total introduction amount of tetracarboxylic dianhydride shall be 0.9-1.1 mol with respect to 1 mol of total diamines.

Moreover, when making polyamic acid obtained by superposing | polymerizing a monomer composition as the polyimide which is a polyamic acid derivative, the obtained polyamic acid solution is made up of acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride which are dehydrating agents, and dehydration ring closure. Polyimide can be obtained by carrying out the imidation reaction at the temperature of 20-150 degreeC with tertiary amines, such as triethylamine, a pyridine, and a collidine which are catalysts. Or from the obtained polyamic acid solution, polyamic acid is precipitated using a large amount of poor solvents (alcohol solvents, such as methanol, ethanol, and isopropanol, and a glycol solvent), and the precipitated polyamic acid, such as toluene, xylene, etc. Polyimide can also be obtained by imidation reaction at the temperature of 20-150 degreeC with said dehydrating agent and dehydration ring-closure catalyst in a solvent.

In this imidation reaction, it is preferable that the ratio of a dehydrating agent and a dehydration ring-closure catalyst is 0.1-10 (molar ratio). It is preferable that the total usage-amount of a dehydrating agent and a dehydration ring closure catalyst is 1.5-10 times mole with respect to the sum total of the molar amount of the tetracarboxylic dianhydride used for the synthesis | combination of the said polyamic acid. By adjusting the dehydrating agent used for this imidation reaction, catalyst amount, reaction temperature, and reaction time, the degree of imidation can be controlled, and thereby the partial polyimide which only a part of polyamic acid imidated other than polyimide can be obtained. . The obtained polyimide or partial polyimide may be separated from the solvent used for the reaction, redissolved in another solvent and used as a liquid crystal aligning agent, or may be used as a liquid crystal aligning agent without separating from the solvent.

The polyamic acid ester is synthesized by reacting a polyamic acid obtained by polymerizing a monomer composition with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or a tetracarboxylic acid diester or tetracarboxylic acid diester derived from tetracarboxylic dianhydride. It can obtain by the method of synthesize | combining by making dichloride and diamine react. The tetracarboxylic acid diester derived from tetracarboxylic dianhydride can be obtained, for example, by reacting the tetracarboxylic dianhydride with 2 equivalents of alcohol and ring opening, and the tetracarboxylic acid diester dichloride has 2 equivalents of tetracarboxylic acid diester. It can obtain by making it react with a chlorinating agent (for example, chlorinated thionyl etc.). In addition, the polyamic acid ester may have only a dark acid ester structure, and may be a partial ester compound in which a dark acid structure and a dark acid ester structure coexist.

The liquid crystal aligning agent for photo-alignment of this invention may include only one type of these polymers or its derivative (especially polyamic acid or its derivative), and may contain it two or more types.

It is preferable that it is 7,000-500,000 in weight average molecular weight (Mw) of polystyrene conversion, and, as for the molecular weight of polyamic acid or its derivatives, it is more preferable that it is 10,000-200,000. The molecular weight of polyamic acid or its derivative can be calculated | required from the measurement by a gel permeation chromatography (GPC) method.

The polyamic acid or derivatives thereof obtained by polymerizing the monomer composition, and the derivatives produced from the polyamic acid, are analyzed by analyzing the solids obtained by precipitation with a large amount of poor solvent by IR (infrared spectroscopy) or NMR (nuclear magnetic resonance analysis). You can check it. In addition, extracts obtained by organic solvents of polyamic acids or decomposition products of derivatives thereof with aqueous solutions of strong alkalis such as KOH and NaOH are subjected to GC (gas chromatography), HPLC (high-speed liquid chromatography) or GC-MS (gas chromatography mass spectrometry). By analyzing by, the monomer used can be confirmed.

<Preferred Embodiment of Polymer Component>

The liquid crystal aligning agent of this invention may contain one type of photoreactive polymer component obtained from the single monomer composition, and may contain two or more types of photoreactive polymer components from which the composition of a monomer composition differs. In the case of focusing on the liquid crystal alignment of the liquid crystal alignment film formed by using the liquid crystal aligning agent of the present invention, the photoreactive polymer component is preferably made of polyamic acid or a derivative thereof, and the liquid crystal aligning agent is composed of polyamic acid or a derivative thereof. It is preferable to contain two or more types of photoreactive polymer components.

In addition, in this specification, the liquid crystal aligning agent containing only one type of polymer component may be called a single-layer liquid crystal aligning agent. Moreover, the liquid crystal aligning agent containing 2 or more types of polymer components may be called a blend type liquid crystal aligning agent. At least 1 sort (s) may be a photoreactive polymer component, and the some polymer component in a blend type liquid crystal aligning agent may contain the non-photoreactive polymer component. Here, a "non-photoreactive polymer component" is a polymer component which consists of a polymer which polymerizes a monomer composition, or its derivative (s), and means that a monomer composition consists of a non-photoreactive monomer.

When placing importance on the balance of the storage stability of a liquid crystal aligning agent, the printability to the display element substrate of a liquid crystal aligning agent, and the characteristic of the liquid crystal aligning film formed, it is preferable that it is a blend type liquid crystal aligning agent. As a preferable example of a blend type liquid crystal aligning agent, it is a monomer composition containing the 1st photoreactive polymer component obtained from the monomer composition containing at least a 1st monomer and a 2nd monomer, and at least a 1st monomer and a 2nd monomer, Blend type liquid crystal aligning agent which combined the 2nd photoreactive polymer component obtained from the monomer composition from a monomer composition used as a photoreactive polymer, and the photoreactive polymer component obtained from the monomer composition containing at least a 1st monomer and a 2nd monomer. And a blend type liquid crystal aligning agent obtained by combining a non-photoreactive polymer component. Here, it is preferable that the non-photoreactive polymer component is obtained from the monomer composition containing the monomer for synthesize | combining a polyamic acid or its derivative (s). For preferred ranges and specific examples of the tetracarboxylic dianhydride, diamine, and other monomers used for the monomer of the non-photoreactive polymer component, (non-photoreactive tetracarboxylic dianhydride), (non-photoreactive diamine and non-reactive dihydrazide) And description of the columns of (monoisocyanate).

In the case of using such two kinds of polymer components, for example, one selects a polymer component having excellent performance in liquid crystal alignment and the other selects a polymer component having excellent performance in improving electrical characteristics of the liquid crystal display device. There is an aspect. In this case, the process of apply | coating the liquid crystal aligning agent which melt | dissolved these polymer components in the solvent to a board | substrate, and performing preliminary drying, and forming a thin film by controlling the structure and molecular weight of the polymer which each polymer component contains, are mentioned later. In the above, the polymer component having the excellent liquid crystal alignment ability can be segregated in the upper layer of the thin film, and the polymer component having the excellent performance in improving the electrical characteristics of the liquid crystal display element in the lower layer of the thin film. The phenomenon in which the polymer component which consists of a polymer with a small surface energy is isolate | separated to the upper layer, and the polymer component which consists of a polymer with a large surface energy in a lower layer is applicable to this mixed polymer component. Confirmation of such layer separation can be confirmed if the surface energy of the formed liquid crystal aligning film is the same as or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer component intended to segregate to an upper layer.

As a method of expressing layer separation, it is also possible to reduce the molecular weight of the polymer in the polymer component to be segregated in the upper layer.

Moreover, in the liquid crystal aligning agent which consists of mixing of polyamic acids, layer separation can also be expressed by making the polymer component to segregate to an upper layer from polyimide.

The first monomer and the second monomer may be contained in the monomer composition for the polymer component segregating in the upper layer of the thin film, in the monomer composition for the polymer component segregating in the lower layer of the thin film, or in both monomer compositions. You may make it contain. For the preferable ranges and specific examples of the first monomer and the second monomer for obtaining the polyamic acid or derivatives thereof, reference may be made to the descriptions of the columns of the [first monomer] and the [second monomer].

When the polymer component which segregates in the upper layer of a thin film consists of polyamic acid or its derivative (s), it can select as a tetracarboxylic dianhydride used for the synthesis, without restricting from the well-known tetracarboxylic dianhydrides illustrated above.

For example, tetracarboxylic dianhydride is formula (AN-1-1), formula (AN-2-1), formula (AN-3-1), formula (AN-4-5), and formula (AN The compound represented by -4-17) is preferable, and a formula (AN-4-17) is more preferable. In Formula (AN-4-17), m = 4 or 8 is preferable and m = 8 is more preferable.

Moreover, when the polymer component segregated in the upper layer of a thin film consists of polyamic acid or its derivative (s), it is a non-photoreactive diamine and non-photoreactive dihydrazide used for the synthesis | combination, The well-known diamine and dihai mentioned above are mentioned. We can choose without being limited from drazide.

For example, as non-photoreactive diamine and non-photoreactive dihydrazide, formula (DI-4-1), formula (DI-4-13), formula (DI-4-15), formula (DI-5- It is preferable to use the compound represented by 1), a formula (DI-7-3), and a formula (DI-13-1). Especially, it is more preferable to use the compound represented by Formula (DI-4-13), Formula (DI-4-15), Formula (DI-5-1), and Formula (DI-13-1). In formula (DI-5-1), m = 1, 2 or 4 is preferable and m = 4 is more preferable. In formula (DI-7-3), m = 3 and n = 1 are preferable.

It is preferable to contain 30 mol% or more of aromatic diamine in the total amount of a non-photoreactive diamine, and, as for the non-photoreactive diamine used for synthesis | combination, it is more preferable to contain 50 mol% or more.

When the polymer component which segregates in the lower layer of a thin film consists of polyamic acid or its derivative (s), it can select as tetracarboxylic dianhydride used for the synthesis, without restricting from the well-known tetracarboxylic dianhydride illustrated above.

For example, tetracarboxylic dianhydride is a formula (AN-1-1), a formula (AN-1-13), a formula (AN-2-1), a formula (AN-3-2), and a formula (AN The compound represented by -4-21) is preferable, and a formula (AN-1-1), a formula (AN-2-1), and a formula (AN-3-2) are more preferable.

It is preferable to contain 10 mol% or more of aromatic tetracarboxylic dianhydride in the total amount of tetracarboxylic dianhydride, and, as for the tetracarboxylic dianhydride used for synthesis, it is more preferable to contain 30 mol% or more.

When the polymer component which segregates in the lower layer of a thin film consists of polyamic acid or its derivative (s), it can select as a diamine and dihydrazide used for the synthesis, without restrict | limiting from the well-known diamine illustrated above.

For example, diamine and dihydrazide are formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-18), formula (DI-4-19), formula (DI-5-9), formula (DI-5-28), formula (DI-5-30), formula (DI-13-1), and formula (DIH-2 The compound represented by -1) is preferable. Especially, it is represented by Formula (DI-4-1), Formula (DI-4-18), Formula (DI-4-19), Formula (DI-5-9), and Formula (DI-13-1). More preferred are compounds. In formula (DI-5-30), the diamine whose k = 2 is preferable.

It is preferable to contain 30 mol% or more of aromatic diamine with respect to all diamine, and, as for the diamine used for synthesis | combination, it is more preferable to contain 50 mol% or more.

As for the polymer component which consists of polyamic acid or its derivative which segregates in the upper layer of a thin film, 5 weight%-50 weight% are preferable with respect to the total amount of this polymer component and the polymer component which consists of polyamic acid or its derivative which segregates in the lower layer of a thin film. 10 weight%-40 weight% are more preferable.

<Other components of the liquid crystal aligning agent>

The liquid crystal aligning agent contains at least the polymer component (photoreactive polymer component) which has a structural unit containing a photoreactive structure, and may contain the other component. As another component, the polymer component (non-photoreactive polymer component) which does not have a structural unit containing a photoreactive structure, a solvent, and an additive are mentioned.

For the description of the non-photoreactive polymer component, reference may be made to the corresponding description in the column of <Preferred Embodiment of Polymer Component>.

[solvent]

The liquid crystal aligning agent of this invention may contain the solvent further from a viewpoint of adjustment of the applicability | paintability of a liquid crystal aligning agent, and the density | concentration of a polymer component. The solvent can be applied without particular limitation as long as it is a solvent having the ability to dissolve the polymer constituting the polymer component. As a solvent, the solvent etc. which are normally used for the manufacturing process of polymer components, such as a polyamic acid and a soluble polyimide, and various uses can be used, for example, It can select suitably according to a use purpose. 1 type may be sufficient as a solvent, or 2 or more types of mixed solvents may be sufficient as it.

As a solvent, the solvent of polyamic acid or its derivative (s), and the other solvent for the purpose of improving applicability | paintability are mentioned.

For example, an aprotic polar organic solvent that is a solvent of polyamic acid or a derivative thereof can be used. Specifically, N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam , N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, N, N-dimethyl Lactone, such as isobutyl amide, (gamma) -butyrolactone, and (gamma) -valerolactone, is mentioned.

Examples of other solvents for the purpose of improving coating properties include diisobutyl ketone, alkyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, 4-methyl-2-pentanol, and diisobutyl carbinol. Diethylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ethers such as tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether, and diethylene Diethylene glycol dialkyl ethers such as glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, ethylene glycol monoalkyl or phenyl acetate, tri Propylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ether, propylene glycol monomethyl ether, 1-butoxy-2-propanol, and malonic acid dialkyls such as diethyl malonic acid and dipropylene Dip, such as glycol monomethyl ether Propylene glycol monoalkyl emitter to a call, there may be mentioned esters of these compounds, such as acetates.

In these, the solvent of a liquid crystal aligning agent is N-methyl- 2-pyrrolidone, dimethyl imidazolidinone, (gamma) -butyrolactone, (gamma) -valerolactone, diisobutyl ketone, and 4-methyl- 2- Pentanol, diisobutylcarbinol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene More preferred are glycol butyl methyl ether, 1-butoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and butyl cellosolve acetate.

For example, when the liquid crystal aligning agent which used polyamic acid for the photoreactive polymer component contains a solvent, it is preferable that the density | concentration of the polyamic acid in a liquid crystal aligning agent is 0.1-40 weight%. When apply | coating this liquid crystal aligning agent to a board | substrate, the operation which dilutes the polyamic acid contained with the solvent in advance may be needed for adjustment of a film thickness.

Solid content concentration in a liquid crystal aligning agent is not specifically limited, It is preferable to select suitably according to the coating method of a liquid crystal aligning agent. In order to suppress the nonuniformity, pinhole, etc. at the time of application | coating, Usually, it is 0.1-30 weight% with respect to liquid crystal aligning agent whole quantity, More preferably, it is 1-10 weight%.

Although the viscosity of a liquid crystal aligning agent changes with the method used for application | coating of a liquid crystal aligning agent, the kind and concentration of the polymer contained as a polymer component, the kind and concentration of a solvent, etc., when apply | coating a liquid crystal aligning agent with a printing machine, for example, , It is preferable that it is 5-100 mPa * s, and it is more preferable that it is 10-80 mPa * s. Thereby, printing nonuniformity can be suppressed and a liquid crystal aligning film can be formed with sufficient film thickness. Moreover, when apply | coating a liquid crystal aligning agent by a spin coat, it is preferable that it is 5-200 mPa * s, and, as for the viscosity of a liquid crystal aligning agent, it is more preferable that it is 10-100 mPa * s. When apply | coating a liquid crystal aligning agent with an inkjet coating apparatus, it is preferable that it is 5-50 mPa * s, and, as for the viscosity of a liquid crystal aligning agent, it is more preferable that it is 5-20 mPa * s.

The viscosity of a liquid crystal aligning agent is measured by the rotational viscosity measuring method, and is measured (measurement temperature: 25 degreeC), for example using a rotational viscometer (The TVE-20L type made by Toki Sangyo).

[additive]

The liquid crystal aligning agent of this invention may contain the various additives further. Various additives can be selected and used according to the respective purposes in order to improve various characteristics of the alignment film. An example is shown below.

(Alkenyl Substituted Nadiimide Compound)

For example, the liquid crystal aligning agent of this invention may contain the alkenyl substituted nadiimide compound further in order to stabilize the electrical characteristic of a liquid crystal display element for a long term. An alkenyl substituted nadiimide compound may be used by 1 type, and may use 2 or more types together. It is preferable that content of an alkenyl substituted nadiimide compound is 1-50 weight% with respect to polyamic acid or its derivative | guide_body, It is more preferable that it is 1-30 weight%, It is 1-20 weight% More preferred. It is preferable that an alkenyl substituted nadiimide compound is a compound which can be dissolved in the solvent which melt | dissolves the polyamic acid or its derivative (s) used by this invention. As a preferable alkenyl substituted nadiimide compound, the alkenyl substituted nadiimide compound disclosed by Unexamined-Japanese-Patent No. 2008-096979, Unexamined-Japanese-Patent No. 2009-109987, and Unexamined-Japanese-Patent No. 2013-242526 is mentioned. Particularly preferred alkenyl substituted nadiimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane, N, N'-m-xyl Reylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboxyimide) is mentioned.

(Compound having a radical polymerizable unsaturated double bond)

For example, the liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond in order to stabilize the electrical characteristic of a liquid crystal display element for a long term. 1 type of compounds may be sufficient as the compound which has a radically polymerizable unsaturated double bond, and 2 or more types of compounds may be sufficient as it. However, an alkenyl substituted nadiimide compound is not contained in the compound which has a radically polymerizable unsaturated double bond. Preferred examples of the compound having a radically polymerizable unsaturated double bond include N, N'-methylenebisacrylamide, N, N'-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4'-methylene. Bis (N, N-dihydroxyethylene acrylate aniline), cyanuric acid triallyl, and others, JP-A-2009-109987, JP-A-2013-242526, JP-A-2014 / 119682, The compound which has a radically polymerizable unsaturated double bond as disclosed in international publication 2015/152014 is mentioned. It is preferable that it is 1-50 weight% with respect to polyamic acid or its derivative | guide_body, and, as for content of the compound which has a radically polymerizable unsaturated double bond, it is more preferable that it is 1-30 weight%.

(Oxazine compound)

For example, the liquid crystal aligning agent of this invention may contain the oxazine compound further in order to stabilize the electrical characteristic in a liquid crystal display element for a long term. The oxazine compound may be one kind of compound or two or more kinds of compounds. It is preferable that content of an oxazine compound is 0.1-50 weight% with respect to polyamic acid or its derivative | guide_body for said objective, It is more preferable that it is 1-40 weight%, It is more preferable that it is 1-20 weight%. .

An oxazine compound is soluble in the solvent which melt | dissolves polyamic acid or its derivative (s), and the oxazine compound which has ring-opening polymerization property is preferable. Preferred oxazine compounds include oxazine compounds represented by formula (OX-3-1), formula (OX-3-9) and formula (OX-3-10), in addition, JP 2007-286597, The oxazine compound disclosed in Unexamined-Japanese-Patent No. 2013-242526 is mentioned.

[Formula 135]

(Oxazoline compound)

For example, the liquid crystal aligning agent of this invention may contain the oxazoline compound further in order to stabilize the electrical characteristic in a liquid crystal display element for a long term. An oxazoline compound is a compound which has an oxazoline structure. An oxazoline compound may be 1 type of compounds, or 2 or more types of compounds may be sufficient as it. It is preferable that content of an oxazoline compound is 0.1-50 weight% with respect to polyamic acid or its derivative | guide_body for said objective, It is more preferable that it is 1-40 weight%, It is more preferable that it is 1-20 weight%. . As a preferable oxazoline compound, the oxazoline compound disclosed by Unexamined-Japanese-Patent No. 2010-054872 and Unexamined-Japanese-Patent No. 2013-242526 is mentioned. More preferably, 1, 3-bis (4, 5- dihydro-2-oxazolyl) benzene is mentioned.

(Epoxy compound)

For example, the liquid crystal aligning agent of this invention further adds an epoxy compound for the purpose of stabilizing the electrical property in a liquid crystal display element for a long term, the objective of improving the hardness of a film, or the objective of improving adhesiveness with a sealing compound. You may contain it. 1 type of compounds may be sufficient as an epoxy compound, and 2 or more types of compounds may be sufficient as it. It is preferable that content of an epoxy compound is 0.1-50 weight% with respect to polyamic acid or its derivative (s) for the said objective, It is more preferable that it is 1-20 weight%, It is more preferable that it is 1-10 weight%.

As the epoxy compound, various compounds having one or two or more epoxy rings in the molecule can be used.

For the purpose of improving the hardness of the film or the purpose of improving the adhesion with the sealing agent, a compound having two or more epoxy rings in the molecule is preferable, and a compound having three or four is more preferable.

As an epoxy compound, the epoxy compound disclosed by Unexamined-Japanese-Patent No. 2009-175715, Unexamined-Japanese-Patent No. 2013-242526, Unexamined-Japanese-Patent No. 2016-170409, and International Publication 2017/217413 is mentioned. Preferred epoxy compounds include N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3,3 ', 4,4'-diepoxy) bicyclohexyl, 1, 4-butanediol glycidyl ether, isocyanuric acid tris (2,3-epoxypropyl), 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-m-xylenediamine is mentioned.

In addition to the above, an oligomer or a polymer having an epoxy ring can be added. As an oligomer or polymer which has an epoxy ring, the oligomer and polymer disclosed by Unexamined-Japanese-Patent No. 2013-242526 can be used.

(Silane compound)

For example, the liquid crystal aligning agent of this invention may contain the silane compound further in order to improve adhesiveness with a board | substrate and a sealing compound. It is preferable that content of a silane compound is 0.1-30 weight% with respect to polyamic acid or its derivative | guide_body for said objective, It is more preferable that it is 0.5-20 weight%, It is more preferable that it is 0.5-10 weight%. .

As a silane coupling agent, the silane coupling agent disclosed by Unexamined-Japanese-Patent No. 2013-242526, Unexamined-Japanese-Patent No. 2015-212807, Unexamined-Japanese-Patent No. 2018-173545, and International Publication No. 2018/181566 can be used. .

As preferred silane coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, para Aminophenyltrimethoxysilane, and 3-aminopropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-trimethoxypropyl succinic acid, 3-triethoxypropyl succinic acid, 3-isocyanate propyl triethoxy silane and 3-ureidopropyl triethoxy silane are mentioned.

In addition to the additives described above, a compound having a cyclocarbonate group, a compound having a hydroxyalkylamide moiety or a hydroxyl group may be added for the purpose of increasing the strength of the alignment film or stabilizing the electrical properties of the liquid crystal display device in the long term. have. As a specific compound, the compound disclosed by Unexamined-Japanese-Patent No. 2016-118753 and international publication 2017/110976 is mentioned. As a preferable compound, the following formula (HD-1)-a formula (HD-4) are mentioned. It is preferable that these compounds are 0.5-50 weight% with respect to polyamic acid or its derivatives, It is more preferable that it is 1-30 weight%, It is more preferable that it is 1-10 weight%.

[Formula 136]

Moreover, when the improvement of antistatic is required, the imidation catalyst can also be used, when imidation advances at an antistatic agent and low temperature. As an imidation catalyst, the imidation catalyst disclosed by Unexamined-Japanese-Patent No. 2013-242526 is mentioned.

Liquid crystal alignment film

Next, the liquid crystal aligning film of this invention is demonstrated.

The liquid crystal aligning film of this invention is formed with the liquid crystal aligning agent for photoalignments of this invention.

For description, preferred ranges, and specific examples of the liquid crystal aligning agent for photoalignment of the present invention, description of the column of the liquid crystal aligning agent for photo alignment can be referred to.

Below, an example of the formation method of the liquid crystal aligning film by the liquid crystal aligning agent (liquid crystal aligning agent) for photo-alignment of this invention is demonstrated.

The liquid crystal aligning film of this invention can be obtained by the normal method of manufacturing a liquid crystal aligning film from a liquid crystal aligning agent. The liquid crystal aligning film of this invention irradiates light to the process of forming the coating film of the liquid crystal aligning agent of this invention, the process of heating-drying a coating film, and forming the film of a liquid crystal aligning agent, and anisotropy, for example. It can obtain by passing through the process (orientation process) which gives a (crystallization process), and the process (heat baking process) which heat-calculates the film of the liquid crystal aligning agent which provided the anisotropy. In this heat baking, in this invention, the 1st structural unit of the polymer which comprises the polymer chain of a liquid crystal aligning film, or its derivative (s) produces a chemical reaction, the photoreactive group for photo-alignment loses, and the number of photoreactive groups in the whole film | membrane is lost. Or no photoreactive group is present. For this reason, the formed liquid crystal aligning film hardly generate | occur | produces a radical even when exposed to strong light, and shows high stability with respect to light. At this time, since the second structural unit of the polymer or its derivative does not cause a chemical reaction but maintains the structure immediately after the photoalignment treatment, the structure effectively contributes to the anisotropy of the polymer main chain. Thereby, the formed liquid crystal aligning film exhibits favorable liquid crystal alignability in addition to having high stability with respect to light.

A coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to manufacture of a normal liquid crystal aligning film. Substrate, ITO (IndiumTinOxide), IZO ( In 2 O 3 -ZnO), IGZO (In-Ga-ZnO 4) electrode or the like in the electrode and the color filter, such as a glass, silicon nitride claim, the acrylic, polycarbonate, which may come Substrate, such as the agent made by polyimide, is mentioned.

As a method of apply | coating a liquid crystal aligning agent to a board | substrate, the spinner method, the printing method, the dipping method, the dropping method, the inkjet method, etc. are generally known. These methods are similarly applicable to this invention.

As a heat drying process, the method of heat-processing in oven or an infrared furnace, the method of heat-processing on a hotplate, etc. are generally known. It is preferable to perform a heat drying process at the temperature within the range which can evaporate a solvent, and it is more preferable to carry out at relatively low temperature with respect to the temperature in a heat baking process. Specifically, the heat drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

The heat firing step can be performed, for example, under conditions necessary for the polyamic acid or its derivative constituting the photoreactive polymer component to exhibit a dehydration and ring closure reaction. As the baking of a coating film, the method of heat-processing in oven or infrared furnace, the method of heat-processing on a hotplate, etc. are generally known. These methods are similarly applicable in this invention. It is preferable that heating temperature is 40-300 degreeC, It is more preferable that it is 100-300 degreeC, It is more preferable that it is 120-280 degreeC, It is still more preferable that it is 150-250 degreeC. It is preferable that heating time is 1 minute-3 hours, It is more preferable that it is 5 minutes-1 hour, It is more preferable that it is 15 minutes-45 minutes. It is preferable to adjust heating time according to heating temperature, For example, when heating temperature is 40-180 degreeC, it is preferable that heating time is 10 minutes-3 hours, and when heating temperature is 180-300 degreeC, heating time is It is preferable that it is 1 minute-1 hour. Especially, since the reaction efficiency can be improved, it is more preferable that heating time is 10 minutes-1 hour at 150-280 degreeC, and heating time is 15 minutes-45 minutes at 180-250 degreeC of heating temperature. More preferred.

Moreover, heat baking can also be performed in multiple times at different temperature. At this time, you may use the some heating apparatus set to the other temperature, and you may carry out, changing to another temperature one by one using one heating apparatus. When heat-firing twice at another temperature, it is preferable to carry out at the temperature of 90-180 degreeC for the 1st time, and the temperature of 185 degreeC or more for the 2nd time. Moreover, it can bake by changing a temperature from low temperature to high temperature. When baking is performed by changing temperature, 90-180 degreeC of initial temperature is preferable. 185-300 degreeC is preferable and, as for final temperature, 190-230 degreeC is more preferable.

In the formation method of the liquid crystal aligning film of this invention, in order to orientate a liquid crystal to one direction with respect to a horizontal and / or a vertical direction, a well-known optical orientation method can be used suitably as a means of providing anisotropy to a thin film.

The formation method of the liquid crystal aligning film of this invention by the photo-alignment method is demonstrated in detail. The liquid crystal aligning film of this invention using the photo-alignment method can be formed by giving anisotropy to a thin film by irradiating linearly polarized light or non-polarization of radiation to the thin film after heat-drying a coating film, and heating and baking the film. Alternatively, the coating film can be formed by heating and drying the film, followed by heating and baking, to irradiate linearly polarized light or non-polarized light on the thin film. It is preferable to perform a radiation irradiation process before a heat baking process from an orientation point.

Moreover, in order to raise the liquid crystal aligning ability of a liquid crystal aligning film, you may irradiate linearly polarized light or non-polarization of radiation, heating a coating film. Irradiation of a radiation may be performed in the process of heat-drying a coating film, or the process of heat baking, and may be performed between a heat drying process and a heat baking process. The heat-drying temperature in the process is preferably in the range of 30 ° C to 150 ° C, more preferably in the range of 50 ° C to 120 ° C. Moreover, it is preferable that the heating baking temperature in the process is the range of 30 to 300 degreeC, and also the range of 50 to 250 degreeC.

As a radiation, although the ultraviolet-ray or visible light containing the light of the wavelength of 150-800 nm can be used, the ultraviolet-ray containing 300-400 nm light is preferable, for example. Moreover, linearly polarized light or non-polarized light can be used. Although these lights will not be specifically limited if it is the light which can provide liquid crystal aligning ability to the said thin film, linear polarization is preferable when it is going to express strong orientation control force with respect to a liquid crystal.

The liquid crystal aligning film of this invention can exhibit high liquid crystal aligning ability also by the low energy light irradiation. It is preferable that it is 0.05-20J / cm <^2> , and, as for the irradiation amount of the linearly polarized light in the said irradiation process, 0.5-10J / cm <^2> is more preferable. Moreover, it is preferable that it is 200-400 nm, and, as for the wavelength of linearly polarized light, it is more preferable that it is 300-400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not specifically limited, In order to express the strong orientation control force with respect to a liquid crystal, it is preferable from a viewpoint of shortening an orientation processing time that it is as perpendicular | vertical as possible with respect to a film surface. Moreover, the liquid crystal aligning film of this invention can orientate a liquid crystal in a perpendicular | vertical direction with respect to the polarization direction of linearly polarized light by irradiating linearly polarized light.

The light source used in the process of irradiating linearly polarized light or polarized light of radiation includes ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, Deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, Mercury xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, LED lamps, sodium lamps, microwave excited electrodeless lamps and the like can be used without limitation.

The liquid crystal aligning film of this invention is obtained suitably by the method further including the process other than the above-mentioned process. For example, the liquid crystal aligning film of this invention does not make the process of wash | cleaning the film | membrane after baking or irradiation with a washing | cleaning liquid, but a washing | cleaning process can be provided in the circumstances of another process.

As a washing | cleaning method with a washing | cleaning liquid, brushing, jet spray, steam washing | cleaning, ultrasonic washing | cleaning, etc. are mentioned. These methods may be performed independently or may be used together. As a washing | cleaning liquid, various alcohols, such as pure water or methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons, such as benzene, toluene, and xylene, halogen solvents, such as methylene chloride, ketones, such as acetone and methyl ethyl ketone Although it can use, it is not limited to these. Of course, these washing | cleaning liquids use those with few impurities refine | purified fully. Such a cleaning method can be applied also to the said washing process in formation of the liquid crystal aligning film of this invention.

In order to raise the liquid-crystal aligning ability of the liquid crystal aligning film of this invention, the annealing process by heat and light can be used before and after a heating baking process or before and after the irradiation of polarized light or polarized light. In the annealing treatment, the annealing temperature is 30 to 180 ° C, preferably 50 to 150 ° C, and the time is preferably 1 minute to 2 hours. Moreover, UV lamp, fluorescent lamp, LED lamp etc. are mentioned as annealing light used for an annealing process. It is preferable that the irradiation amount of light is 0.3-10J / cm <^2> .

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal aligning film of this invention can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer.

The liquid crystal aligning film of this invention has the anisotropy of especially large orientation, It is characterized by the above-mentioned. The magnitude of such anisotropy can be evaluated by the method using polarization IR as described in Unexamined-Japanese-Patent No. 2005-275364. Moreover, it can also evaluate by the method using ellipsometry. In detail, the retardation value of a liquid crystal aligning film can be measured with a spectral ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer backbone. That is, when the film | membrane of the polymer which has a big retardation value has a big orientation degree, and is used as a liquid crystal aligning film, it is thought that the liquid crystal aligning film which has larger anisotropy has a big orientation regulation force with respect to a liquid crystal composition.

The liquid crystal aligning film of this invention can be used suitably for the liquid crystal display element of a transverse electric field system. When used for a transverse electric field type liquid crystal display element, the smaller the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state, and the contrast is improved. As for Pt angle, 0.1 degrees or less are preferable.

The liquid crystal aligning film of this invention can be used for orientation control of the liquid crystal composition for liquid crystal displays, such as a smartphone, a tablet, a vehicle monitor, and a television. In addition to the orientation use of the liquid crystal composition for liquid crystal displays, it can use for the orientation control of an optical compensation material and all other liquid crystal materials. Moreover, since the liquid crystal aligning film of this invention has big anisotropy, it can be used independently for an optical compensation material use.

Liquid crystal display device

Next, the liquid crystal display element of this invention is demonstrated.

The liquid crystal display element of this invention has the characteristics in the point which has the liquid crystal aligning film of this invention. The description of the column of a liquid crystal aligning film can be referred for description, a preferable range, and a specific example of the liquid crystal aligning film of this invention, its formation method.

If the liquid crystal aligning film of this invention is a case where a liquid crystal aligning film of this invention is equipped with a high brightness backlight, high voltage retention will be maintained and high display quality can be implement | achieved. Moreover, the liquid crystal aligning film excellent in the liquid crystal aligning film is high, contrast is high, and a clear contrast display can be implement | achieved.

The liquid crystal display element of this invention is demonstrated in detail. The present invention provides a pair of substrates that are arranged to face each other, an electrode formed on one or both sides of a surface of each of the pair of substrates, and a surface formed on the surface of each of the pair of substrates. In a liquid crystal display element having a liquid crystal alignment film, a liquid crystal layer formed between the pair of substrates, and a pair of polarizing films, backlights, and driving devices provided between the opposing substrates, the liquid crystal alignment film according to the present invention. It is comprised by the liquid crystal aligning film.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. As such an electrode, ITO, a metal vapor deposition film, etc. are mentioned, for example. Moreover, the electrode may be formed in the whole surface of one surface of a board | substrate, for example, may be formed in the desired shape patterned. As said desired shape of an electrode, a comb shape or a zigzag structure etc. are mentioned, for example. An electrode may be formed in one board | substrate among a pair of board | substrates, and may be formed in both board | substrates. Formation of the electrode varies depending on the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element (transverse electric field type liquid crystal display element), an electrode is arranged on one side of the pair of substrates, and other liquid crystal displays. In the case of an element, electrodes are arrange | positioned at both of the said pair of board | substrates. The liquid crystal alignment layer is formed on the substrate or the electrode.

In the case of the liquid crystal display element (for example, IPS, FFS, etc.) of homogeneous orientation, as a structure, it is a backlight, a 1st polarizing film, a 1st board | substrate, a 1st liquid crystal aligning film, a liquid crystal layer, a 2nd board | substrate from the backlight side at least. It has a 2nd polarizing film, and the deflection axis of the said polarizing film is provided so that the deflection axis (direction of polarization absorption) of a 1st polarizing film and the deflection axis of a 2nd polarizing film may cross (preferably orthogonally). At this time, the deflection axis of the first polarizing film and the liquid crystal alignment direction may be parallel or perpendicular to each other. The liquid crystal display element provided so that the deflection axis | shaft of a 1st polarizing film and the liquid crystal aligning direction may become parallel is O-mode, and the liquid crystal display element provided so that it may orthogonally be called E-mode. The liquid crystal aligning film of this invention can be applied to both O-mode and E-mode, and can be selected according to the objective.

In many photoisomerizable materials, compounds having dichroism are used. For this reason, if the polarization axis of the polarization irradiated in order to add anisotropy with respect to a liquid crystal aligning agent is aligned in parallel with the polarization axis of the polarization from the polarizing film arrange | positioned at the backlight side (when using the liquid crystal aligning agent of this invention, When the mode is arranged, the transmittance in the light absorption wavelength range of the liquid crystal alignment film is increased. For this reason, the transmittance | permeability of a liquid crystal display element can further be improved.

The said liquid crystal layer is formed in the form which a liquid crystal composition is clamped by the said pair of board | substrate which the surface in which the liquid crystal aligning film was formed opposes. In formation of a liquid crystal layer, the spacer which forms a suitable space | interval through said pair of board | substrates, such as microparticles | fine-particles and a resin sheet, can be used as needed.

As a method of forming the liquid crystal layer, a vacuum injection method and an ODF (One Drop Fill) method are known.

In the vacuum injection method, a space | gap (cell gap) is provided so that a liquid crystal aligning film surface may oppose, the injection hole of a liquid crystal will be left, a sealing compound will be printed, and a board | substrate can be bonded. After injecting and filling a liquid crystal using a vacuum differential pressure in the cell gap partitioned by the board | substrate surface and the sealing compound, an injection hole is sealed and a liquid crystal display element is manufactured.

In the ODF method, after a sealing compound is printed on the outer periphery of one liquid crystal aligning film surface among a pair of board | substrates, a liquid crystal is dripped in the area inside of a sealing compound, the other board | substrate is bonded together so that a liquid crystal aligning film surface may oppose. And a liquid crystal is expanded to the whole surface of a board | substrate, and then ultraviolet light is irradiated to the whole surface of a board | substrate, hardening a sealing compound, and a liquid crystal display element is manufactured.

Thermosetting types are also known to the sealing compound used for bonding of a board | substrate in addition to a UV hardening type. Printing of a sealing compound can be performed by the screen printing method, for example.

There is no restriction | limiting in particular in a liquid crystal composition, Various liquid crystal compositions with positive or negative dielectric constant anisotropy can be used. Preferable liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent Publication No. 3086228, Japanese Patent Publication No. 2635435, Japanese Patent Application Laid-open No. Hei 5-501735, Japanese Patent Application Laid-open No. Hei 8-157826, Japanese Patent Application Laid-open No. Hei 8-231960, Japan Japanese Patent Application Laid-Open No. 9-241644 (EP885272A1), Japanese Patent Application Laid-Open No. 9-302346 (EP806466A1), Japanese Patent Application Laid-Open No. 8-199168 (EP722998A1), Japanese Patent Application Laid-open No. 9-235552, and Japanese Laid-Open Patent Publication. Japanese Patent Laid-Open No. 9-255956, Japanese Patent Laid-Open No. 9-241643 (EP885271A1), Japanese Patent Laid-Open No. 10-204016 (EP844229A1), Japanese Patent Laid-Open No. 10-204436, Japanese Patent Laid-Open No. 10 The liquid crystal composition disclosed by -231482, Unexamined-Japanese-Patent No. 2000-087040, Unexamined-Japanese-Patent No. 2001-48822, etc. are mentioned.

As a preferable example of the liquid-crystal composition which has the said negative dielectric constant anisotropy, Unexamined-Japanese-Patent No. 57-114532, Unexamined-Japanese-Patent No. 2-4725, Unexamined-Japanese-Patent No. 4-224885, Unexamined-Japanese-Patent No. 8- 40953, Japanese Patent Application Laid-Open No. Hei 8-104869, Japanese Patent Application Laid-open No. Hei 10-168076, Japanese Patent Application Laid-open No. Hei 10-168453, Japanese Patent Application Laid-open No. Hei 10-236989, and Japanese Patent Application Laid-Open No. 236990, Japanese Patent Laid-Open No. 10-236992, Japanese Patent Laid-Open No. 10-236993, Japanese Patent Laid-Open No. 10-236994, Japanese Patent Laid-Open No. 10-237000, Japanese Patent Laid-Open No. 10-236992 237004, Japanese Patent Laid-Open No. 10-237024, Japanese Patent Laid-Open No. 10-237035, Japanese Patent Laid-Open No. 10-237075, Japanese Patent Laid-Open No. 10-237076, Japanese Patent Laid-Open No. 10-370 237448 (EP967261A1), Japanese Unexamined Patent Publication No. Hei 10-287874, Japanese Unexamined Patent Publication No. Hei 10-287875, Japan Japanese Patent Application Laid-Open No. Hei 10-291945, Japanese Patent Application Laid-Open No. 11-029581, Japanese Patent Application Laid-Open No. 11-080049, Japanese Patent Application Laid-Open No. 2000-256307, Japanese Patent Application Laid-Open No. 2001-019965, Japanese Patent Application Laid-Open Japanese Unexamined Patent Publication No. 2001-072626, Japanese Unexamined Patent Publication No. 2001-192657, Japanese Unexamined Patent Publication No. 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Japanese Patent Publication No. 2010-537010 The liquid crystal composition disclosed by Unexamined-Japanese-Patent No. 2012-077201, Unexamined-Japanese-Patent No. 2009-084362, etc. are mentioned.

The dielectric anisotropy may be used by adding one or more optically active compounds to a positive or negative liquid crystal composition.

For example, the liquid crystal composition used for the liquid crystal display element of this invention may add an additive further from a viewpoint of improving orientation, for example. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerization initiators, polymerization inhibitors and the like. Examples of preferred photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators and polymerization inhibitors include oxazine compounds disclosed in JP-A-2013-242526.

In order to make it suitable for the liquid crystal display element of a PSA (polymer sustained alignment) mode, the compound which can be superposed | polymerized can be mixed with a liquid crystal composition. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxylane, oxetane), vinyl ketone and the like. As a preferable compound, the compound disclosed by Unexamined-Japanese-Patent No. 2013-242526 etc. is mentioned.

Example

Hereinafter, the features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the specific example shown below.

Measurement and Evaluation Methods

[Measurement of Weight Average Molecular Weight (Mw)]

The weight average molecular weight of polyamic acid was measured by GPC method using 2695 Separation module 2414 differential refractometer (made by Waters), and was calculated | required by polystyrene conversion. The sample used for the measurement was obtained by diluting the obtained polyamic acid with a phosphoric acid-DMF mixed solution (phosphate / N, N-dimethylformamide = 0.6 / 100: by weight mixed solution) so that the polyamic acid concentration was about 2% by weight. will be. HSPgel RT MB-M (made by Waters) was used for the column, and it measured on the conditions of a column temperature of 50 degreeC, and a flow rate of 0.40 mL / min using the phosphoric acid-DMF mixed solution as a developing solvent. TSK standard polystyrene manufactured by Tosoh Corporation was used for standard polystyrene.

[Evaluation of Voltage Retention Rate (VHR) Reliability]

The voltage retention (VHR) of the liquid crystal display element is applied to a cell with a wave height of ± 5 V at 60 ° C. by the method described in "Mizushima et al. 14th Liquid Crystal Discussion Preliminary Proceedings p78 (1988)". Measured by. The voltage retention is an index indicating how much the applied voltage is held after the frame period, and when this value is 100%, it means that all charges are held. VHR reliability was evaluated by exposing the cell to an LED backlight for 300 hours and measuring VHR again. The larger the VHR after 300 hours, the higher the reliability of the optical stress of the formed alignment film. If VHR after 300 hours is 90% or more, VHR reliability is favorable, and 95% or more means that it is remarkably good.

[Evaluation of Transmittance]

The liquid crystal aligning film was formed on the transparent glass substrate, the transmittance | permeability of 380 nm-430 nm was measured with the ultraviolet-visible spectrophotometer V-660 (made by Nihon Bunco Co., Ltd.), and the average value of the transmittance | permeability in 380 nm-430 nm was calculated | required. As this numerical value is large, the coloring of the alignment film is suppressed, which means that the alignment film has good light transmission characteristics.

[Measurement of AC Afterimage and Contrast (Evaluation of Liquid Crystal Orientation)]

AC afterimage was measured by the method described in the international publication 2000/43833 pamphlet.

Specifically, the luminance-voltage characteristic (B-V characteristic) of the produced liquid crystal cell was measured, and this was made into the luminance-voltage characteristic: B (before) before stress application. Next, after applying alternating current of 4.5V and 60Hz to a liquid crystal cell for 20 minutes, it shortened for 1 second and measured brightness-voltage characteristic (B-V characteristic) again. This was made into the luminance-voltage characteristic: B (after) after stress application. And the brightness | variation change rate (DELTA) B (%) was calculated | required by the following formula using the brightness | luminance in the voltage of 1.3V of each B-V characteristic measured. The smaller the value of ΔB (%) means that the generation of AC afterimage can be suppressed, that is, the better liquid crystal orientation.

ΔB (%) = [B (after) _1.3 -B (before) _1.3 ] / B (before) _1.3 × 100

In the formula, B (before) _1.3 represents the luminance at 1.3 V in the BV characteristic before stress application, and B (after) _1.3 represents the luminance at _1.3 V in the BV characteristic after stress application.

The luminance change rate (DELTA) B was evaluated based on the following references | standards.

ΔB (%) is less than 1.5%: ◎

ΔB (%) is 1.5% or more but less than 2.0%: ○

ΔB (%) is 2.0% or more but less than 3.0%: Δ

ΔB (%) is 3.0% or more: ×

Moreover, contrast CR was calculated | required using the ratio of the minimum brightness | luminance and the maximum brightness | luminance in B-V characteristic before stress application. The larger the value of CR, the clearer the contrast display.

CR = B (before) _max / B (before) _min

In the formula, B (before) _max represents the maximum luminance in the BV characteristic before stress application, and B (before) _min represents the minimum luminance in the BV characteristic before stress application.

Contrast CR evaluated the following references | standards for every liquid crystal composition to be used.

<When Negative Liquid Crystal Composition A is Used>

CR is more than 3500: ◎

CR is 3250 or more and less than 3500: ○

CR is 3000 or more and less than 3250: △

CR less than 3000: ×

<When positive type liquid crystal composition B is used>

CR 3250 or more: ◎

CR is greater than 3000 and less than 3250: ○

CR is more than 2750 and less than 3000: △

CR less than 2750: ×

Compounds and Solvents Used

The diamine used for preparation of varnish in this Example is divided into the photoreactive diamine which has thermal reactivity, the photoreactive diamine which does not have thermal reactivity, and a non-photoreactive diamine, and is shown below. In addition, the diamine represented by Formula (2) was used for the photoreactive diamine which has thermal reactivity.

[Photoreactive Diamine with Thermal Reactivity]

[Formula 137]

"Photoreactive diamines not having thermal reactivity"

[Formula 138]

[Non-Photoreactive Diamine]

[Formula 139]

Tetracarboxylic dianhydride

The tetracarboxylic dianhydride used for preparation of varnish in this Example is shown below.

[Formula 140]

[additive]

The additive used for preparation of the liquid crystal aligning agent in a present Example is shown below.

AD-1: 2,2 '-(1,3-phenylene) bis- (2-oxazoline) (abbreviated: 1,3-PBO)

AD-2: Celoxide 8000

AD-3: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (abbreviated: S530)

AD-4: 3-trimethoxypropyl succinic anhydride

AD-5: isocyanuric acid tris (2-hydroxyethyl)

[solvent]

The solvent used for preparation of the liquid crystal aligning agent in a present Example is shown below.

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

Varnish

The varnish used in the present Example was prepared by the following procedure. Here, in the preparation examples of varnishes 1-21, the photoreactive diamine used by each preparation example below is the photoreactive diamine which does not have thermal reactivity with the photoreactive diamine which has thermal reactivity, and the preparation of the comparative varnish 1 In the example, it is only photoreactive diamine which has thermal reactivity, and in preparation example of the comparative varnish 2, it is only photoreactive diamine which does not have thermal reactivity. Varnishes 1-8 for blends are varnishes which do not incorporate a photoreactive structure and are blended into other varnishes for use.

[Preparation of Varnish 1] Preparation of Varnish 1

In a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 2.2567 g of a thermally reactive photoreactive diamine (4-3) and a photoreactive diamine (V-2-1) having no thermal reactivity were placed. 0.4725g, 0.0852g of non-photoreactive diamine (DI-4-13) and 0.0597g of non-photoreactive diamine (DI-13-1) were put, and 64.0g of N-methyl- 2-pyrrolidone was added. To the solution, 1.8094 g of (AN-4-17, m = 8), 0.6549 g of (AN-2-1), and 0.6616 g of (AN-1-1) were added as tetracarboxylic dianhydride to room temperature. Stirred for 24 hours. 30.0 g of butyl cellosolves were added to this reaction liquid, and it heat-stirred at 70 degreeC until the produced polymer component became the target weight average molecular weight. As a result, varnish 1 having a weight average molecular weight of the polymer component of 13,000 and a resin powder concentration (polymer concentration as a solid content) of 6% by weight was obtained.

[Preparation Example 2-21 of Varnish]

Except having changed the compound and compounding ratio used as a diamine and tetracarboxylic dianhydride as shown in Table 1, it carried out similarly to the preparation example 1, and prepared varnish 2-21 whose resin powder concentration is 6 weight%. At this time, the synthesis conditions of the polymer component were adjusted so that a weight average molecular weight might be in the range of 5,000-20,000. Table 1 shows the weight average molecular weight of the resulting polymer component. In addition, in Table 1, in the preparation example in which two or more compounds are listed as a diamine, it means that all the compounds were used together as a diamine, In the preparation example in which two or more compounds are listed as tetracarboxylic dianhydride, It means what used all the compounds together as tetracarboxylic dianhydride. The numerical value in square brackets shows a compounding ratio (mol%), and "-" means that the compound corresponding to a column is not used. The same is true in Tables 2 and 3.

Comparative Comparative Examples 1 and 2 of Varnish Preparation of Comparative Varnishes 1 and 2

Comparative varnishes 1 and 2 having a resin powder concentration of 6% by weight were prepared in the same manner as in Preparation Example 1, except that the compound and the compounding ratio used as the diamine and tetracarboxylic dianhydride were changed as shown in Table 2. The weight average molecular weight of the produced polymer component is shown in Table 2.

[Preparation Examples 1 to 8 of Varnishes for Blends] Preparation of Varnishes 1 to 8 for Blends

Except having changed the compound and compounding ratio used as a diamine and tetracarboxylic dianhydride as shown in Table 3, it carried out similarly to the preparation example 1, and prepared the varnish 1-8 for blends whose resin powder concentration is 6 weight%. Table 3 shows the weight average molecular weight of the resulting polymer component.

TABLE 1

TABLE 2

TABLE 3

Preparation of liquid crystal aligning agent

The liquid crystal aligning agent was prepared by the following procedure using varnishes 1-21, varnishes 1-8 for blends, and comparative varnishes 1 and 2 which were prepared by said each preparation example.

Example 1 Preparation of Alignment Agent 1

Into a 50 mL eggplant flask equipped with a stirring blade and a nitrogen inlet tube, varnish 1 (10.0 g) was weighed and put therein, N-methyl-2-pyrrolidone (1.4 g) and butyl cellosolve (0.6 g). ) Was added and stirred at room temperature for 1 hour to obtain an alignment agent 1 having a resin powder concentration of 5% by weight.

EXAMPLES 2-21 Preparation of orientation agents 2-21

Except using the varnish shown in Table 4 instead of varnish 1, it carried out similarly to Example 1, and prepared the orientation agents 2-21.

Example 22 Preparation of Alignment Agent 22

Into a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introduction tube, varnish 1 (3.0 g) and varnish 1 (7.0 g) for blending were weighed and put therein, and N-methyl-2-pyrrolidone (3.5) was added thereto. g) and butyl cellosolve (1.5 g) were added, and it stirred at room temperature for 1 hour, and obtained the aligning agent 22 of 4 weight% of resin powder concentration.

[Examples 23-59] Preparation of the alignment agents 23-59

Instead of varnish 1 and varnish 1 for blends, the alignment agents 23-59 were prepared like Example 22 except having used the varnish shown in Table 5 and the varnish for blends, respectively.

Example 60 Preparation of Aligner 60

Into a 50 mL eggplant flask equipped with a stirring blade and a nitrogen inlet tube, varnish 1 (3.0 g) and varnish 1 (7.0 g) for blending were weighed in each, and additive (AD-1) was added to 1 weight of the total solids. Wt%, and N-methyl-2-pyrrolidone (3.5 g) and butyl cellosolve (1.5 g) were added thereto, followed by stirring at room temperature for 1 hour to obtain an alignment agent having a resin powder concentration of 4 wt% 60. Got.

[Examples 61-65] Preparation of the alignment agents 61-65

Instead of varnish 1 and varnish 1 for blends, the varnishes shown in Table 5 and the varnishes for blends were used, respectively, except that the additives were added to the total solids weight as shown in Table 5, and the orientations were the same as in Example 60. 61-65 was prepared.

Comparative Examples 1 and 2 Preparation of Comparative Alignment Agents 1 and 2

Instead of varnish 1, the comparative alignment agents 1 and 2 were prepared like Example 1 except having used the comparative varnish shown in Table 6.

Comparative Examples 3 and 4 Preparation of Comparative Alignment Agents 3 and 4

Instead of varnish 1 and varnish 1 for blends, the comparative alignment agents 3 and 4 were prepared like Example 22 except having used the comparative varnish and the blend varnish shown in Table 7, respectively.

The varnish used for preparation of the liquid crystal aligning agent in each Example and each comparative example is shown to Tables 4-7.

TABLE 4

TABLE 5

TABLE 6

TABLE 7

evaluation

[Evaluation of Voltage Retention Rate (VHR) Reliability]

The liquid crystal aligning agent prepared in Examples 1-65 and Comparative Examples 1-4 was dripped at the glass substrate with an IPS electrode, and the glass substrate with a column spacer, and was apply | coated by rotating a board | substrate for 15 second by 2,000 rpm by the spinner method. The film | membrane of the liquid crystal aligning agent was formed by heating a board | substrate at 60 degreeC after application | coating for 1 minute after application | coating, and evaporating a solvent. Ultraviolet linearly polarized light with a wavelength of 365 nm is 2.0 ± 0.1 J / cm ² from the vertical direction with respect to the substrate using a multi-light ML-501C / B manufactured by Ushio Denki Co., Ltd. to the film of this liquid crystal aligning agent. It irradiated and performed the photo-alignment process. The film of the liquid crystal aligning agent which performed this photo-alignment process was heat-baked for 30 minutes at 220 degreeC, and the liquid crystal aligning film of 100 nm of film thickness was formed. Subsequently, two board | substrates with a liquid crystal aligning film were bonded together so that the surface in which the liquid crystal aligning film is formed, and also the space for inject | pouring a liquid crystal composition between the opposing liquid crystal aligning film may be formed. At this time, the direction of the board | substrate was made into the direction in which the polarization directions of the linearly polarized light which irradiated each liquid crystal aligning film at the time of photo-alignment process become mutually parallel. The negative liquid crystal composition A of the following composition was inject | poured into the space | gap between this bonded substrates, and the liquid crystal cell (liquid crystal display element) of 7 micrometers of cell thicknesses was produced.

<Negative Liquid Crystal Composition A>

Formula 141

(Property value)

Phase transition temperature NI: 75.7 degreeC, dielectric constant anisotropy (DELTA) epsilon: -4.1, refractive index anisotropy (DELTA) n: 0.101, viscosity (eta): 14.5 mPa * s.

About each produced liquid crystal cell, voltage retention (initial voltage retention) was measured at 5V and 30Hz. Subsequently, the liquid crystal cell was put up on the backlit tester (Fuji Film Co., Ltd. make, FujiCOLOR LED Viewer Pro HR-2; brightness 2,700 cd / m <^2> ) made light for 300 hours, and the voltage retention after the light irradiation was measured. The results are shown in Tables 8 to 10.

TABLE 8

TABLE 9

TABLE 10

As shown in Table 8, the alignment agent 22-65 which mixed varnishes 1-8 with blends varnishes 1-21 prepared using both the photoreactive diamine which has thermal reactivity, and the photoreactive diamine which does not have thermal reaction. The liquid crystal cell using was showing a voltage retention of 90% or more after 300 hours of backlight irradiation, and was able to obtain good VHR reliability. On the other hand, as shown in Table 9, 10, as a photoreactive diamine, it blends for the liquid crystal cell by the comparative aligning agent 2 of the comparative varnish 2 prepared using only the photoreactive diamine which does not have thermal reactivity, and the comparative varnish 2 In the liquid crystal cell using the comparative alignment agent 4 which mixed varnish 1, the voltage retention after backlight irradiation was less than 90%. This is considered to be because the electrical property of the liquid crystal aligning film deteriorated with the photochemical reaction of the azobenzene structure which arises by irradiation of a backlight. In addition, in the orientation agents 22-65, although the photoreactive diamine which does not have thermal reactivity is used together in preparation of a varnish, favorable VHR reliability is obtained, Intramolecular chemistry of the photoreactive diamine which has thermal reactivity is obtained. It is assumed that the structure formed by the reaction is very stable with respect to light.

[Evaluation of Transmittance]

Using the liquid crystal aligning agent prepared in Examples 1-65 and Comparative Examples 1-4, the coating film of the liquid crystal aligning agent was formed on the transparent glass substrate on the conditions similar to evaluation of voltage retention. Subsequently, the board | substrate was heat-baked at 220 degreeC for 30 minutes, the liquid crystal aligning film of thickness 100nm was formed, the ultraviolet visible transmittance spectrum of the board | substrate was measured, and the average value of the transmittance in the range of 380nm-430nm was calculated | required. . The results are shown in Tables 11-14.

TABLE 11

TABLE 12

TABLE 13

TABLE 14

As shown in Table 13, the transmittance | permeability was 71% in the liquid crystal aligning film by the comparative aligning agent 2 of the comparative varnish 2 prepared using only the photoreactive diamine which does not have thermal reactivity as photoreactive diamine. On the other hand, as shown in Table 11, the liquid crystal aligning film of the aligning agents 1-21 containing varnishes 1-21 prepared using both the photoreactive diamine which has thermal reactivity, and the photoreactive diamine which does not have thermal reactivity has Both showed the transmittance | permeability higher than the liquid crystal aligning film of the comparative aligning agent 2.

In addition, as shown in Tables 12 and 14, the same tendency was observed also in the system using the blend varnish. That is, the transmittance | permeability was 79% in the liquid crystal aligning film of the comparative aligning agent 4 which mixed the varnish 1 for blends with the comparative varnish 2 prepared using only the photoreactive diamine which does not have thermal reactivity as photoreactive diamine. On the other hand, the liquid crystal aligning film of the aligning agents 22-65 which mixed the varnish 1-8 with the varnish 1-21 prepared using both the photoreactive diamine which has thermal reactivity, and the photoreactive diamine which does not have thermal reactivity is All showed the transmittance | permeability higher than the liquid crystal aligning film by the comparative aligning agent 4. As shown in FIG.

The high transmittance in the system using the photoreactive diamine having thermal reactivity is that the azobenzene structure derived from the photoreactive diamine having thermal reactivity forms an indazole ring by thermal firing of the membrane, so that the absorption band derived from the azobenzene structure ( It is considered that the absorbance at 380 nm to 430 nm) is due to a decrease. From this point, it was confirmed that the thermal reactivity introduced into the liquid crystal aligning film by using the photoreactive diamine having thermal reactivity functioned as a structure which chemically changes by the heating and baking of the film.

[Evaluation of AC Afterimage and Contrast Characteristics (Evaluation of Liquid Crystal Orientation)]

Using the liquid crystal aligning agent prepared in Examples 1-65 and Comparative Examples 1-4, the liquid crystal aligning film of thickness 100nm was formed on the glass substrate with an FFS electrode and the glass substrate with a column spacer on the conditions similar to evaluation of voltage retention. . Two board | substrates with these liquid crystal aligning films were bonded together so that the surface in which the liquid crystal aligning film is formed may be made, and the space | gap for inject | pouring a liquid crystal composition between the opposing liquid crystal aligning films is formed. At this time, the direction of the board | substrate was made into the direction in which the polarization direction of the linearly polarized light which irradiated each liquid crystal aligning film at the time of photo-alignment process becomes mutually parallel. The negative liquid crystal composition A or the following positive liquid crystal composition B of the said composition was injected into the space | gap between this bonded board | substrates, the injection hole was sealed with the photocuring agent, and the liquid crystal cell (liquid crystal display element) of cell thickness of 4 micrometers was produced. About the obtained liquid crystal cell, the ratio of brightness change rate (DELTA) B in 1.3V before stress application and after stress application, and the maximum brightness | luminance and minimum brightness | luminance in B-V characteristic were measured, and AC residual characteristic and contrast characteristic were evaluated. The results are shown in Tables 15-18.

<Positive Liquid Crystal Composition B>

[Formula 142]

(Property value)

Phase transition temperature NI: 100.1 degreeC, dielectric constant anisotropy (DELTA) epsilon: 5.1, refractive index anisotropy (DELTA) n: 0.093, viscosity (eta): 25.6 mPa * s.

TABLE 15

TABLE 16

TABLE 17

TABLE 18

As shown in Tables 15 and 16, alignment agents 1 to 21 and varnishes 1 to 21 containing varnishes 1 to 21 prepared by using both of a photoreactive diamine having thermal reactivity and a photoreactive diamine having no thermal reactivity. In each liquid crystal cell using the alignment agents 22-65 which mixed varnish 1-8 for blends, respectively, the luminance change rate (DELTA) B by stress application was less than 3.0% ((triangle | delta)-(◎)), and showed favorable AC residual characteristic. Moreover, in each liquid crystal cell using the aligning agents 1-65, ratio CR of maximum brightness and minimum brightness was 3000 or more ((triangle | delta)-(◎)), and the contrast was able to display the contrast with high contrast. Especially when each liquid crystal cell using the aligning agent 1, 2, 8, 22, 23, 33, 35, 36 used either of 2 types of liquid crystal compositions A and B, evaluation of (DELTA) B is (circle) and CR is Evaluation of (circle) was (circle), and showed the outstanding AC residual characteristic, and the contrast display was able to be performed with very high contrast.

On the other hand, each using the comparative alignment agent 1 by the comparative varnish 1 prepared using only the photoreactive diamine which has thermal reactivity as photoreactive diamine, or the comparative alignment agent 3 which mixed the varnish 1 for blends with the comparative varnish 1, respectively. CR was lower than the liquid crystal cell using the alignment agents 1-65, and the liquid crystal cell was unclear. On the other hand, each using the comparative alignment agent 2 by the comparative varnish 2 prepared by using only the photoreactive diamine which does not have thermal reactivity as photoreactive diamine, or the comparative alignment agent 4 which mixed the comparative varnish 2 and the varnish 1 for blends, respectively. (DELTA) B was larger than the liquid crystal cell using the alignment agents 1-65, and the liquid crystal cell was inferior to AC residual characteristic.

From the above results, by using the varnish prepared by using together the photoreactive diamine which does not have thermal reactivity to the photoreactive diamine which has thermal reactivity, for the liquid crystal aligning agent, the transmittance and VHR reliability of the liquid crystal aligning film are hardly impaired, In the liquid crystal cell to which this liquid crystal aligning film was applied, it turned out that both AC afterimage characteristic and contrast characteristic can be improved significantly.

[Evaluation of Liquid Crystal Alignment Film Formed by Baking in Two Steps]

Using the alignment agents 3 and 24 prepared in Examples 3 and 24, a liquid crystal alignment film was formed in the same manner as described above, except that the heating and firing of the coating films of the respective alignment agents were performed in two steps, a low temperature firing step and a high temperature firing step. And the average transmittance in the 380-430 nm, the voltage retention of the liquid crystal cell to which this liquid crystal aligning film was applied, luminance change rate (DELTA) B by stress application, and ratio CR of the maximum brightness and the minimum brightness were measured.

Here, in a low temperature baking process, baking of a coating film was performed at 110 degreeC-170 degreeC low temperature, and in a high temperature baking process, baking of a coating film was performed at 210 degreeC-230 degreeC high temperature. Table 19 shows the specific conditions of each firing step and the measurement results of the respective properties.

TABLE 19

As shown in Table 19, in the system using the aligning agent 3, ΔB compared with the case of performing a one-step high temperature baking at 220 ° C. for 30 minutes by performing a low temperature baking step in the range of 140 to 170 ° C. before the high temperature baking step. (AC residual characteristic) was improved, and the contrast CR was improved. Moreover, in the system using the aligning agent 24, (DELTA) B (AC residual characteristic) compared with the case where 1-step high temperature baking of 220 degreeC is performed by performing a low temperature baking process in the range of 130-170 degreeC before a high temperature baking process. Is improved, and the contrast CR is improved. From this point, it was found that the AC afterimage characteristic and the contrast characteristic of the liquid crystal cell to which the liquid crystal aligning film was applied can be further improved by performing the baking of the film of the liquid crystal aligning agent in two stages and by appropriately adjusting the baking temperature. This is because, in one-step high-temperature calcination, various reactions caused by heat, including imidization and indazole ring formation, occur at about the same time. In the two-step calcination of the low-temperature and high-temperature calcination processes, these reactions occur stepwise. It is thought that this is because the polymer chain is more uniformly oriented.

When the liquid crystal aligning agent for photo-alignment of this invention is used, high voltage retention and light resistance can be maintained also in long time use, and the high liquid crystal display element of a display quality can be provided. The liquid crystal aligning agent for photoalignments of this invention can be applied suitably to a transverse electric field type liquid crystal display element. Moreover, the liquid crystal aligning film of this invention can be used also for the broadband variable ideal phase | channel with a microwave millimeter wave using liquid crystal. This wideband variable phase shifter can be used suitably for an antenna for phase control of electromagnetic wave signals, and the like.

Claims (27)

As a liquid crystal aligning agent for photoalignments containing the polymer component which has a structural unit containing a photoreactive structure,
The polymer component is composed of a polymer obtained by polymerizing a monomer composition containing at least a first monomer and a second monomer, or a derivative thereof,
The first monomer includes a photoreactive structure in a portion forming the structural unit of the polymer, and a portion in which the structural unit of the polymer forms a chemical reaction by heating;
The second monomer has a photoreactive structure in a portion forming the structural unit of the polymer, and the portion forming the structural unit of the polymer does not cause a chemical reaction by heating. My. The method according to claim 1,
The liquid crystal aligning agent for photoalignment whose said chemical reaction in a said 1st monomer is a cyclization reaction. The method according to claim 1 or 2,
The said 1st monomer contains the photoreactive structure which has at least one of the structure represented by following formula (a-1), and the structure represented by following formula (a-2), The liquid crystal aligning agent for photoalignments.
[Formula 1]

[In Formula (a-1), R ^<a> is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl carbon. Represents a niyl group;
In formula (a-2), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or Unsubstituted arylcarbonyl group;
In formulas (a-1) and (a-2), * represents a bonding position with a photoreactive group.] The method according to any one of claims 1 to 3,
The said 1st monomer contains the photoreactive structure which has a photoisomerization structure or an optical freeze dislocation structure, The liquid crystal aligning agent for photoalignments. The method according to any one of claims 1 to 4,
The said 1st monomer contains the photoreactive structure which has a structure represented by following formula (1), The liquid crystal aligning agent for photoalignments.
[Formula 2]

[In Formula (1), R <^1> and R <^2> respectively independently represents the group represented by a hydrogen atom, following formula (1-1), or following formula (1-2), At least one of R <^1> and R <^2> is , A group represented by the following formula (1-1) or the following formula (1-2);
* Represents a bonding position in the benzene ring, and is either one of a position capable of substituting with a hydrogen atom in one benzene ring or one of positions capable of being substituted with a hydrogen atom of the other benzene ring;
The hydrogen atom of the benzene ring may be substituted with a substituent.]
[Formula 3]

[In Formula (1-1) and Formula (1-2), R <^4> and R <^5> is respectively independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane oil group, a substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group;
* Represents a bonding position to the benzene ring in formula (1).] The method according to any one of claims 1 to 5,
The polymer or derivative thereof formed by polymerizing the monomer composition is at least one selected from polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer and polyamideimide,
The liquid crystal aligning agent for photoalignment whose said 1st monomer is diamine represented by following formula (2).
[Formula 4]

[In Formula (2), R <^1> and R <^2> respectively independently represents the group represented by a hydrogen atom, a formula (1-1), or a formula (1-2), At least ^{1 of} R <^1> and R <^2> is a formula Group represented by (1-1) or formula (1-2);
R ⁶ and R ⁸ are each independently a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) -Or represent a single bond, and in R ⁶ and R ⁸ , one of -CH ₂ -or two non-adjacent groups of the linear alkylene group may be substituted with -O-;
R ⁷ and R ⁹ each independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond;
The bonding position of H ₂ NR ⁷ -R ⁶ -is any one of positions replaceable with a hydrogen atom in one benzene ring, and the bonding position of H ₂ NR ⁹ -R ⁸ -is bonded to the other benzene ring. Any of hydrogen atom and a position which can be substituted;
The hydrogen atom in the benzene ring may be substituted with a substituent.]
[Formula 5]

[In Formula (1-1) and Formula (1-2), R <^4> and R <^5> is respectively independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane oil group, a substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group;
* Represents a bonding position to the benzene ring in formula (2).] The method according to claim 5 or 6,
The liquid crystal aligning agent for photoalignments whose R <^1> is group represented by Formula (1-1) and R <^2> is a hydrogen atom. The method according to claim 7,
The liquid crystal aligning agent for photoalignment whose R <^4> is a hydrogen atom or a substituted or unsubstituted alkyl group. The method according to claim 6,
The diamine represented by said Formula (2) is a diamine represented by either of following formula (3)-(6), The liquid crystal aligning agent for photoalignments.
[Formula 6]

[In formula (3)-(6), R <^4> is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or substituted or unsubstituted independently A substituted arylcarbonyl group;
The hydrogen atom of the benzene ring may be substituted with a substituent;
In formulas (5) and (6), R ⁵ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted group. Substituted arylcarbonyl group is shown.] The method according to claim 6 or 9,
The diamine represented by said formula (2) has following formula (3-1)-formula (3-9), formula (4-1)-formula (4-9), formula (5-1), formula (5) The liquid crystal aligning agent for photoalignments which is diamine represented by -2), Formula (6-1), and Formula (6-2).
[Formula 7]

[Formula 8]

[Wherein Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, ⁱ Pr represents an isopropyl group, Bu represents a butyl group, and ^t Bu represents a t-butyl group, respectively.] The method according to any one of claims 1 to 10,
The said 2nd monomer contains the photoreactive structure which has a photoisomerization structure or a photodimerization structure, The liquid crystal aligning agent for photoalignments. The method according to claim 11,
The said 2nd monomer contains the photoreactive structure which has a photoisomerization structure, The liquid crystal aligning agent for photoalignments. The method according to any one of claims 6 to 12,
Liquid crystal aligning agent for photoalignments whose said 2nd monomer is diamine. The method according to any one of claims 6 to 13,
The liquid crystal aligning agent for photoalignments in which the said monomer composition contains tetracarboxylic dianhydride. The method according to any one of claims 1 to 14,
The compounding quantity of the said 1st monomer in the said monomer composition is 15-85 mol% with respect to the total mole number of the said 1st monomer and said 2nd monomer, The liquid crystal aligning agent for photoalignments. The method according to any one of claims 1 to 15,
The liquid crystal aligning agent further contains a second polymer component,
The said 2nd polymer component is a liquid crystal aligning agent for photoalignments which consists of a polymer which polymerizes the monomer composition which consists of a monomer which does not contain a photoreactive structure, or its derivative (s). The method according to claim 16,
The polymer or derivative thereof formed by polymerizing the monomer composition is at least one member selected from polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide. My. The method according to any one of claims 1 to 17,
The liquid crystal aligning agent for photoalignments used for formation of the liquid crystal aligning film of a transverse electric field type liquid crystal display element. The liquid crystal aligning film formed with the liquid crystal aligning agent for photoalignments in any one of Claims 1-18. The liquid crystal display element which has a liquid crystal aligning film of Claim 19. The film | membrane which consists of a liquid crystal aligning agent for photo-alignments of any one of Claims 1-18 has the orientation process which irradiates polarization, and gives anisotropy, and the heating baking process which heats and bakes the said film which provided anisotropy,
The formation method of the liquid crystal aligning film which reduces a photoreactive group by generating a cyclization reaction in the photoreactive structure of the polymer component which the said liquid crystal aligning agent for photo-alignment contains at the time of the said heating baking process. The method according to claim 21,
A method for forming a liquid crystal alignment film, wherein the heating and baking step is performed in a step of two or more steps by changing the heating temperature. The manufacturing method of the liquid crystal display element which forms a liquid crystal aligning film using the formation method of the liquid crystal aligning film of Claim 21 or 22. The method according to claim 23,
The manufacturing method of the liquid crystal display element whose liquid crystal display element to manufacture is a transverse electric field type liquid crystal display element. As a polyamic acid or its derivative formed by superposing | polymerizing the monomer composition containing a 1st monomer, a 2nd monomer, and a non-photoreactive tetracarboxylic dianhydride,
The first monomer is a diamine represented by the following formula (2),
The second monomer is represented by the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (IV-3), formula (V-1), formula (V-2), formula (V-3), formula (VI-1), formula (VI-2), formula (VII-1), formula ( VIII-1), and the polyamic acid or a derivative thereof which is a compound represented by any one of formulas (VIII-2).
[Formula 9]

[In Formula (2), R <^1> and R <^2> respectively independently represents the group represented by a hydrogen atom, a formula (1-1), or a formula (1-2), At least ^{1 of} R <^1> and R <^2> is a formula Group represented by (1-1) or formula (1-2);
R ⁶ and R ⁸ are each independently a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) -Or represent a single bond, and in R ⁶ and R ⁸ , one of -CH ₂ -or two non-adjacent groups of the linear alkylene group may be substituted with -O-;
R ⁷ and R ⁹ each independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond;
The bonding position of H ₂ NR ⁷ -R ⁶ -is any one of positions replaceable with a hydrogen atom in one benzene ring, and the bonding position of H ₂ NR ⁹ -R ⁸ -is bonded to the other benzene ring. Any of hydrogen atom and a position which can be substituted;
The hydrogen atom in the benzene ring may be substituted with a substituent.]
[Formula 10]

[In Formula (1-1) and Formula (1-2), R <^4> and R <^5> is respectively independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane oil group, a substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted arylcarbonyl group;
* Represents a bonding position to the benzene ring in formula (2).]
[Formula 11]

[Formula 12]

(Formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (IV-3), Formula (V-1), Formula (V-2), Formula (V-3), Formula (VI-1), Formula (VI-2), Formula (VII-1), Formula (VIII-1), and In formula (VIII-2), the group in which the bond position is not fixed to any one of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary, and in formula (IV-3), r is an integer from 1 to 10, in the formula (V-2), r ⁶ independently represent the _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently 0 to 2 an integer, formula according to (V-3), ring a and ring B is at least one is each independently selected from the just recalled cyclic hydrocarbon, a condensed polycyclic hydrocarbon, and clothing, R ¹¹ is 1 to 20 carbon atoms straight chain alkylene, -COO-, -OCO-, -NHCO-, -CONH- , -N (CH 3) CO-, or -CON (CH ₃₎ - represents the, R ¹² are, of 1 to 20 carbon atoms Straight chain alkylene, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, Or -CON (CH ₃ )-, and in R ¹¹ and R ¹² , one or two of -CH ₂ -of the linear alkylene may be substituted with -O-, and R ⁷ to R ¹⁰ are each -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH are independently represented, b to e are each independently an integer of 0 to 4, and in formula (VII-1), R ⁴ and R ⁶ is independently C1-C20 linear alkylene, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ )-, or in the shown, R ⁴ and R ⁶ bond, -CH ₂ of the linear alkylene-two not one of or adjacent are optionally substituted by -O-, R ⁵ and R ⁷ is a monocyclic hydrocarbon independently Hydrogen, a condensed polycyclic hydrocarbon, a heterocycle, or a single bond.) The method according to claim 25,
The second monomer is represented by the following formula (V-2-1), formula (V-3-2), formula (VI-2-1), formula (VII-1-1) and formula (VII-1-2) Polyamic acid or a derivative thereof that is a compound represented by any one of
[Formula 13]

The method according to claim 25 or 26,
The polyamic acid or its derivative (s) which consists of at least 1 sort (s) chosen from a polyamic acid, a polyimide, a partial polyimide, a polyamic acid ester, a polyamic acid-polyamide copolymer, and a polyamideimide.