TWI755517B - Manufacturing method of liquid crystal element - Google Patents

Abstract

Provided is a method of manufacturing a liquid crystal element capable of sufficiently generating a difference in pretilt angle between one substrate and the other substrate. A liquid crystal element is manufactured by the following method, the method includes: coating a liquid crystal alignment agent on each of the first substrate and the second substrate; The step of heating; and after the heating, the first substrate and the second substrate are arranged opposite to each other with the surfaces coated with the liquid crystal alignment agent facing each other to construct a liquid crystal cell, and the liquid crystal alignment agent contains a liquid crystal alignment agent having a function of being released by heating In the step of heating the substrate, the compound of the thermally releasable group is subjected to a high-temperature heat treatment in which one of the first substrate and the second substrate is heated at a higher temperature than the other substrate.

Description

Manufacturing method of liquid crystal element

The present invention relates to a method for manufacturing a liquid crystal element and a liquid crystal alignment agent.

As a liquid crystal element, a horizontal alignment mode using a nematic liquid crystal having positive dielectric anisotropy, typified by a twisted nematic (TN) type, a super twisted nematic (STN) type, and the like Various liquid crystal elements, such as a vertical alignment type liquid crystal element using a homeotropic alignment mode of nematic liquid crystal having negative dielectric anisotropy, are also known. These liquid crystal elements include a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. As materials constituting the liquid crystal alignment film, polyamide, polyimide, polyamide, polyamide, polyester, polyorganosiloxane, etc. are known (refer to Patent Literature 1 to Patent Literature). 3).

As one of the alignment treatment methods, a Polymer Sustained Alignment (PSA) method is known. The PSA method is a technique in which a polymerizable compound is contained in a liquid crystal layer provided in a gap between a pair of substrates, and the polymerizable compound is polymerized by irradiating ultraviolet rays in a state where a voltage is applied between the substrates, thereby exhibiting pretilt angle characteristics and controlling the liquid crystal orientation direction. According to this technology, it is possible to expand the viewing angle and speed up the response of liquid crystal molecules, and it is also possible to solve the problem of multi-domain vertical alignment. The problem of insufficient transmittance and contrast of the Multi-domain Vertical Alignment (MVA) type panel.

In addition, in recent years, along with the expansion of the use of liquid crystal panels, development of liquid crystal panels having complex shapes such as a curved display with a curved display surface is progressing. Regarding a curved display, generally, a liquid crystal cell is produced by laminating a pair of substrates in a state in which a liquid crystal layer is arranged between the substrates, and then the liquid crystal cell is bent and produced. However, since the liquid crystal cell is bent in order to manufacture a curved display, a region where a deviation of the pretilt angle occurs between one of the pair of substrates and the other substrate may occur. In this case, in the region where the pretilt angle is uneven, dark parts are visible on the screen, and the image quality may be degraded.

In view of the above-mentioned aspects, it has been proposed to manufacture a curved display by using a liquid crystal cell constructed by laminating the liquid crystal alignment film of one substrate and the liquid crystal alignment film of the other substrate with a different pretilt angle. Variation in the pretilt angle between substrates when the liquid crystal cell is bent (for example, refer to Patent Document 4).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 4-153622

[Patent Document 2] Japanese Patent Laid-Open No. 56-91277

[Patent Document 3] Japanese Patent Laid-Open No. 11-258605

[Patent Document 4] Japanese Patent Laid-Open No. 2015-26074

With the conventional method, it is difficult to generate a sufficient difference in pretilt angle between one substrate and the other substrate. Therefore, there is a fear that the image quality cannot be sufficiently ensured when applied to a curved display.

The present invention has been made in view of the above-mentioned facts, and one of its objects is to provide a method of manufacturing a liquid crystal element that can sufficiently generate a difference in pretilt angle between one substrate and the other substrate. In addition, another object is to provide a liquid crystal aligning agent that can obtain a liquid crystal element having a sufficiently large difference in pretilt angle between one substrate and the other substrate.

The present invention employs the following methods in order to solve the above-mentioned problems.

<1> A method of manufacturing a liquid crystal element, comprising: a step of coating a liquid crystal alignment agent on each of a first substrate and a second substrate (coating step); The step of heating the first substrate and the second substrate (heating step); and after the heating, the first substrate and the second substrate are opposed to the surfaces on which the liquid crystal aligning agent is applied A step of constructing a liquid crystal cell by arranging in opposite directions (a cell constructing step), wherein the liquid crystal aligning agent contains a compound having a thermally releasable group that is desorbed by heating, and in the step of heating, the One of the first substrate and the second substrate is subjected to a high-temperature heat treatment that is heated at a higher temperature than the other substrate.

<2> A liquid crystal aligning agent containing a compound having a thermally releasable group that is released by heating, and the thermally releasable group has a compound selected from the group consisting of the following (A), (B) and (C) At least one partial structure in the group of .

(A) At least one partial structure selected from the group consisting of a hindered amine structure, a hindered phenol structure, and an aniline structure.

(B) A group capable of expressing at least any one of a radical generating function that generates radicals by light irradiation and a photosensitizing function that exhibits a sensitizing action by light irradiation.

(C) A partial structure represented by the following formula (C-1) (however, it is limited to a partial structure having 8 or more carbon atoms).

[Chemical 1]*-R ²² -R ²¹ -R ²⁰ -R ¹⁹ (C-1)

(In formula (C-1), R ¹⁹ is an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a fluorinated alkane having 1 to 30 carbon atoms. Oxygen, optionally substituted cycloalkyl group with 3 to 10 carbon atoms, optionally substituted phenyl group with 6 to 20 carbon atoms, or hydrocarbon group with steroid skeleton with 17 to 51 carbon atoms. R ²⁰ is a single bond , -O-, -COO- or -OCO-. R ²¹ is a single bond, alkanediyl with 1 to 20 carbon atoms, phenylene, biphenylene, cyclohexylene, double cyclohexylene, the following formula A group represented by (C-1-1) or a group represented by the following formula (C-1-2). R ²² is a single bond or a divalent organic group. Wherein, when R ²⁰ is a single bond, R ²¹ is a single key. "*" means a bond key)

[hua 2]

(In formula (C-1-2), R ²³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. "**" represents a bond with R ²² ).

According to the liquid crystal aligning agent, a difference in pretilt angle can be sufficiently generated between one substrate and the other substrate. In addition, a difference in pretilt angle occurs between the substrates due to the difference in the heating conditions at the time of film formation. Therefore, even when a liquid crystal alignment film is formed using the same liquid crystal aligning agent for one substrate and the other substrate, the A sufficient difference in pretilt angle between substrates is excellent in productivity.

Hereinafter, the manufacturing method of a liquid crystal element is demonstrated. The liquid crystal element of the present disclosure can be manufactured by a method including a coating step, a heating step, and a cell construction step. Hereinafter, the manufacturing method of the liquid crystal element of this disclosure is demonstrated in detail.

In addition, the "hydrocarbon group" in this specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain and branched hydrocarbon group that does not include a cyclic structure but consists only of a chain structure. Among them, the chain hydrocarbon group may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that includes only an alicyclic hydrocarbon as a ring structure, and does not include an aromatic ring structure. in, The alicyclic hydrocarbon group does not need to be composed of only the structure of the alicyclic hydrocarbon, and includes those having a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. Among them, it is not necessary to consist only of an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

In the present specification, "tetracarboxylic acid derivative" means a tetracarboxylic dianhydride, a tetracarboxylic acid diester, and a tetracarboxylic acid diester dihalide. In addition, the meaning of "(meth)acrylate" includes acrylate and methacrylate.

"Coating Steps"

When manufacturing a liquid crystal element, first, a liquid crystal aligning agent is apply|coated to each board|substrate surface of a pair of board|substrates containing a 1st board|substrate and a 2nd board|substrate. As the substrate, for example, glass including float glass, soda glass, etc.; polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate, polycarbonate, poly(alicyclic olefin), etc. can be used Plastic transparent substrate. An electrode including a transparent conductive film or the like is formed on at least one of the pair of substrates. As the transparent conductive film, for example, a Nessa (NESA) film containing tin _oxide ( _{SnO 2} ) (registered trademark of U.S. PPG Corporation ₎ , an indium tin oxide ( Indium Tin Oxide, ITO) film and so on. When manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, when manufacturing an In-Plane-Switching (IPS) type or Fringe Field Switching (FFS) type liquid crystal element, a substrate provided with electrodes patterned in a comb-shaped pattern is used. , and the opposite substrate without electrodes. Any method can be applied to the coating of the liquid crystal aligning agent on the substrate, and it is preferably performed on the electrode formation surface by a lithographic method, a spin coating method, a roll coater method, a flexographic printing method or an inkjet printing method.

<Liquid crystal alignment agent>

Next, the liquid crystal aligning agent used for the manufacturing method of this disclosure is demonstrated in detail. The liquid crystal aligning agent is a polymer composition obtained by dissolving or dispersing a polymer component in an organic solvent.

Regarding the polymer component in the liquid crystal aligning agent, the main skeleton of the polymer is not particularly limited, and examples thereof include polyamide, polyimide, polyamide, polyamide, polyorganosiloxane , polyester, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, etc. as the polymer of the main skeleton. Among these, it is preferable to be selected from the group consisting of polyamide, polyimide, At least one of the group consisting of amino acid ester and polyorganosiloxane. In addition, as a polymer component, 1 type may be used individually, and 2 or more types may be used together.

The liquid crystal aligning agent used for the production method of the present disclosure contains a compound (hereinafter also referred to as "compound (P)") having a thermally detachable group which is detached by heating. The compound (P) can be any one of a polymer component and other components, preferably a polymer component, and particularly preferably selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane at least one of the group consisting of.

The thermally detachable group possessed by the compound (P) is not substantially detached by heating under the first temperature condition, and can be detached by heating under the second temperature condition higher than the first temperature condition The basis is not particularly limited. thermally detachable group The temperature at which the bond is disconnected (hereinafter also referred to as "release temperature") is preferably in the range of 100°C to 300°C, more preferably in the range of 150°C to 250°C, and further preferably in the range of 180°C. It is the range of 200 degreeC - 220 degreeC especially preferably.

The compound (P) preferably has a partial structure represented by the following formula (1) or formula (2) as a partial structure having a thermally releasable group.

(In formula (1), R ¹ is a single bond or a divalent organic group. X ¹ is a single bond, -O-, -S- or -NR ^II - (wherein, R ^II is a hydrogen atom or a hydrocarbon group, which can be combined with R ¹ is bonded to form a ring, and may also be a divalent hydrocarbon group contained in the main chain). Y ¹ is the thermally detachable group that cleaves the bond between Y ¹ and the oxycarbonyl group to be detached, or X ¹ The thermally detachable group that is severed from the oxycarbonyl group and simultaneously or separately from the oxycarbonyl group. "*" represents a bond)

[Chemical 4]*-R ¹ -Y ² (2)

(In formula (2), R ¹ is a single bond or a divalent organic group. Y ² is the thermally releasable group having the structure of the following formula (3). "*" represents a bond)

[hua 5]

(In formula (3), X ¹ is a single bond, -O-, -S- or -NR ^II - (wherein, R ^II is a hydrogen atom or a monovalent organic group, which may be bonded to R ¹ to form a ring). R ^III is a monovalent organic group. "**" represents a bond with R ¹ )

In X ¹ of the above-mentioned formula (1) and formula (3), the monovalent organic group of R ^II includes, for example, a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^II in X ¹ of the formula (1) is preferably a hydrogen atom or a monovalent hydrocarbon group.

From the viewpoint of securing the transparency of the film after thermal release, X ¹ in the above formulas (1) and (3) is preferably a single bond, -O- or -S-. In terms of good releasability by heating, Y ² in the above formula (2) is preferably bonded to a tertiary carbon atom which R ¹ has. As a divalent organic group of R ¹ , a divalent hydrocarbon group etc. are mentioned, for example.

The compound (P) preferably has a partial structure represented by the above formula (1) as having a thermally detachable substance from the viewpoint that the substance desorbed by heating is relatively easily volatilized and the substance is easily removed from the film. Part of the structure of the sex base. Specific examples of the partial structure represented by the formula (1) include a partial structure represented by the following formula (1-1), a partial structure represented by the following formula (1-2), and a partial structure represented by the following formula ( 1-3) The partial structure etc. shown.

[hua 6]

(In formula (1-1) to formula (1-3), R ³¹ , R ³² , R ³⁵ and R ³⁷ are each independently a monovalent organic group, R ³³ , R ³⁴ , R ³⁶ , R ³⁸ and R ³⁹ Each independently is a hydrogen atom or a monovalent organic group. Wherein, in formula (1-1), R ³² and R ³⁴ can be bonded to form a ring structure, and R ³³ and R ³⁴ can be bonded to form a ring structure. Formula ( In 1-3), R ³⁸ and R ³⁹ may be bonded to form a ring structure. R ¹ and X ¹ have the same meaning as in the formula (1))

In the above formulae (1-1) to (1-3), the monovalent organic groups of R ³¹ , R ³² , R ³⁵ and R ³⁷ are preferably monovalent hydrocarbon groups having 1 to 20 carbon atoms. As the monovalent organic group of R ³³ , R ³⁴ , R ³⁶ , R ³⁸ and R ³⁹ , for example, a monovalent hydrocarbon group having 1 to 40 carbon atoms having at least one -O- , -S-, -NR ^V -, -CO-, -COO-, -CO-NR ^V - (R ^V is a hydrogen atom or a monovalent hydrocarbon group with a carbon number of 1 to 10) and other heteroatom-containing groups, heteroatoms Ring base etc. Furthermore, at least one hydrogen atom possessed by the hydrocarbon group may be substituted with a substituent (eg, a halogen atom, a hydroxyl group, a cyano group, and the like).

Examples of the ring structure formed by ^R32 and ^{R34 bonding, the ring structure formed by R33 and R34 bonding ,} and the ring structure formed by ^R38 and ^R39 bonding include, for example, aliphatic rings, aromatic The structure of a ring such as a hydrocarbon ring, a heterocyclic ring, etc., and these rings may also have a substituent. X ¹ is preferably a single bond in that a polar group (carboxyl group) can be generated by thermal detachment.

The thermal desorption reactions in the partial structures represented by the formulas (1-1) to (1-3) are shown in the following Schemes 1 to 3, respectively. In addition, in Scheme 1, when X ¹ is -O-, -S- or -NR ^II -, CO ₂ is further removed to become "*-R ¹ -X ¹ H".

Regarding the compound (P), since the solvent in the liquid crystal aligning agent applied to the substrate can be removed, and the detachment temperature appears in the temperature range where the upper limit temperature set to protect the substrate is lower than the lower temperature side, these Among them, Y ¹ in the formula (1) is preferably bonded to an oxycarbonyl group with a tertiary carbon atom. It is particularly preferable that the compound (P) has a partial structure represented by the above formula (1-1) as a partial structure having a thermally releasable group. Furthermore, in the above formula (1-1), when X ¹ is a single bond, "-C(R ³¹ R ³² )-CH(R ³³ R ³⁴ )" corresponds to a thermally releasable group, and X 1 When ¹ is -O-, -S- or -NR ^II- , "-COO-C(R ³¹ R ³² )-CH(R ³³ R ³⁴ )" corresponds to a thermally releasable group.

Y ¹ in the formula (1) and R ^III in the formula (3) preferably have a function of imparting a pretilt angle to liquid crystal molecules, or a photo-radical generating function of generating radicals by light irradiation. , A functional functional group with specific functions, such as a photosensitizing function that exhibits a sensitizing action by light irradiation, and a polymerization inhibitor function that inhibits a polymerization reaction. When Y ¹ and R ^III have at least one of the above-mentioned functional functional groups (vertical alignment group, radical generating group, and polymerization inhibitor group), it can be determined according to the temperature conditions during heating during film formation. From this point of view, it is preferable to control the degree of expression of the functions of the liquid crystal alignment film formed on the first substrate and the liquid crystal alignment film formed on the second substrate.

(Vertical alignment group)

The vertical alignment group is a functional group that imparts a function of inducing a desired pretilt angle to liquid crystal molecules to a coating film formed using a liquid crystal alignment agent. This vertical alignment group exhibits a property of vertically aligning liquid crystal molecules independently of light irradiation. In the case where Y ¹ and R ^III have vertical alignment groups, the pre-tilt angle of the liquid crystal molecules induced by the liquid crystal alignment film can be changed between the first substrate and the second substrate by changing the vertical alignment restraint force of the liquid crystal alignment film. Substrates are sufficiently different.

Specific examples of the vertical alignment group include an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a fluorinated group having 1 to 30 carbon atoms. An alkoxy group, a group having a skeleton formed by linking at least one of a cyclohexane ring and a benzene ring in total, a group having a steroid skeleton, and the like. The vertical alignment group is preferably a group having a partial structure represented by the following formula (C-1).

[Chemical 10]*-R ²² -R ²¹ -R ²⁰ -R ¹⁹ (C-1)

(In formula (C-1), R ¹⁹ is an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a fluorinated alkane having 1 to 30 carbon atoms. Oxygen, optionally substituted cycloalkyl group with 3 to 10 carbon atoms, optionally substituted phenyl group with 6 to 20 carbon atoms, or hydrocarbon group with steroid skeleton with 17 to 51 carbon atoms. R ²⁰ is a single bond , -O-, -COO- or -OCO-. R ²¹ is a single bond, alkanediyl with 1 to 20 carbon atoms, phenylene, biphenylene, cyclohexylene, double cyclohexylene, the following formula A group represented by (C-1-1) or a group represented by the following formula (C-1-2). R ²² is a single bond or a divalent organic group. Wherein, when R ²⁰ is a single bond, R ²¹ is a single bond. R ²⁰ , R ²¹ and R ²² are single bonds, and R ¹⁹ is an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms. Or in the case of a fluorinated alkoxy group having 1 to 30 carbon atoms, R ¹⁹ has a straight chain structure. "*" represents a bond)

[Chemical 11]

(In formula (C-1-2), R ²³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. "**" represents a bond with R ²² )

In the formula (C-1), R ²⁰ , R ²¹ and R ²² are single bonds, and R ¹⁹ is an alkyl group with 1 to 30 carbon atoms, a fluoroalkyl group with 1 to 30 carbon atoms, and a fluoroalkyl group with 1 to 30 carbon atoms. In the case of an alkoxy group having 30 or a fluorinated alkoxy group having 1 to 30 carbon atoms, from the viewpoint of inducing a sufficiently high pretilt angle to liquid crystal molecules, the linear structure of R ¹⁹ is more preferably a carbon number of 5 or more. , more preferably 8 or more, particularly preferably 10 or more. As a C17-C51 hydrocarbon group which has a steroid skeleton, a cholestyl group, a cholestenyl group, a lanostane group, etc. are mentioned, for example.

The vertical alignment group preferably has a straight-chain structure having 8 or more carbon atoms, and has a total of two or more rings that connect at least one of a cyclohexane ring and a benzene ring from the viewpoint of high ability to impart a pretilt angle to liquid crystal molecules. The group of the resulting skeleton or the group having a steroid skeleton is more preferably a group having a skeleton formed by linking at least one of at least one of a cyclohexane ring and a benzene ring in total, or a group having a steroid skeleton.

Specific examples of the vertical alignment group include groups represented by the following formulae (c1-1) to (c1-10), for example. In the case where Y ¹ of the formula (1) is a vertical alignment group, R ²⁶ in the following formula is preferably -C(R ^IV ) ₂ -(wherein R ^IV is relative to the oxycarboxyl group) A monovalent hydrocarbon group having 1 to 10 carbon atoms. The same applies hereinafter.) When R ^III of the formula (3) is a vertical alignment group, it is preferably a single bond.

(In the formula, R ²⁶ is a single bond or a substituted or unsubstituted divalent hydrocarbon group. "*" represents a bond)

(radical generating group)

The radical generating group is not particularly limited as long as it is a functional group that exhibits at least any one of a photoradical generating function and a photosensitizing function. When Y ¹ and R ^III have a radical generating group, the reactivity of the photopolymerizable compound mixed into the liquid crystal layer to light in the PSA mode can be promoted, thereby enabling the prepositioning of the liquid crystal molecules induced by the liquid crystal alignment film. The inclination angle is sufficiently different between the first substrate and the second substrate.

As the radical generating group, a functional group derived from a known photoradical generating agent can be used. As a photoradical generator, for example, a phenalkyl ketone type compound can be mentioned. compounds, benzoin-based compounds, ketal-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthraquinone-based compounds and other radical generating group-containing compounds.

The radical generating group is preferably a group having at least one selected from the group consisting of a partial structure represented by the following formula (B-1) and a partial structure represented by the following formula (B-2).

(In the formula (B-1), Ar ¹ is a divalent aromatic ring group which may have a substituent, Ar ² is a monovalent aromatic ring group which may have a substituent, and Ar ¹ and Ar ² can pass through -O-, -S -, carbonyl or -NR ²³ - (R ²³ is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms) and are connected to each other. R ¹⁴ is a single bond or a divalent organic group. "*" represents a bond)

(In formula (B-2), Ar ³ is a divalent aromatic ring group which may have a substituent. R ¹⁵ and R ¹⁶ are each independently a monovalent organic group, and R ¹⁵ and R ¹⁶ may be bonded to form a ring. R ¹⁷ is a hydroxyl group or a monovalent organic group. R ¹⁸ is a single bond or a divalent organic group. "*" represents a bond)

The divalent aromatic ring groups of Ar ¹ and Ar ² in the formula (B-1) and Ar ³ in the formula (B-2) are two groups removed from the ring moiety of the substituted or unsubstituted aromatic ring. A base made of hydrogen atoms. As an aromatic ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example, Preferably it is a benzene ring. As a substituent which an aromatic ring may have, a C1-C6 alkyl group, an alkoxy group, a fluoroalkyl group, a fluorine atom, a hydroxyl group, etc. are mentioned, for example.

Among R ¹⁵ to R ¹⁷ in the formula (B-2), as a monovalent organic group, for example, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms can be listed. Substituted or unsubstituted alkoxy, benzyl, phenethyl, etc. As a substituent which an alkyl group and an alkoxy group may have, a fluorine atom, a hydroxyl group, etc. are mentioned, for example.

In R ¹⁴ in the formula (B-1) and R ¹⁸ in the formula (B-2), the divalent organic group includes, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a methylene group of the hydrocarbon group. A group substituted by -O-, -S- or -NR ^IV - (wherein, R ^IV is a hydrogen atom or a monovalent organic group. The same applies hereinafter), at least one hydrogen atom of the hydrocarbon group is substituted by a fluorine atom, an alkoxy group etc. substituted bases, etc. The monovalent organic group of R ^IV is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms.

As a specific example of the radical generating group, the partial structure represented by the formula (B-1) includes, for example, groups represented by the following formulae (B-1-1) to (B-1-4), respectively, and the like. ; The partial structure represented by the said formula (B-2), for example, the group represented by the following formula (B-2-1) ~ formula (B-2-7), etc. are mentioned, for example. In the case where Y ¹ of the above formula (1) is a radical generating group, R ²⁵ in the following formula is preferably a group bonded with -C(R ^IV ) ₂ - with respect to the oxycarboxyl group, When R ^III of the said formula (3) is a radical generating group, it is preferable that it is a single bond.

[Chemical 15]

(In the formula, R ²⁵ is a single bond or a divalent hydrocarbon group. "*" represents a bond)

(polymerization inhibitor base)

The polymerization inhibitor group acts as a peroxide decomposer that inactivates peroxy radicals or hydroperoxides generated by energy such as ultraviolet rays or heat, or traps radical intermediates in the middle of the polymerization and inhibits the progress of the polymerization reaction free radical scavengers to function. By containing the compound (P) having such a polymerization inhibitor group in the liquid crystal alignment film, the reaction of the photopolymerizable compound mixed into the liquid crystal layer in the PSA mode by light irradiation can be suppressed. Therefore, the pretilt angle of the liquid crystal molecules induced by the liquid crystal alignment film can be sufficiently different between the first substrate and the second substrate.

The polymerization inhibitor group is preferably a group having at least one selected from the group consisting of a hindered amine structure, a hindered phenol structure, and an aniline structure. Specifically, the hindered amine structure is preferably a partial structure represented by the following formula (A-1), the hindered phenol structure is preferably a partial structure represented by the following formula (A-2), and the aniline structure is preferably the following The partial structure represented by the formula (A-3).

[Chemical 16]

(In formula (A-1), R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or 1,3-dioxo Butyl. R ³ ~R ⁶ are independently an alkyl group with 1 to 6 carbons, an aryl group with 6 to 12 carbons, or an aralkyl group with 7 to 13 carbons. R ⁷ is a hydrogen atom or a carbon number of 1 to 13. The monovalent hydrocarbon group of 10. R ⁸ is a single bond or a divalent organic group. X ² is a single bond, -O-, carbonyl or * ² -CONH-. X ³ to X ⁶ are independently a single bond, -O- , carbonyl, * ² -CH ₂ -CO-, or * ² -CH ₂ -CH(OH)-. "* ² " represents a bond to a piperidine ring. "*" represents a bond)

(In formula (A-2), R ⁹ is an alkyl group having 1 to 16 carbon atoms, or an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or a combination of two or more of these in the skeleton chain of the alkyl group. The monovalent group of the base. n is an integer from 0 to 4. R ¹⁰ is a single bond or a divalent organic group. "*" represents a bond)

[Chemical 18]

(In formula (A-3), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 16 carbon atoms, or an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or the These are monovalent groups of groups obtained by combining two or more types. R ¹³ is a single bond or a divalent organic group. "*" represents a bonding bond)

R ² in the above formula (A-1) includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group as the alkyl group having 1 to 6 carbon atoms.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 3-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-isopropylphenyl, and 4-n-butylphenyl , 3-chloro-4-methylphenyl, 4-pyridyl, 2-phenyl-4-quinolinyl, 2-(4'-tert-butylphenyl)-4-quinolinyl, 2- (2'-phenylthio)-4-quinolinyl, etc.; Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group, a phenethyl group, and the like.

As the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the aralkyl group having 7 to 13 carbon atoms of R ³ to R ⁶ , the description of the above R ² can be applied.

When R ⁸ is a single bond, R ⁷ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

X ² to X ⁶ are each preferably a single bond.

As a specific example of the group represented by the said formula (A-1), the group etc. which are respectively represented by the following formula (A-1-1) - a formula (A-1-4) are mentioned, for example. When Y ¹ in the formula (1) is a polymerization inhibitor group, R ⁷ in the following formula is preferably a methyl group or an ethyl group, and R ^III in the formula (3) is a polymerization inhibitor group In the case of , R ⁷ in the following formula is preferably a hydrogen atom.

(In the formula, "*" represents a bond bond)

Regarding R ⁹ in the above formula (A-2), the alkyl group having 1 to 16 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a butyl group, and a hexyl group. , octyl, decyl, etc. Preferable specific examples of R ⁹ include tert-butyl, 1-methylpentadecyl, 1-ethylpentadecyl, octylthiomethyl, decylthiomethyl, Dodecylthiomethyl, tetradecylthiomethyl, etc.

The bonding position of R ⁹ is not particularly limited, but it is preferably bonded to at least the ortho position with respect to the phenolic hydroxyl group. n is preferably 1 to 4, more preferably 2.

As a specific example of the group represented by the said formula (A-2), the group etc. which are each represented by the following formula (A-2-1) - a formula (A-2-4) are mentioned, for example. In the case where Y ¹ of the above formula (1) is a polymerization inhibitor group, R ¹⁰ in the following formula is preferably a group bonded with -C(R ^IV ) ₂ - with respect to the oxycarboxyl group, When R ^III of the formula (3) is a polymerization inhibitor group, R ¹⁰ in the following formula is preferably a single bond.

(In the formula, "*" represents a bond bond)

Regarding R ¹¹ and R ¹² in the above formula (A-3), as an alkyl group having 1 to 16 carbon atoms, either a straight chain or a branch may be used. As a preferable specific example of ^R11 and ^R12 , a methyl group, an ethyl group, a propyl group, a tertiary butyl group etc. are mentioned, for example.

As a specific example of the group represented by the said formula (A-3), the group etc. which are respectively represented by the following formula (A-3-1) - a formula (A-3-4) are mentioned, for example. When Y ¹ of the above formula (1) is a polymerization inhibitor group, R ¹³ in the following formula is preferably a group bonded with -C(R ^IV ) ₂ - with respect to the oxycarboxyl group, In the case where R ^III of the formula (3) is a polymerization inhibitor group, R ¹³ in the following formula is preferably a single bond.

(In the formula, "*" represents a bond bond)

In the case where the thermally detachable group (Y ¹ ) in the formula (1) is detached by heating and thereby polar groups such as a carboxyl group, an amine group, and an amide group appear, the detachment of Y ¹ can be used to remove the group. The vertical alignment restraint force of the liquid crystal alignment film is changed (decreased). Therefore, the difference in the pretilt angle between the substrates can be increased by changing the heating conditions between the pair of substrates to vary the degree of detachment of Y ¹ . In this case, the compound (P) preferably has a partial structure in which X ¹ is a single bond and R ¹ is a divalent hydrocarbon group in the formula (1) as a partial structure having a thermally releasable group. Specifically, other than the case where Y ¹ in the above-mentioned formula (1) is a vertical alignment group, a radical generating group, or a polymerization inhibitor group, for example, the following formulas (8-1) to (8) are exemplified. -5) In the case where the partial structures shown respectively are partial structures having a thermally releasable group, and the like.

(In the formula, R ^VII is a divalent hydrocarbon group. "* ¹ " represents a bond to an atom in the main chain, and "*" represents a bond)

The compound (P) can be synthesized by appropriately combining conventional methods of organic chemistry according to the main skeleton. Hereinafter, the polymer of each of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane will be described.

<Polyamide>

In the case where the compound (P) is a polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid (P)") can be reacted with, for example, a tetracarboxylic dianhydride and a diamine compound. and obtained. At the time of this reaction, at least one of the tetracarboxylic dianhydride and the diamine compound uses a monomer having a thermally releasable group. It is preferable that at least a part of the diamine compound used in the synthesis contains a diamine ( Also referred to as "specific diamine" hereinafter).

(specific diamine)

As long as the specific diamine has a thermally releasable group and two primary amine groups, other structures are not particularly limited. The specific diamine is preferably at least one selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5). In these compounds, the thermally detachable group (Y ¹ ) is detached by heating, thereby generating a polar group.

(In formula (4), Y ¹ is a thermally releasable group)

[Chemical 24]

(In formula (5), R ⁴⁶ is a divalent organic group, and R ⁴⁷ is a single bond or a divalent organic group. Y ³ is a protective group that is desorbed by heat. t is an integer of 1 to 3, and s is 0 or 1)

The Y ¹ of the formula (4) preferably has one selected from the group consisting of a vertical alignment group, a radical generating group and a polymerization inhibitor group. The above description can be applied to specific examples and preferred examples of the vertical alignment group, the radical generating group, and the polymerization inhibitor group. It is preferable that the two primary amine groups which the diaminophenyl group has are bonded to the 2,4-position or the 3,5-position with respect to the other groups.

As the divalent organic group of R ⁴⁶ and R ⁴⁷ in the formula (5), for example, a divalent hydrocarbon group having 1 to 20 carbon atoms; CO-, -COO-, -COS-, -NR ^a -, -CO-NR ^a -, -Si(R ^a ) ₂ - (wherein R ^a is a monovalent hydrocarbon group with 1 to 12 carbon atoms), -N= A divalent group substituted by N-, -SO ₂ -, etc.; at least one of the hydrogen atoms bound to the carbon atom of the hydrocarbon group is replaced by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl, Divalent groups, etc., substituted with cyano groups, etc. Y ³ is preferably tert-butoxycarbonyl. t is preferably 1, and s is preferably 0.

Specific examples of the specific diamine include compounds represented by the formula (4), for example, compounds represented by the following formulae (4-1) to (4-31), and the like; As a compound represented, the compound etc. which are each represented by following formula (5-1) - formula (5-6) are mentioned, for example. Furthermore, as the specific diamine, these can be used alone one, or a combination of two or more.

[Chemical 27]

(In the formula, TMS represents a trimethylsilyl group)

(other diamines)

When synthesizing the polyamic acid (P), only the specific diamine may be used as the diamine compound, but the specific diamine may be used together with other diamines other than the specific diamine. as its Other diamines are not particularly limited as long as they do not have a thermally releasable group, and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine organosiloxanes. As specific examples of these, aliphatic diamines include, for example, m-xylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, and the like; The formula diamines include, for example, p-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), and the like; Examples of aromatic diamines include dodecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholestyalkoxydiaminobenzene, cholesteryl Alkenyloxydiaminobenzene, cholestyl diaminobenzoate, cholestyl diaminobenzoate, lanostalyl diaminobenzoate, 3,6-bis(4-amine) benzyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-butylcyclohexane, 2,5-diamino-N,N-diallylaniline, the following formula (DE-1)

(In formula (DE-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single A bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b do not become 0 at the same time )

Side chain type diamines such as the indicated compounds: p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-ethylidene diphenylamine, 4,4'-diaminodiphenylamine, 4,4'-diamine Diphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,2-bis (4-Aminophenoxy)ethane, 1,5-bis(4-aminophenoxy)pentane, N,N'-bis(4-aminophenoxy)-N,N'-di Methylethylenediamine, bis[2-(4-aminophenyl)ethyl]adipic acid, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methane amine, 1,4-bis(4-aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis [4-(4-Aminophenoxy)phenyl]propane, 4,4'-(phenylenediisopropylidene)dianiline, 1,4-bis(4-aminophenoxy)benzene , 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine) -1,4-diyl)] non-side-chain diamines such as diphenylamine; diaminoorganosiloxane, for example: 1,3-bis(3-aminopropyl)-tetramethyldisiloxane alkane and the like, and the diamine compound described in Japanese Patent Laid-Open No. 2010-97188 can be used. Furthermore, when synthesizing the polyamic acid (P), other diamines may be used alone or in combination of two or more.

From the viewpoint of sufficiently obtaining the effects of the present disclosure, the use ratio of the specific diamine is preferably 1 mol % or more with respect to the total amount of the diamine compounds used when synthesizing the polyamic acid (P). More preferably, it is 5 mol% or more, and still more preferably 10 mol% or more.

The specific diamine can be obtained by appropriately combining conventional methods of organic chemistry. As an example, the diamine represented by the above formula (4) includes: A dinitro intermediate having a nitro group as a primary amine group in the above formula (4), and then, a method of amination of the nitro group of the obtained dinitro intermediate using an appropriate reducing system, and the like. The method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound, and examples thereof include a method of reacting acyl chloride having a dinitrophenyl group with a tertiary alcohol having a thermally releasable group.

In addition, as for the diamine represented by the above formula (5), for example, diamine having "-NH-CO-" and di-tert-butyl dicarbonate can be prepared by using a strong base such as dimethylaminopyridine. The reaction was carried out in the presence of . However, the synthesis method of the specific diamine is not limited to the above method.

(tetracarboxylic dianhydride)

The tetracarboxylic dianhydride used for the synthesis of polyamic acid (P) is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Wait. As specific examples of these, aliphatic tetracarboxylic dianhydrides include, for example, ethylenediaminetetraacetic acid dianhydride, and the like; alicyclic tetracarboxylic dianhydrides include, for example, 1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2 ,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxo Tetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxo Tetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3 ,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentane Tetracarboxylic dianhydride, etc.; Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylene bis(trimellitic acid monoester) anhydride), ethylene glycol bis(trimellitic anhydride), 1,3-propanediol bis(trimellitic anhydride), 3,3',4,4'-benzophenone tetracarboxylic anhydride, etc. In addition, Japanese The tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(Synthesis of Polyamide)

Polyamic acid (P) can be carried out by combining the above-mentioned tetracarboxylic dianhydride and diamine compound with a molecular weight modifier (for example, acid monoanhydride, monoamine compound, monoisocyanate compound, etc.) if necessary obtained by the reaction. The use ratio of the tetracarboxylic dianhydride and the diamine compound to be used in the synthesis reaction of the polyamic acid (P) is preferably 0.2 for the acid anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amine group of the diamine compound. The ratio of equivalents to 2 equivalents.

The synthesis reaction of polyamide (P) is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. As an organic solvent used for a reaction, an aprotic polar solvent, a phenol type solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc. are mentioned, for example. The particularly preferred organic solvent is selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butylene One or more of the group consisting of lactone, tetramethylurea, hexamethylphosphoric triamine, m-cresol, xylenol and halogenated phenols are used as solvents, or one or more of these and other organic solvents ( For example, a mixture of butyl silosol, diethylene glycol diethyl ether, etc.). The use amount of the organic solvent is preferably set to The total amount of the tetracarboxylic dianhydride and the diamine compound is an amount of 0.1% by mass to 50% by mass relative to the total amount of the reaction solution. The reaction solution obtained by dissolving the polyamic acid (P) can be directly used for the preparation of the liquid crystal alignment agent, or the polyamic acid (P) contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

<Polyurethane>

The polyamide ester as the compound (P) can be obtained, for example, by reacting a tetracarboxylic acid diester and a diamine compound having a thermally releasable group. The reaction of the tetracarboxylic acid diester and the diamine is preferably carried out in an organic solvent in the presence of a dehydration catalyst and a base. The use ratio of the tetracarboxylic acid diester and the diamine to be used for the reaction is preferably a ratio of 0.2 to 2 equivalents of the carboxyl group of the tetracarboxylic acid diester with respect to 1 equivalent of the amine group of the diamine.

When the tetracarboxylic acid diester and the diamine are reacted, at least one compound selected from the group consisting of a tetracarboxylic dianhydride and a tetracarboxylic acid diester having no thermally detachable group may be used in combination. In this case, the use of the tetracarboxylic dianhydride and the tetracarboxylic acid diester having no thermal releasable group relative to the total of the tetracarboxylic acid diester and the tetracarboxylic dianhydride used in the synthesis of the polyamic acid ester The ratio (the total amount when two or more types are used) is preferably 50 mol % or less, more preferably 40 mol % or less, and still more preferably 30 mol % or less.

As the organic solvent used for the reaction, the organic solvents exemplified as those used in the synthesis of polyamic acid (P) can be mentioned. Examples of the dehydration catalyst used in the reaction include halogenated 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine, carbonylimidazole , Dicyclohexylcarbodiimide, phosphorus-based condensing agent, etc. Relative to 1 mole of tetracarboxylic acid diester, the use ratio of these dehydration catalysts is preferably set to 2 mol ~ 3 mol. As the base, for example, tertiary amines such as pyridine and triethylamine can be preferably used. The use ratio of the base is preferably 2 mol to 4 mol relative to 1 mol of the diamine. In addition, the reaction may be performed in the presence of a Lewis acid for the purpose of promoting the progress of the reaction. As a Lewis acid, lithium halides, such as lithium chloride, etc. are mentioned, for example. The reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours.

The reaction solution obtained in the above manner can be directly used for the preparation of the liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution can be separated and then used for the preparation of the liquid crystal aligning agent. The isolation and purification of the polyamic acid ester can be performed according to a known method.

Furthermore, in addition to the method of reacting the tetracarboxylic acid diester with the diamine, the polyamide ester as the compound (P) can be prepared by, for example, making the polyamide acid (P) and an esterification agent (such as methanol or A method for reacting ethanol, N,N-dimethylformamide diethyl acetate, etc.), a method for reacting a tetracarboxylic acid diester dihalide having a thermally releasable group, and a diamine compound, etc. get.

<Polyimide>

The polyimide as the compound (P) is a polymer having a thermally releasable group. This polyimide can be obtained, for example, by dehydrating and ring-closing the polyimide (P) synthesized as described above, followed by imidization. The polyimide may be a complete imide obtained by dehydrating and ring-closing all the amide structures of the polyamide (P), which is a precursor thereof, or only a part of the amide structure. A partial amide imide compound in which an amide acid structure and an amide ring structure coexist by dehydration and ring closure. The polyimide preferably has an imidization rate of 40% to 100%, more preferably 60% to 90%. The imidization rate is expressed as a percentage with respect to the number of imide ring structures relative to the number of imide structures of polyimide and The ratio of the total number of imide ring structures. Here, a part of the imide ring may be an isoimide ring.

The dehydration and ring closure of the polyamide acid (P) is preferably performed by the following method: dissolving the polyamide acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. As the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used, for example. The amount of the dehydrating agent used is preferably 0.01 mol to 20 mol with respect to 1 mol of the amide structure of the polyamide acid. As the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration closed-loop catalyst used is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. As the organic solvent to be used, the organic solvent exemplified as the one used for the synthesis of the polyamic acid (P) can be mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0°C to 180°C, and the reaction time is preferably 1.0 hours to 120 hours. The polyimide-containing reaction solution obtained in this way can be directly used for the preparation of a liquid crystal alignment agent, or the polyimide can be separated and then used for the preparation of a liquid crystal alignment agent.

When made into a solution with a concentration of 10% by weight, the viscosity of the solution of polyamide, polyamide ester and polyimide is preferably 10mPa. s~800mPa. s of the solution viscosity, it is better to have 15mPa. s~500mPa. s is the solution viscosity. In addition, the solution viscosity (mPa.s) is for a polymer with a concentration of 10% by mass prepared using a good solvent for these polymers (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). solution, measured at 25°C using an E-type rotational viscometer.

Determination of polystyrene exchange by gel permeation chromatography (Gel Penetration Chromatography, GPC) of polyamides, polyamides and polyimides The calculated weight average molecular weight (Mw) is preferably 1,000 to 500,000, more preferably 5,000 to 100,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. In addition, the polyamic acid, polyamic acid ester, and polyimide contained in the liquid crystal aligning agent may be only one type, or two or more types may be combined.

<Polyorganosiloxane>

The polyorganosiloxane having a thermally releasable group (hereinafter also referred to as "specific polyorganosiloxane") can be hydrolyzed by, for example, a hydrolyzable silane compound. obtained by condensation. Specifically, the following [1] or [2] can be mentioned: [1] A hydrolyzable silane compound (ms-1) having an epoxy group, or a combination of the silane compound (ms-1) and another silane compound The mixture is hydrolyzed and condensed to synthesize an epoxy-containing polyorganosiloxane, and then the obtained epoxy-containing polyorganosiloxane and a carboxylic acid having a thermally releasable group (hereinafter also referred to as "specific carboxylate") are synthesized. [2] A method of hydrolyzing a hydrolyzable silane compound (ms-2) having a thermally releasable group, or a mixture of the silane compound (ms-2) and other silane compounds, etc. . Among these methods, the method [1] is simple and can improve the introduction rate of the photoalignment group in the polyorganosiloxane, and is preferred in this respect.

Specific examples of the silane compound (ms-1) include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyl Alkylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4 - Epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, etc. As the silane compound (ms-1), one of these can be used alone, or two or more of them can be used in combination.

The other silane compound is not particularly limited as long as it is a silane compound showing hydrolyzability, and examples thereof include tetramethoxysilane, methyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-aminopropyl trimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltrimethoxysilane, p-benzene Vinyl trimethoxy silane, trimethoxy silyl propyl succinic anhydride, etc. Other silane compounds may be used alone or in combination of two or more.

Hydrolysis of silane compounds. The condensation reaction can be performed by reacting one or more of the above-mentioned silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent.

In the above-mentioned method [1], the epoxy group-containing polyorganosilicon is not only capable of sufficiently introducing photoalignment groups into the polymer, but also suppresses side reactions caused by excess epoxy groups. The epoxy equivalent of the oxane is preferably 100 g/mol to 10,000 g/mol. hydrolysis. During the condensation reaction, the use ratio of water is preferably 0.5 mol to 100 mol, more preferably 1 mol to 30 mol, relative to 1 mol of the silane compound (total amount).

as hydrolysis. Examples of catalysts used in the condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. The amount of the catalyst used varies depending on the type of the catalyst, reaction conditions such as temperature, and the like, and should be appropriately set. For example, it is preferably 0.01 to 3 moles relative to the total amount of the silane compound. do for the hydrolysis. Examples of the organic solvent used in the condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols, and the like. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The usage ratio of the organic solvent is preferably 10 parts by mass to 10,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, with respect to 100 parts by mass in total of the silane compound used in the reaction.

The hydrolysis. The condensation reaction is preferably carried out by heating with, for example, an oil bath or the like. hydrolysis. In the condensation reaction, the heating temperature is preferably 130° C. or lower, and the heating time is preferably 0.5 to 12 hours. After the completion of the reaction, the organic solvent layer separated from the reaction solution is dried with a desiccant if necessary, and the solvent is removed, whereby the target polyorganosiloxane can be obtained. Furthermore, the synthesis method of polyorganosiloxane is not limited to the hydrolysis. The condensation reaction can be performed, for example, by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

In the method [1], the epoxy group-containing polyorganosiloxane obtained by the reaction is then reacted with a specific carboxylic acid. Thereby, the epoxy group which the epoxy-group-containing polyorganosiloxane has reacts with a carboxylic acid, and the polyorganosiloxane which has a thermally releasable group can be obtained. The specific carboxylic acid is not particularly limited as long as it has a thermally releasable group, and a carboxylic acid having a partial structure represented by the above formula (1-1) is preferably used. A specific carboxylic acid can be used individually by 1 type or in combination of 2 or more types.

The specific carboxylic acid is preferably a carboxylic acid represented by the following formula (6). Specific examples thereof include compounds represented by the following formulae (6-1) to (6-24), for example. As a divalent organic group of R ^<50 >, a C1-C20 divalent hydrocarbon group, a heterocyclic group, etc. are mentioned, for example.

(In formula (6), R ⁵⁰ is a divalent organic group, and Y ¹ is a thermally releasable group)

[Chemical 33]

Furthermore, when the epoxy group-containing polyorganosiloxane is reacted with a specific carboxylic acid, a carboxylic acid (other carboxylic acid) which does not have a thermally releasable group may be used in combination. There is no restriction|limiting in particular as other carboxylic acid used, For example, (meth)acrylic acid, methyl (meth)acrylate, etc. are mentioned. In addition, other carboxylic acid may be used individually by 1 type or in combination of 2 or more types.

When the epoxy group-containing polyorganosiloxane is reacted with a carboxylic acid, the proportion of the carboxylic acid used relative to the total 1 mole of the epoxy groups contained in the epoxy group-containing polyorganosiloxane In the case of two or more kinds, the total amount) is preferably 0.001 mol to 0.99 mol, more preferably 0.01 mol to 0.9 mol. The use ratio of the specific carboxylic acid (the total amount when two or more types are used) is preferably set to 0.001 with respect to 1 mole of the total epoxy groups contained in the epoxy group-containing polyorganosiloxane. Molar or more, more preferably 0.01 mol to 0.8 mol.

The reaction of the epoxy group-containing polyorganosiloxane with the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst, for example, an organic base, a compound known as a so-called curing accelerator that accelerates the reaction of an epoxy compound, and the like can be used. Among them, a tertiary organic amine or a quaternary organic amine is preferable. relative to epoxy-containing For 100 parts by mass of organosiloxane, the use ratio of the catalyst is preferably 0.01 parts by mass to 100 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass.

Examples of the organic solvent used in the reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols, and the like. Among these, at least one selected from the group consisting of ethers, esters and ketones is preferred from the viewpoints of solubility of raw materials and products, and easiness of purification of products, as particularly preferred solvents. Specific examples include 2-butanone, 2-hexanone, methyl isobutyl ketone, butyl acetate, and the like. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total mass of the components other than the solvent in the reaction solution to the total mass of the solution) becomes 0.1 mass % or more, more preferably It is used in a ratio of 5% by mass to 50% by mass.

The reaction temperature in the reaction is preferably 0°C to 200°C, and the reaction time is preferably 1.0 hour to 50 hours. After the completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. The reaction solution containing the photoalignment polyorganosiloxane can be directly used for the preparation of the liquid crystal alignment agent, or the photoalignment polyorganosiloxane contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

About a specific polyorganosiloxane, the polystyrene conversion weight average molecular weight (Mw) measured by GPC, Preferably it exists in the range of 100-50,000, More preferably, it exists in the range of 200-10,000. When the weight-average molecular weight of the specific polyorganosiloxane is in the above-mentioned range, it is easy to handle when producing a liquid crystal alignment film, and the obtained film has sufficient material strength and properties.

"Other Ingredients"

The liquid crystal aligning agent of the present disclosure may also contain other than the compound (P) as necessary. his ingredients. Examples of the other components include polymers without thermally detachable groups (hereinafter also referred to as "other polymers"), compounds having at least one epoxy group in the molecule, functional silane compounds, and metal chelates. Compounds, hardening accelerators, surfactants, fillers, dispersants, etc. The compounding ratio of these can be suitably selected according to each compound within the range which does not impair the effect of this disclosure.

Other polymers can be used for the purpose of suppressing the decrease in the voltage holding ratio or for the purpose of improving the alignment of liquid crystals. The main skeleton of the other polymer is not particularly limited, and is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. As a preferable aspect of the polymer component in a liquid crystal aligning agent, the following (i) and (ii) are mentioned.

(i) The polymer component contains only at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and the polymer has a thermally releasable group.

(ii) The polymer component contains at least one polymer (Q) and polyorganosiloxane selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and polymer (Q) A form in which the polyorganosiloxane does not have a thermally releasable group and has a thermally releasable group.

When other polymers are prepared in the liquid crystal alignment agent, the blending ratio is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass relative to the total amount of polymers in the liquid crystal alignment agent. , more preferably 15% by mass to 80% by mass.

<Solvent>

The liquid crystal aligning agent of the present disclosure is a compound (P) and other compounds used as needed. It is prepared as a liquid composition in which other components are dispersed or dissolved in an appropriate solvent.

As the organic solvent to be used, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butane can be mentioned. Lactone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol mono Methyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol- Isopropyl ether, ethylene glycol-n-butyl ether (butyl silosol), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isobutyric acid Isoamyl ester, diisoamyl ether, ethylene carbonate, propyl carbonate, etc. These can be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) can be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably The range of 1 mass % to 10 mass %. That is, the liquid crystal alignment agent is applied on the surface of the substrate as described later, preferably by heating, to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. At this time, when the solid content concentration is less than 1 mass %, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10 mass %, there is a tendency that the film thickness of the coating film becomes too large, making it difficult to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases and the coating Decreased sex.

The content ratio of the compound (P) in the liquid crystal aligning agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, with respect to 100 parts by mass in total of the solid content (components other than the solvent) in the liquid crystal aligning agent, and further Preferably it is 30 mass parts or more.

"Heating Steps"

After the liquid crystal aligning agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing sagging of the applied liquid crystal aligning agent and ensuring the uniformity of the coating film. The prebaking temperature is preferably 30°C to 150°C, more preferably 50°C to 120°C. The pre-baking time is preferably 0.25 minutes to 10 minutes, more preferably 1 minute to 5 minutes. After that, the solvent is completely removed, and if necessary, calcination (post-baking) is performed for the purpose of thermal imidization of the amide acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80° C. to 300° C., and the post-baking time is preferably 5 minutes to 200 minutes. In addition, the post-baking time of a 1st board|substrate and a 2nd board|substrate may mutually be the same or different.

When the substrate to which the liquid crystal aligning agent is applied is heated, a high-temperature heat treatment in which one of the first substrate and the second substrate is heated at a higher temperature than the other substrate is performed. Since the liquid crystal aligning agent containing the compound (P) is used in the coating step, the thermally releasable groups in the liquid crystal aligning films formed on the first substrate and the second substrate can be released according to the temperature conditions during heating. The degrees differ from each other. As a result, the first substrate and the second substrate can exhibit different pretilt angles between the substrates. Furthermore, in the heating step, in order to increase the difference in the degree of detachment of the thermally detachable group, the heating time of the substrate to be subjected to the high-temperature heat treatment among the first substrate and the second substrate may be set longer. The other is longer.

Regarding the heating of the first substrate and the second substrate, for the first substrate and the second substrate Among the substrates, the substrate (for example, the first substrate) that is not subjected to high-temperature heat treatment is subjected to the first temperature condition in which the thermally detachable group possessed by the compound (P) is not substantially released; for the substrate that is subjected to high-temperature heat treatment (for example, The second substrate) is carried out under the second temperature condition which is higher than the first temperature condition and in which the thermally detachable group of the compound (P) can be detached. From the viewpoint of sufficiently increasing the difference in the pretilt angle between the pair of substrates, the heating temperature under the second temperature condition is preferably a temperature higher than that of the first temperature condition by 20° C. or more. The difference in heating temperature between a pair of substrates is more preferably 30°C or more, and more preferably 40°C to 100°C.

Specifically, the first temperature condition is preferably 80°C to 210°C, more preferably 130°C to 200°C, and still more preferably 150°C to 180°C from the viewpoint of the heat resistance temperature of the substrate and the boiling point of the solvent. The second temperature condition is preferably 180°C to 300°C, more preferably 200°C to 250°C, and still more preferably 200°C to 230°C.

The aspect which makes the heating temperature of a 1st board|substrate and a 2nd board|substrate different is not specifically limited, For example, the following method is mentioned.

[1] After pre-baking at a predetermined pre-baking temperature, post-baking is performed at a temperature higher than the pre-baking temperature, and at this time, one of the first substrate and the second substrate is A method of post-baking under the first temperature condition and post-baking the other substrate under the second temperature condition.

[2] After pre-baking at a predetermined pre-baking temperature, the first substrate and the second substrate are subjected to a first temperature condition higher than the pre-baking temperature, that is, the first substrate and the second substrate Post-baking is performed under the same conditions, and after the post-baking, only one of the first substrate and the second substrate is further heated under the second temperature condition method.

Among these methods, the method [1] is preferable in that the number of steps can be reduced as much as possible when manufacturing a liquid crystal element. The film thickness of the film formed by such heat treatment is preferably 0.001 μm to 1 μm.

<Contact step>

When manufacturing a liquid crystal element, after post-baking and before constructing a liquid crystal cell, a contact step of at least contacting the coating surface of the liquid crystal aligning agent in the substrate heated at high temperature with water or a liquid containing an organic solvent may be further included. By carrying out such a contact process, the compound released by the heat treatment can be removed from the film, which is preferable in that display failure can be suppressed in the obtained liquid crystal element. Here, as the organic solvent, for example, methanol, ethanol, 1-propanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cylosol, ethyl lactate, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone. Among these, the solvent used in the contacting step is preferably water, isopropanol and a mixture of these.

As a contact method of a liquid crystal aligning film and a solvent, a spray process, a shower process, a dipping process, a liquid coating process, etc. are mentioned, for example, However, It is not limited to these. At this time, in order to make the liquid crystal alignment film and the solvent fully contact, it is also effective to, for example, perform a series of processes of supplying and contacting the liquid crystal alignment film on the substrate with the solvent multiple times, or stirring or shaking the solvent. The contact time between the liquid crystal alignment film and the solvent is not particularly limited, but is, for example, 5 seconds to 15 minutes. For the purpose of removing the contacted liquid from the liquid crystal alignment film, a heat treatment of the coating film may be further performed after the contacting step.

"Unit Construction Steps"

In this step, a liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed, and disposing liquid crystal between the two substrates arranged to face each other. When manufacturing a liquid crystal cell, for example, two substrates are arranged to face each other through a gap so that the liquid crystal alignment films face each other, and the peripheral parts of the two substrates are bonded together using a sealant, and the surface of the substrate is placed on the surface of the substrate with the sealant. A method of injecting and filling liquid crystal into the enclosed cell space to form a liquid crystal layer, and then sealing the injection hole; a method of using a liquid crystal drop filling (one drop filling, ODF) method, and the like. As the sealing agent, for example, epoxy resin containing a curing agent and alumina balls as spacers can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferred.

When a liquid crystal element of the PSA system is produced, after the liquid crystal compound and the photopolymerizable compound are allowed to exist in the liquid crystal layer, and after the construction of the liquid crystal cell, a voltage is applied to the liquid crystal between the conductive films included in the pair of substrates. The unit is subjected to light irradiation treatment. As the liquid crystal compound, a nematic liquid crystal having negative dielectric anisotropy can be preferably used. As the photopolymerizable compound, for example, a compound having a functional group capable of radical polymerization, such as a (meth)acryloyl group and a vinyl group, can be used. It is preferable that the compounding ratio of a photopolymerizable compound shall be 0.05 mass % - 0.8 mass % with respect to the total amount of a liquid crystal compound and a photopolymerizable compound.

In the PSA treatment, as the light to be irradiated to the liquid crystal cell, for example, ultraviolet rays or visible rays including light having a wavelength of 150 nm to 800 nm can be used. Among them, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferred. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an excimer laser or the like is used. The irradiation amount of light is preferably 1 J/m ² to 10 J/m ² , more preferably 2 J/m ² to 8 J/m ² .

When applied to a curved display, it can be manufactured by bending the liquid crystal cell obtained above. Here, when a curved display is manufactured by bending a liquid crystal cell, a pretilt angle may vary between one substrate and the other of the pair of substrates, and a region in which the alignment of the liquid crystal is disturbed may occur. In this case, there is a fear that a dark part will appear in the screen in the area where the alignment disorder has occurred, and the image quality may be degraded. In this respect, in the liquid crystal element of the present disclosure, a sufficiently large difference in inclination can be generated between the substrates in the liquid crystal cell before bending. For example, the inclination angle of one substrate side of the pair of substrates is set to be substantially vertical, and the inclination angle of the other substrate side is set to a smaller angle in advance. Therefore, even when the liquid crystal cell is bent, the variation of the pretilt angle between the substrates can be suppressed. In other words, according to the manufacturing method of the present disclosure, the difference in inclination between the substrates can be sufficiently generated, whereby the image quality can be sufficiently ensured even when applied to a curved display. Moreover, when forming a liquid crystal alignment film on a 1st board|substrate and a 2nd board|substrate, it is sufficient to use the same liquid crystal aligning agent, and the said effect can be achieved by a simple method.

Next, a polarizing plate is bonded to the outer surface of a liquid crystal cell as needed, and a liquid crystal element is produced. Examples of the polarizing plate include a polarizing plate in which a polarizing film called "H film" is sandwiched between a cellulose acetate protective film, or a polarizing plate including an H film itself, which is made of polyvinyl alcohol while mixing polyvinyl alcohol. The extension alignment is formed by absorbing iodine on one side.

The obtained liquid crystal element is preferably the pretilt angle of the liquid crystal molecules induced by the liquid crystal alignment film formed on the first substrate and the pretilt angle of the liquid crystal molecules formed on the second substrate. The difference in the pretilt angle of the liquid crystal molecules induced by the liquid crystal alignment film (hereinafter also referred to as "tilt difference") is 0.8° or more. In this case, when applied to a curved display, the effect of suppressing the degradation of the image quality can be sufficiently obtained, which is preferable. From such a viewpoint, the difference in the pretilt angle between the pair of substrates is more preferably 1.0° or more, more preferably 1.5° to 5.0°, and particularly preferably 1.8° to 4.0°.

The liquid crystal element of the present disclosure can be effectively used in various applications such as clocks, portable game machines, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), Digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices, or dimming films, etc. In addition, the liquid crystal element of the present disclosure can also be applied to a retardation film.

[Example]

Hereinafter, the present invention is not limited to these examples, although it will be described in more detail with reference to the examples.

The weight average molecular weight Mw of the polymer, the imidization rate of the polyimide, the solution viscosity, and the epoxy equivalent in this Example were measured by the following methods.

[Weight Average Molecular Weight Mw]

The weight average molecular weight Mw is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

String: Tosoh Co., Ltd., TSKgel IGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40℃

Pressure: 68kgf/cm ²

[Imidation rate of polyimide]

The solution of polyimide was poured into pure water, the obtained precipitate was fully dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfite, and measured at room temperature using tetramethylsilane as a reference material. Hydrogen spectrum nuclear magnetic resonance ( ¹ H-nuclear magnetic resonance, ¹ H-NMR). From the obtained ¹ H-NMR spectrum, the imidization rate [%] was determined by the formula represented by the following numerical formula (1).

Imidization rate [%]=(1-A ¹ /A ² ×α)×100…(1)

(In the formula (1), A ¹ is the peak area of a proton derived from an NH group appearing in the vicinity of a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of the polymer (polyamide The ratio of the number of other protons in the amine acid) to one proton of the NH group)

[Solution viscosity of polymer solution]

Using a predetermined solvent, the solution viscosity (mPa·s) of the polymer solution was measured at 25°C using an E-type rotational viscometer for a solution adjusted to a polymer concentration of 10% by mass.

[Epoxy equivalent]

Measured according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

The structures and abbreviations of the main compounds used in the following examples are as follows.

(tetracarboxylic dianhydride)

t-1: 2,3,5-tricarboxycyclopentylacetic dianhydride

t-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

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

t-4: pyromellitic dianhydride

(specific diamine)

DA-1 to DA-5: compounds represented by the following formulae (DA-1) to (DA-5), respectively

(other diamines)

d-1 to d-13: compounds represented by the following formulae (d-1) to (d-13), respectively

(Specific Carboxylic Acids and Other Carboxylic Acids)

Specific carboxylic acids CA-6 to CA-10: compounds represented by the following formulae (CA-6) to (CA-10), respectively

Other carboxylic acids c-1 to c-2: compounds represented by the following formulas (c-1) and (c-2), respectively

[Chemical 37]

(Silane compound)

<Synthesis of specific diamine>

[Synthesis Example 1]

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

‧Synthesis Example 1-1: Synthesis of Compound (1-1-1)

[Chemical 39]

50 mL of methanol was added to the beaker, and 5 mL of sulfuric acid was added while cooling with ice. 16.50 g of compound (1-1-a), 150 mL of tetrahydrofuran, and the total amount of the methanol solution of sulfuric acid prepared before were added to a 500 mL-capacity eggplant-shaped flask equipped with a reflux tube, followed by heating under reflux for 14 hours. The reaction solution was concentrated to about half of the liquid volume, diluted with 200 mL of ethyl acetate, washed once with 150 mL of saturated sodium bicarbonate water, and three times with 150 mL of distilled water. The aqueous phases were combined and extracted once with 150 mL of ethyl acetate. After the organic phases were combined and dried over magnesium sulfate, the solvent was distilled off and dried to obtain 17.17 g of a crude product of compound (1-1-1).

‧Synthesis Example 1-2: Synthesis of Compound (1-1-2)

13.72 g of compound (1-1-1) was placed in a three-necked flask with a capacity of 300 mL provided with a reflux tube, a nitrogen gas introduction tube, and a dropping funnel, followed by nitrogen substitution, and 40 mL of dehydrated tetrahydrofuran was added and dissolved. 120 mL of methylmagnesium chloride (about 1 M tetrahydrofuran solution) was prepared in a dropping funnel, and was added dropwise to the solution of compound (1-1-1) over about 1.5 hours while cooling with ice. After the dropwise addition, the temperature was increased, and the temperature was 70 °C. Stir for 1 hour. In a 2-L conical flask, 400 mL of ethyl acetate and 400 mL of a 5 wt % aqueous solution of sodium hydrogen sulfate were prepared, and the reaction solution after being left to cool was added and vigorously stirred. After removing the aqueous layer, the organic phase was further washed three times with 300 mL of distilled water, and dried with magnesium sulfate, and then the solvent was distilled off and dried to obtain 13.05 g of a crude product of compound (1-1-2).

‧Synthesis Example 1-3: Synthesis of Compound (1-1-3)

12.53 g of compound (1-1-2) and 1.92 g of sodium hydride (60% by weight, dispersed in liquid paraffin) were put into a three-necked flask with a nitrogen introduction tube and a dropping funnel with a capacity of 300 mL, and the system was subjected to nitrogen gas. Substitution, 40 mL of dehydrated tetrahydrofuran was added and dissolved. A liquid obtained by dissolving 11.03 g of 3,5-dinitrobenzyl chloride in 20 mL of dehydrated tetrahydrofuran was prepared in a dropping funnel, and it was added dropwise over about 1 hour while cooling with ice. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the precipitate was separated by filtration, the filtrate was concentrated to less than half of the liquid volume. To this, 150 mL of ethyl acetate was added and diluted, and then washed three times with 200 mL of distilled water. After drying the organic phase with magnesium sulfate, the solvent was distilled off. The obtained solid was dissolved in a small amount of ethyl acetate and reprecipitated with a large amount of hexane. collect sediment and It was dried to obtain 20.06 g of a crude product of compound (1-1-3).

‧Synthesis Example 1-4: Synthesis of Compound (DA-1)

19.14 g of compound (1-1-3), 23.04 g of zinc (powder), and 7.42 g of ammonium chloride were added to a three-necked flask having a nitrogen introduction tube and a dropping funnel with a capacity of 1000 mL, and the system was replaced with nitrogen. To this, 200 mL of tetrahydrofuran and 100 mL of ethanol were added and stirred. While cooling the solution with ice, 25 mL of distilled water was added dropwise, followed by stirring at room temperature for 4 hours. The insoluble matter was separated by filtration, 500 mL of ethyl acetate was added, and the mixture was washed three times with 300 mL of distilled water. After drying the organic layer with magnesium sulfate, 10.71 g of a crude product of compound (DA-1) was obtained by distilling off the solvent and making it dry. The resultant purified by recrystallization was used in the subsequent polymerization reaction.

[Synthesis Example 2]

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

‧Synthesis Example 2-1: Synthesis of Compound (1-2-1)

[Chemical 43]

Compound (1-2-a) 8.61 g, distilled water 35 mL, copper chloride (I) 0.99 g, and acetaldehyde 12 mL were placed in a 200 mL eggplant-shaped flask equipped with a reflux tube and a dropping funnel, and heated to 70°C. Using a dropping funnel, 16 mL of 30% hydrogen peroxide water was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred at 90°C for 2 hours. After standing to cool, the peroxide was treated with a saturated aqueous sodium thiosulfate solution, and then saturated aqueous sodium bicarbonate was added until the pH of the reaction solution became 11. The reaction solution was extracted twice with 30 mL of ethyl acetate, and the organic layers were combined and dried over magnesium sulfate, and then the solvent was distilled off and dried to obtain 8.30 g of a crude product of compound (1-2-1).

‧Synthesis Example 2-2: Synthesis of Compound (1-2-2)

8.06 g of compound (1-2-1) was placed in a three-necked flask with a capacity of 300 mL provided with a reflux tube, a nitrogen gas introduction tube, and a dropping funnel, followed by nitrogen replacement, and 25 mL of dehydrated tetrahydrofuran was added and dissolved. 100 mL of ethylmagnesium bromide (about 1 M tetrahydrofuran solution) was prepared in a dropping funnel, and it was dripped over 1 hour while cooling with ice. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. 2L triangular roast In the bottle, 200 mL of ethyl acetate and 200 mL of a 5 mass % aqueous solution of sodium hydrogen sulfate were prepared, and the reaction solution after being left to cool was added and vigorously stirred. After removing the aqueous layer, the organic phase was further washed three times with 150 mL of distilled water, and dried with magnesium sulfate, and then the solvent was distilled off and dried to obtain 8.53 g of a crude product of compound (1-2-2).

‧Synthesis Example 2-3: Synthesis of Compound (DA-2)

Compound (1-2-3) was synthesized in the same manner as in Synthesis Example 1-3, except that the starting material was changed to Compound (1-2-2). Using the obtained dinitro compound, compound (DA-2) was synthesized in the same manner as in Synthesis Example 1-4.

[Synthesis Example 3]

The compound (DA-3) was synthesized by performing the same reaction as in Synthesis Example 1-1 to Synthesis Example 1-4 using 4-benzylbenzoic acid as a starting material. Furthermore, 4-benzylbenzoic acid has a ketone structure, so the product in the first stage is a dimethyl ketal, but it is deprotected by post-treatment with an acid in the second stage and restored to ketone structure.

[Synthesis Example 4]

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

‧Synthesis Example 4-1: Synthesis of Compound (1-4-1)

11.26 g of Irgacure 2959 (manufactured by BASF, phenalkyl ketone-based photopolymerization initiator), pyridinium dichromate (pyridinium dichromate) were placed in a 1000 mL eggplant-shaped flask equipped with a reflux tube dichromate, PDC) 65.92 g, dimethylformamide 150 mL, and stirred at room temperature for 18 hours. use B The reaction solution was diluted with 500 mL of ethyl acetate, and extracted with 300 mL of a 5% aqueous sodium hydroxide solution. After the aqueous layer was washed with 100 mL of ethyl acetate and the organic layer was removed, hydrochloric acid was added to the aqueous layer to adjust pH to 3. Extracted twice with 200 mL of ethyl acetate. After the organic layers were combined and dried over magnesium sulfate, the solvent was distilled off and dried to obtain 9.39 g of a crude product of compound (1-4-1).

‧Synthesis Example 4-2: Synthesis of Compound (DA-4)

Using compound (1-4-1) as a raw material, and performing the same reaction as in Synthesis Example 1-1, a methyl ester body was synthesized. After making sodium hydride act on the obtained ester body, it reacts with methyl iodide (methyl iodide), and the tertiary alcohol part is made into a methyl ether. Compound (DA-4) was synthesized by subjecting the obtained compound to the same reaction as in Synthesis Example 1-2 to Synthesis Example 1-4.

<Synthesis of specific carboxylic acid>

[Synthesis Example 5]

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

‧Synthesis Example 5-1: Synthesis of Compound (6-1-1)

A compound was synthesized in the same manner as in Synthesis Example 1-3, except that 3,5-dinitrobenzyl chloride was changed to methyl p-(chlorocarbonyl)benzoate in Synthesis Example 1-3. (6-1-1).

‧Synthesis Example 5-2: Synthesis of Compound (CA-6)

In a 100 mL eggplant-shaped flask equipped with a reflux tube, 7.39 g of compound (6-1-1), 1.38 g of lithium hydroxide monohydrate, 40 mL of tetrahydrofuran, 10 mL of methanol, and 10 mL of distilled water were placed, and stirred at room temperature for 2 hours. . The reaction solution was diluted with 200 mL of ethyl acetate, and neutralized with 100 mL of 5% aqueous sodium bisulfate solution. Then, the organic layer was washed three times with 100 mL of distilled water. After drying the organic layer with magnesium sulfate, the solvent was distilled off, and it was made to dry. To the obtained solid, 100 mL of ethyl acetate was added and stirred, and the insoluble matter was separated by filtration, and then hexane was added for recrystallization to obtain 3.02 g of compound (CA-6).

[Synthesis Example 6]

Compound (CA-7) to compound (CA-9) were synthesized by performing the same reaction as in Synthesis Example 5 with respect to the three intermediates synthesized in Synthesis Example 2 to Synthesis Example 4, respectively.

<Synthesis of polyimide and polyimide>

[Synthesis Example 7]

100 mol parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 20 mol parts of cholestanoloxy-2,4-diaminobenzene as diamine , 10 mol parts of 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)] diphenylamine, 10 mol parts of p-phenylenediamine and 4 , 30 mol parts of ,4'-diaminodiphenyl ether was dissolved in N-Methyl-2-Pyrrolidone (N-Methyl-2-Pyrrolidone, NMP), and reacted at room temperature for 4 hours to obtain a solution containing A 10 mass % solution of polyamic acid (this is referred to as polymer (P-1)). The solution viscosity of the polyamide acid solution is 43.8mPa. s.

[Synthesis Example 8]

50 mol parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 50 mol parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 10 mol parts of cholestanoloxy-2,4-diaminobenzene as diamine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4 -Diyl)] 10 mol parts of diphenylamine, 30 mol parts of 4,4'-diaminodiphenyl ether, 10 mol parts of compound (d-10) and 2,2'-trifluoromethyl- 20 mol parts of 4,4'-diaminobiphenyl was dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 4 hours to obtain 10% by mass of polyamic acid. solution.

Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7 wt %, and were added successively by 1.3 times the total amount of the tetracarboxylic dianhydride used. Molar pyridine and acetic anhydride were dehydrated and ring-closed at 110°C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new NMP to obtain an imidization rate of about 50% containing 16% by mass. of polyimide (referred to as "polymer (P-2)").

[Synthesis Example 10, Synthesis Example 11, Synthesis Example 14]

Except that the kind and usage amount of tetracarboxylic dianhydride and diamine were as described in the following Table 1, in the same manner as in Synthesis Example 7, respectively, polyamic acid (polymer (P-4) was synthesized in the same manner as in Synthesis Example 7. ), polymer (P-5), polymer (Q-3)).

[Synthesis Example 9, Synthesis Example 12, Synthesis Example 13, Synthesis Example 15]

Except for changing the kind and usage amount of tetracarboxylic dianhydride and diamine as described in the following Table 1, in the same manner as in Synthesis Example 8, respectively, polyimide (polymer (P-3) was synthesized. ), polymer (Q-1), polymer (Q-2), polymer (Q-4)).

<Synthesis of Polyamide>

[Synthesis Example 16]

Tetracarboxylate was synthesized in the same manner as in Synthesis Example 1-3, except that 3,5-dinitrobenzyl chloride was changed to 2,3,5-tricarboxycyclopentylacetic dianhydride Acid diester (this is referred to as "compound (AE-1)").

Next, 20 mol parts of compound (AE-1), 40 mol parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride and ethanol were mixed 40 mol parts of the reaction product (referred to as "compound (es-1)") was dissolved in N-methyl-2-pyrrolidone (NMP), and cholestanol as a diamine was added thereto. Alkyl-2,4-diaminobenzene 10 mol parts, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine 10 40 mol parts of p-phenylenediamine, and 40 mol parts of 4,4'-diaminodiphenyl ether were dissolved. To this solution was added 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine chloride (DMT-MM, 15±2 mass % hydrated 300 mol parts of compound), and reacted at room temperature for 4 hours to obtain a solution containing the polymer (E-1) as a polyamic acid ester. When the polymer solution was left to stand at 20°C for 3 days, it did not gel, and the storage stability was good.

[Synthesis Example 17]

A polymer (F-1)-containing solution was obtained in the same manner as in Synthesis Example 16, except that the types and usage amounts of the tetracarboxylic acid derivative and the diamine were as described in Table 2 below.

<Synthesis of polyorganosiloxane>

[Synthesis Example 18]

2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (the formula (sa- 1) 100.0 g of the compound represented by 1), 500 g of methyl isobutyl ketone as a solvent, and 10.0 g of triethylamine as a catalyst were mixed at room temperature. In this, after adding 100 g of deionized water dropwise over 30 minutes from the dropping funnel, the reaction was performed at 80° C. for 6 hours while mixing under reflux. After the completion of the reaction, the organic layer was extracted and washed with a 0.2 mass % ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid. In the form of polyorganosiloxane with epoxy groups. The epoxy equivalent of this epoxy group-containing polyorganosiloxane was measured and found to be 186 g/equivalent.

Next, in a 200 mL three-necked flask, 10.0 g of the epoxy-group-containing polyorganosiloxane obtained above, 30.28 g of methyl isobutyl ketone as a solvent, and 4-(4-pentyl as a carboxylic acid) were added. Cyclohexyl)benzoic acid 3.10 g (equivalent to 20 mol % with respect to the silicon atom of epoxy-containing polyorganosiloxane), compound (CA-10) 2.51 g (relative to epoxy-containing polyorganosiloxane) The silicon atom of polyorganosiloxane is equivalent to 20 mol%) and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst, and reacted at 100° C. under stirring for 48 hours. After the completion of the reaction, ethyl acetate was added to the reaction mixture, the obtained solution was washed three times with water, and the solvent was distilled off to obtain a polyorganosiloxane (S-1) 13.6 having a pretilt angle developing group. g. The weight average molecular weight Mw of the obtained polymer was 1107.

[Synthesis Example 19 to Synthesis Example 23]

Except having made the kind and usage amount of carboxylic acid as described in following Table 3, it carried out similarly to Synthesis Example 18 to obtain polymer (S-2) - polymer (S-5), polymer ( R-1). In addition, in Table 3, the numerical value of a monomer shows the usage ratio (mol%) with respect to the sum total of the monomers used for superposition|polymerization of epoxy-group-containing polyorganosiloxane. The numerical value of the carboxylic acid represents the usage ratio (mol %) of the carboxylic acid with respect to the silicon atom which the epoxy group-containing polyorganosiloxane has.

[Example 1]

(1) Preparation of liquid crystal alignment agent

Using the solution of the polymer (Q-3) obtained in Synthesis Example 14 and the polymer (S-1) obtained in Synthesis Example 18, the compounding ratio was polymer (Q-3):polymer (S-1) The polymer (Q-3) and the polymer (S-1) were prepared in a manner of =90:10 (solid content conversion mass ratio), and were diluted with NMP and butyl cylosol (BC) to obtain a solid content concentration of 4.0 mass %, the solvent composition ratio is a solution of NMP:BC=45:55 (mass ratio). This solution was filtered with a filter having a pore size of 0.2 μm to prepare a liquid crystal aligning agent (W-1).

(2) Preparation of liquid crystal composition

5 mass % of the liquid crystal compound represented by the following formula (L1-1) and 0.3 mass % of the following formula (L2 The photopolymerizable compound represented by -1) is mixed to obtain a liquid crystal composition LC1.

(3) Manufacture of liquid crystal display element

Using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), the liquid crystal alignment agent (W-1) prepared above was coated on each electrode surface of two glass substrates each having a conductive film including an ITO electrode , after 2 minutes of heating (pre-baking) on a hot plate at 80 °C, and 30 minutes of heating (post-baking) on a hot plate, the shape A coating film with an average film thickness of 0.1 μm was formed. Among them, in the post-baking, for one of the two substrates (referred to as "substrate A"), the post-baking temperature was set to 180°C, and for the other substrate (referred to as "substrate B"), the post-baking temperature was The baking temperature was set to 230°C. Through these operations, a pair (two sheets) of substrates having a coating film were obtained. In addition, the pattern of the electrode used is the same pattern as that of the electrode pattern in the PSA mode.

Then, after coating the outer edges of the pair of substrates with the liquid crystal alignment film and adding an epoxy resin adhesive with alumina balls with a diameter of 5.5 μm, the liquid crystal alignment film faces are overlapped and crimped to make the adhesive. Adhesive hardening. Next, after filling the liquid crystal group LC1 prepared above between a pair of substrates through a liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocurable adhesive, thereby producing a liquid crystal cell. Then, 10V alternating current with a frequency of 60Hz was applied between the conductive films of the liquid crystal cell, and while the liquid crystal was driven, ultraviolet rays were irradiated with an irradiation dose of 5 J/m ² using an ultraviolet irradiation device using a metal halide lamp as a light source. In addition, this irradiation amount is the value measured using the photometer which measures based on the wavelength of 365 nm.

(4) Determination of pre-tilt angle

For the liquid crystal display element obtained in the above (3), the pretilt angles of the substrate A and the substrate B were measured, respectively. The measurement of the pretilt angle is based on the non-patent literature "TJ Scheffer et al. Journal of Applied Physics. Vol.19, p.2013 (1980) (TJ Scheffer et.al.J.Appl.Phys.vo.19, p.2013 ( 1980))", the value of the inclination angle of the liquid crystal molecules with respect to the substrate surface was measured by the crystal rotation method using He-Ne laser light, and it was set as the pretilt angle [°]. As a result, the pretilt angle of the substrate A (low-temperature firing) was 89.3°, and the pretilt angle of the substrate B (high-temperature firing) was 88.4°. The difference in pretilt angle is 0.9°.

[Example 2 to Example 13, Comparative Example 1 to Comparative Example 3]

As shown in Table 4 below, the same procedures as in Example 1 were performed except that the type of polymer contained in the liquid crystal aligning agent, the firing temperature (post-baking temperature) of the substrate, and the amount of UV irradiation to the liquid crystal cell were changed. A liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed, and a liquid crystal display element was manufactured to measure the pretilt angle. The evaluation results are shown in Table 4 below. In addition, in Example 2 - Example 9 and Comparative Example 2 - Comparative Example 4, the polymer component was used as one type. In Examples 10 to 13 and Comparative Example 1, two kinds of polymers (polymer I and polymer II) were contained in a compounding ratio of polymer I:polymer II=90:10 (mass ratio in terms of solid content) in liquid crystal alignment agents. In Example 5, after post-baking the board|substrate B at 180 degreeC, it further heated at 230 degreeC (two-stage heating).

From the above results, it was confirmed that by forming a liquid crystal alignment film on the surfaces of a pair of substrates using a liquid crystal aligning agent containing the compound (P), and heating one substrate at a higher temperature than the other substrate, the The difference in pretilt angle can be sufficiently increased between a pair of substrates.

Claims (10)

A method of manufacturing a liquid crystal element, comprising: coating a liquid crystal alignment agent on each of a first substrate and a second substrate; and applying the liquid crystal alignment agent to the first substrate and the second substrate a step of heating a substrate; and a step of constructing a liquid crystal cell by arranging the first substrate and the second substrate so as to face each other so that the surfaces on which the liquid crystal aligning agent is applied are opposed to each other after the heating, and The liquid crystal aligning agent contains a compound having a thermally releasable group that is detached by heating, and in the heating step, one of the first substrate and the second substrate is subjected to a higher temperature than the other. A higher temperature substrate is heated by a high temperature heat treatment. The method for producing a liquid crystal element according to claim 1, wherein in the high-temperature heat treatment, the one substrate is heated at a temperature 20° C. or more higher than the other substrate. The method for producing a liquid crystal element according to claim 1 or claim 2, further comprising a step of irradiating light with a voltage applied to the liquid crystal cell after the liquid crystal cell is constructed. The method for manufacturing a liquid crystal element according to claim 1 or claim 2, wherein the pretilt angle of liquid crystal molecules induced by the liquid crystal alignment film formed on the first substrate and the pretilt angle of the liquid crystal molecules formed on the first substrate 2 Induced by the liquid crystal alignment film on the substrate The difference between the pretilt angles of the liquid crystal molecules produced is 0.8° or more. The method for producing a liquid crystal element according to claim 1 or claim 2, further comprising forming at least the first substrate and the second substrate after the heating and before the construction of the liquid crystal cell. In the step of contacting the coating surface of the liquid crystal aligning agent in the substrate subjected to the high temperature heat treatment with water or a liquid containing an organic solvent. The method for producing a liquid crystal element according to claim 1 or claim 2, wherein the compound having the thermally releasable group is selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyamide At least one of the group consisting of organosiloxanes. The method for producing a liquid crystal element according to claim 1 or claim 2, wherein the compound having the thermally releasable group has a partial structure represented by the following formula (1) or the following formula (2) Part of the structure represented:

In formula (1), R ¹ is a single bond or a divalent organic group; X ¹ is a single bond, -O-, -S- or -NR ^II -, wherein R ^II is a hydrogen atom or a hydrocarbon group, which can be combined with R ¹ bond to form a ring, and may also be a divalent hydrocarbon group contained in the main chain; Y ¹ is the thermally detachable group that cuts off the bond between Y ¹ and the oxycarbonyl group, or X ¹ and oxygen The thermally detachable group that is severed from the bond of the oxycarbonyl group and simultaneously or separately from the oxycarbonyl group; "*" represents a bond, *-R ¹ -Y ² (2) In formula (2), R ¹ is a single bond or a divalent organic group; Y ² is the thermally detachable group having the structure of the following formula (3); "*" represents a bonding bond,

In formula (3), X ¹ is a single bond, -O-, -S- or -NR ^II -, wherein R ^II is a hydrogen atom or a monovalent organic group, which can be bonded to R ¹ to form a ring; R ^III is a monovalent organic group; "**" represents a bond with R ¹ . The method for producing a liquid crystal element according to claim 1 or claim 2, wherein the thermally releasable group has a partial structure represented by the following formula (C-1): *-R ²² -R ²¹ - R ²⁰ -R ¹⁹ (C-1) In formula (C-1), R ¹⁹ is an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Fluorinated alkoxy group with 1 to 30 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms that may have a substituent, phenyl group with 6 to 20 carbon atoms that may have a substituent, or 17 to 17 carbon atoms with a steroid skeleton The hydrocarbon group of 51; R ²⁰ is a single bond, -O-, -COO- or -OCO-; R ²¹ is a single bond, alkanediyl with carbon number 1~20, phenylene, biphenylene, cyclohexylene , a dicyclohexylene group, a group represented by the following formula (C-1-1), or a group represented by the following formula (C-1-2); R ²² is a single bond or a divalent organic group; wherein, When R ²⁰ is a single bond, R ²¹ is a single bond; when R ²⁰ , R ²¹ and R ²² are single bonds, and R ¹⁹ is an alkyl group with 1 to 30 carbon atoms, a fluoroalkyl group with 1 to 30 carbon atoms, In the case of an alkoxy group having 1 to 30 carbon atoms or a fluorinated alkoxy group having 1 to 30 carbon atoms, R ¹⁹ has a straight chain structure; "*" represents a bond,

In formula (C-1-2), R ²³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; "**" represents a bond with R ²² . The method for producing a liquid crystal element according to claim 1 or claim 2, wherein the thermally releasable group has at least one selected from the group consisting of a hindered amine structure, a hindered phenol structure, and an aniline structure. The method for producing a liquid crystal element according to claim 1 or claim 2, wherein the thermally releasable group has a radical generating function capable of generating radicals by light irradiation, and display by light irradiation A base for at least any one of the photosensitizing functions that exhibit sensitization.