JP2017106941A - Urea compound having alkoxysilyl group and liquid crystal aligning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal alignment film that can be aligned either by the rubbing method or optical alignment method to offer a high voltage holding rate, superior liquid crystal alignability, and less residual charge accumulated by DC voltage, and to provide a liquid crystal aligning agent for producing the same.SOLUTION: Disclosed is a liquid crystal aligning agent containing a component (A) and component (B) and an organic solvent where the component (A) represents at least one polymer selected from a group consisting of a polyimide precursor, imidized polymer of the polyimide precursor, and a photosensitive side-chain acrylic polymer that exhibits liquid crystallinity in a predefined temperature range, and the component (B) represents a compound having an alkoxysilyl group and a urea structure in which the position 1 and position 3 are both substituted.SELECTED DRAWING: None

Description

The present invention relates to a urea compound having an alkoxysilyl group and a liquid crystal aligning agent containing the same. More specifically, a liquid crystal aligning agent that provides a liquid crystal alignment film having excellent voltage holding characteristics and charge storage characteristics of a liquid crystal cell, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film, The present invention relates to a compound that gives this liquid crystal aligning agent.

  Currently, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment mainly comprising a polyimide precursor such as polyamic acid, a soluble polyimide, or a solution of an acrylic polymer having a photosensitive side chain or a vertical alignment side chain. A liquid crystal alignment film coated with an agent and baked is mainly used. The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.

  The characteristics required for the liquid crystal alignment film include controllability of liquid crystal alignment, excellent voltage holding ratio, quick relaxation of charges accumulated by DC voltage, and low ion content in the liquid crystal cell. It is done. In recent years, with the increase in size of liquid crystal display elements, liquid crystal display elements that can withstand long-term use have been demanded. In order to be able to be used for a long period of time, it is required that the characteristics do not change even when irradiated with light from the backlight unit or sunlight including ultraviolet rays for a long period. For this reason, a liquid crystal aligning agent whose display characteristics do not change greatly by backlight light or ultraviolet irradiation has been demanded.

In addition to these characteristics, a process for aligning liquid crystals by irradiating ultraviolet rays has been adopted in recent liquid crystal display element manufacturing processes (see, for example, Non-Patent Document 1). Further, in recent liquid crystal display device manufacturing processes, a process of irradiating ultraviolet rays by a liquid crystal dropping method (ODF), a PSA (Polymer Sustained Alignment) process, etc. has been introduced, and a material resistant to ultraviolet rays is required. (For example, refer nonpatent literature 2).
As an effort to increase the light resistance of liquid crystal display elements, for example, Patent Documents 1 and 2 attempt to increase the life of liquid crystals by adding benzotriazole ultraviolet absorbers or benzophenone ultraviolet absorbers to liquid crystal alignment agents. It has been broken. In Patent Document 3, an attempt is made to extend the life of the liquid crystal by further adding an antioxidant to the benzotriazole ultraviolet absorber or the benzophenone ultraviolet absorber. Patent Document 4 reports that an internal offset voltage can be reduced to 100 mV or less by adding a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, or a dialkyldithiocarbamic acid metal salt to the alignment material. Further, Patent Documents 5 and 6 report a method for producing a liquid crystal panel having excellent light resistance by adding a benzotriazole compound or a hindered amine compound to an aligning agent.

  However, although these compounds have an effect of suppressing a decrease in voltage holding ratio (hereinafter also referred to as VHR) due to UV irradiation, there has been a problem that the initial VHR is lowered by addition. Further, when the firing temperature is high, these compounds are sublimated or thermally decomposed, so that the effect is reduced.

JP-A 56-1116012 JP-A-57-84429 JP-A-57-108828 Japanese Patent Laid-Open No. 10-148835 JP 2003-215592 A JP 2004-53685 A

Liquid Crystal Handbook, Maruzen Co., Ltd., Liquid Crystal Handbook Editorial Committee, page 233 Liquid Crystal, Vol. 14, No. 3, 2010, 175 (27)

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment film having a high voltage holding ratio, excellent liquid crystal alignment, little residual charge accumulated by a DC voltage, and a liquid crystal aligning agent that provides the same, both in the rubbing method and the photo alignment method. That is.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the gist of the present invention is as follows.
1. The liquid crystal aligning agent characterized by including the following (A) component, (B) component, and an organic solvent.
Component (A): at least one polymer selected from the group consisting of a polyimide precursor, an imidized polymer of the polyimide precursor, and a photosensitive side chain acrylic polymer that exhibits liquid crystallinity within a predetermined temperature range. .
Component (B): A compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted.
2. 2. The compound according to 1 above, wherein the alkoxysilyl group and a compound having a urea structure in which both the 1-position and the 3-position are substituted are contained in an amount of 0.1 to 20% by mass with respect to the polymer. Liquid crystal aligning agent.
3. 3. The liquid crystal aligning agent according to any one of 1 to 2 above, wherein the compound having the alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted is represented by the following formula (b): .

(In the formula, X ² is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, and R ² is a hydrogen atom. Or an alkyl group, and when n is 2 or more, R ² is alkylene together with other R ² , or when n is 1 to 6, it is also bonded to X ² to form a ring together with X ² May form a structure, L represents an alkylene having 2 to 20 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or (It is an alkynyl group having 2 to 4 carbon atoms, and q represents a natural number of 1 to 3.)
4). 4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein R ³ in formula (b) is a methyl group or an ethyl group.
5). N in Formula (b) is 2 or 1, The liquid crystal aligning agent in any one of said 1 thru | or 4 characterized by the above-mentioned.
6). Q in Formula (b) is 3, The liquid crystal aligning agent in any one of said 1 thru | or 5 characterized by the above-mentioned.
7). The liquid crystal aligning film obtained by apply | coating and baking the liquid crystal aligning agent in any one of said 1-6.
8). The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of said 1 to 6, and irradiating the polarized radiation.
9. 9. A liquid crystal display device comprising the liquid crystal alignment film as described in 7 or 8 above. 9. A lateral electric field drive type liquid crystal display device comprising the liquid crystal alignment film as described in 7 or 8 above.

By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film having a high voltage holding ratio, excellent liquid crystal alignment, and having a small residual charge accumulated by a DC voltage.

The liquid crystal aligning agent of this invention is a liquid crystal aligning agent characterized by containing the following (A) component, (B) component, and an organic solvent.
Component (A): a polyimide precursor having a structural unit represented by the following formula (1), an imidized polymer of the polyimide precursor, and a photosensitive side chain acrylic weight that exhibits liquid crystallinity within a predetermined temperature range. At least one polymer selected from the group consisting of coalescence.
Component (B): A compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted.
Hereinafter, each component will be described in detail.
<(A) component>

  The component (A) contained in the liquid crystal aligning agent of the present invention comprises a polyimide precursor, an imidized polymer of the polyimide precursor, and a photosensitive side chain acrylic polymer that exhibits liquid crystallinity within a predetermined temperature range. It is at least one polymer selected from the group.

<Polyimide precursor>
The polyimide precursor is a polyimide precursor having a structural unit represented by the following formula (1).

In Formula (1), X ₁ is each independently a tetravalent organic group, and Y ₁ is each independently a divalent organic group. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A _{1 to} A ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that may have a substituent, An alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.
Specific examples of the alkyl group in R ₁ include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group. Etc. From the viewpoint of ease of imidization by heating, R ₁ is preferably a hydrogen atom or a methyl group.

In the formula (1), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. Two or more kinds of X ₁ may be mixed in the polyimide precursor. If Specific examples of X _1, include the structures represented by the following formula (X-1) ~ (X -44).

R _{8 to} R ₁₁ in the formula (X-1) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group, or phenyl. It is a group. In the case where R _{8 to} R ₁₁ have a bulky structure, the liquid crystal orientation may be lowered, so that a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable.

In Formula (1), X ₁ preferably contains a structure selected from (X-1) to (X-14) from the viewpoint of availability of monomers.

The preferred ratio of structure selected from the (X-1) ~ (X -14), and the _{X 1} total 20 mol% or more, more preferably 60 mol% or more, even more preferably at least 80 mol% .

In Formula (1), A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have a substituent, or an alkyl group having 2 to 10 carbon atoms that may have a substituent. Or an alkynyl group having 2 to 10 carbon atoms which may have a substituent.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group, and bicyclohexyl group. Examples of the alkenyl group include those obtained by replacing one or more CH—CH structures present in the above alkyl group with C═C structures, and more specifically, vinyl groups, allyl groups, 1-propenyl groups. , Isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like. Alkynyl groups include those in which one or more CH ₂ —CH ₂ structures present in the alkyl group are replaced with C≡C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -A propynyl group etc. are mentioned.

The above alkyl group, alkenyl group, and alkynyl group may have a substituent, and may further form a ring structure by the substituent. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.

Examples of such substituents are halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls. A group, an alkenyl group and an alkynyl group.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

A phenyl group is mentioned as an aryl group which is a substituent. This aryl group may be further substituted with the other substituent described above.

The organooxy group which is a substituent can have a structure represented by OR. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the organooxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.

As the organothio group which is a substituent, the structure represented by -S-R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above. Specific examples of the organothio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

As the organosilyl group which is a substituent, a structure represented by -Si- (R) ₃ can be shown. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

As an ester group which is a substituent, the structure represented by -C (O) O-R or -OC (O) -R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.

As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.

As a phosphate group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.

As the amide group as a substituent, —C (O) NH ₂ , or —C (O) NHR, —NHC (O) R, —C (O) N (R) ₂ , —NRC (O) R The structure represented by can be shown. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.

Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.

Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.

Examples of the alkenyl group as a substituent include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.

Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.

In general, when a bulky structure is introduced, there is a possibility that the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, as A ₁ and A ₂ , a hydrogen atom or a carbon atom that may have a substituent is 1 The alkyl group of ˜5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In Formula (1), Y ₁ is a divalent organic group derived from diamine, and its structure is not particularly limited. If shows a specific example of the structure of Y _1, include Y-1 to Y-119 below.

(In formula (Y-109), m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, and in formula (Y-114), h is an integer of 1 to 3, (In formulas (Y-111) and (Y-117), j is an integer of 0 to 3).)
The structure of Y ₁ is more preferably at least one selected from structures represented by the following formulas (5) and (6) from the viewpoint of liquid crystal alignment properties and pretilt angles of the obtained liquid crystal alignment film.

In the formula (5), R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, a is When R is an integer of 1 to 4 and a is 2 or more, R ₁₂ and R ₁₃ may be the same or different from each other, and R ₁₄ in formula (6) is a single bond, —O—, —S—. , —NR ₁₅ —, an amide bond, an ester bond, a urea bond, or a divalent organic group having 1 to 40 carbon atoms, and R ₁₅ is a hydrogen atom or a methyl group.

Specific examples of Formula (5) and Formula (6) include the following structures.
High structural linearity, since it is possible to enhance the orientation of the liquid crystal when the liquid crystal alignment film, as Y ₁ is, Y-7, Y-21 , Y-22, Y-23, Y-25, Y-43, Y-44, Y-45, Y-46, Y-48, Y-63, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98, Y- 99, Y-100 and Y-118 are more preferable. The proportion of the above structure that can enhance the liquid crystal orientation is preferably 20 mol% or more of Y ₁ as a whole, more preferably 60 mol% or more, and further preferably 80 mol% or more.

When it is desired to increase the pretilt angle of the liquid crystal when the liquid crystal alignment film is used, it is preferable that the side chain has a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination of these in Y _1. . As such Y ₁ , Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y- 86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, Y-97 are preferred. The proportion of the structure when it is desired to increase the pretilt angle is preferably 1 to 30 mol% of the total _{Y 1,} and more preferably 1 to 20 mol%.
Moreover, when using the polyimide (precursor) which has a photo-alignment side chain as a polymer of (A) component, it is preferable to use the polyimide (precursor) which has the following photoreactive side chain.

(R ⁶ represents —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON ( CH ₃ ) — or —N (CH ₃ ) CO—, wherein R ⁷ represents cyclic, unsubstituted or alkylene having 1 to 20 carbon atoms which is substituted by a fluorine atom, where Arbitrary —CH ₂ — may be replaced by —CF ₂ — or —C═C—, and when any of the following groups is not adjacent to each other, these groups may be replaced: --O--, --COO--, --OCO--, --NHCO--, --CONH--, --NH--, carbocycle, heterocycle, R ⁸ represents --CH _2- , --O--, --COO--, --OCO--. , -NHCO -, - NH -, - N (CH 3) -, - CON (C _{3) -, - N (CH} 3) CO-, represent either carbocyclic or heterocyclic,, ^{R 9} is a vinyl phenyl ^{group, -CR} 10 = CH ₂ ^group, -CR 10 (OH) -CH ₃ group , Carbocycle, heterocycle or a structure represented by the following formula, R ¹⁰ represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom.

When producing such a polyimide precursor, it is convenient to use a diamine substituted with a side chain represented by the above formula (b) as the diamine.
Moreover, you may use the polyimide precursor which has a photoalignment group in a principal chain. In this case, it is convenient to use a diamine having a bond containing a photoalignable group between the amine and the amine, as represented by the following formula (1).

(In Formula (1), X ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, X ² is —OCO—CH═CH— or —CH═CH—COO—, and X ³ is a single bond. , An alkylene group having 1 to 10 carbon atoms or a divalent benzene ring, X ⁴ is a single bond, —OCO—CH═CH— or —CH═CH—COO—, and X ⁵ is a single bond or carbon number. 1 to 5 alkylene groups, with one or more cinnamoyl groups)

  Examples of the diamine represented by the formula (1) include the following diamines.

Wherein X is independently a single bond or a linking group selected from ether (—O—), ester (—COO— or —OCO—) and amide (—CONH— or —NHCO—); Is independently a single bond or an alkylene group having 1 to 5 carbon atoms, Z is independently an alkylene group having 1 to 10 carbon atoms or a phenylene group, the bonding position of the amino group on the benzene ring, (The position of the linking group with respect to the benzene ring is not particularly limited.)

  Specific examples of the diamine represented by the formula (1) include the following diamines.

  A liquid crystal alignment film formed using a liquid crystal aligning agent containing a polyimide precursor such as polyamic acid and polyamic acid ester, polyimide and polyamide using the diamine of the present invention represented by the above formula (1) as a raw material Is a change in liquid crystal alignment performance due to AC (alternating current) driving, for example, a change in liquid crystal alignment orientation. Therefore, the liquid crystal display element having this liquid crystal alignment film has a stable liquid crystal alignment performance of the liquid crystal alignment film in AC driving, so that an afterimage is hardly generated by AC driving, that is, an afterimage characteristic by AC driving is very good. There is an effect. Moreover, the liquid crystal aligning film formed using the diamine represented by the said Formula (1) is excellent also in liquid crystal aligning performance itself, and can be made into a thing without an alignment defect substantially.

The polyimide precursor used in the present invention is obtained from a reaction between a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamic acid and polyamic acid ester.

<Production of polyimide precursor-polyamic acid>
The polyamic acid which is a polyimide precursor used in the present invention is produced by the following method.
Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.

The reaction of the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.
When the solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] to formula [D-3]. An organic solvent can be used.

In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. The formula [D-3] Among them, D ³ represents an alkyl group having 1 to 4 carbon atoms.
These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated and dried solvent.

The concentration of the polyamic acid polymer in the reaction system is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.

  The polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine | purified by performing precipitation several times, washing | cleaning with a poor solvent, and normal temperature or heat-drying can be obtained. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

<Production of polyimide precursor-polyamic acid ester>
The polyamic acid ester which is a polyimide precursor used in the present invention can be produced by the following production method (1), (2) or (3).

(1) When manufacturing from polyamic acid A polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be manufactured.

  As the esterifying agent, those that can be easily removed by purification are preferred, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.

Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl- Examples include imidazolidinone. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the above formula [D-1] to formula [D-3] The indicated solvents can be used.

  These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated and dried solvent.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, and these may be used alone or in combination of two or more. Good. The concentration at the time of production is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.

(2) When manufactured by reaction of tetracarboxylic acid diester dichloride and diamine The polyamic acid ester can be manufactured from tetracarboxylic acid diester dichloride and diamine.
Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent are −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., 30 minutes to 24 hours, preferably 1 to 4 hours. It can be produced by reacting.

  As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The amount of the base added is preferably 2 to 4 moles relative to the tetracarboxylic acid diester dichloride from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.

  The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and polymer, and these may be used alone or in combination of two or more. The polymer concentration during production is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the production of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(3) When manufacturing from tetracarboxylic-acid diester and diamine Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine.
Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent are 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, 30 minutes to 24 hours, preferably 3 to 15 hours. It can manufacture by making it react for time.

  Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. As for the addition amount of a condensing agent, 2-3 times mole is preferable with respect to tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base added is preferably 2 to 4 times the molar amount of the diamine component from the viewpoint of easy removal and high molecular weight.

  In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times the mole of the diamine component.

Among the methods for producing the three polyamic acid esters, since the high molecular weight polyamic acid ester is obtained, the production method (1) or (2) is particularly preferable.
The polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

<Polyimide>
The polyimide used in the present invention can be produced by imidizing the aforementioned polyamic acid ester or polyamic acid. When a polyimide is produced from a polyamic acid ester, chemical imidization in which a basic catalyst is added to a polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.

  Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.

  The temperature at which the imidization reaction is performed is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.

  When manufacturing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction with a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.

  Chemical imidation can be performed by stirring the polyamic acid to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.

  The temperature at which the imidization reaction is performed is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amic acid group. Is double. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.

In the solution after the imidation reaction of polyamic acid ester or polyamic acid, the added catalyst and the like remain, so the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent. Thus, the liquid crystal aligning agent of the present invention is preferable.

The polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

<Photosensitive side chain acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range>
One aspect of the component (A) is a photosensitive side-chain acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range.

  (A) The side chain type acrylic polymer should react with light in the wavelength range of 250 nm to 400 nm and exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.

The (A) side chain type acrylic polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
(A) The side chain type acrylic polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

  (A) The side chain type acrylic polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light. The structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type acrylic polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but preferably has a rigid mesogenic component in the side chain structure. In this case, when the side chain type acrylic polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

  The structure of the acrylic polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group. A structure having a photosensitive group that is bonded to the tip and that undergoes a cross-linking reaction or an isomerization reaction in response to light, or a main chain and a side chain bonded thereto, and the side chain also serves as a mesogenic component, And it can be set as the structure which has the phenylbenzoate group which carries out a photo-Fries rearrangement reaction.

  More specific examples of the structure of the photosensitive side chain acrylic polymer exhibiting liquid crystallinity in a predetermined temperature range include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ- A main chain composed of at least one selected from the group consisting of radically polymerizable groups such as butyrolactone, styrene, vinyl, maleimide, norbornene, and a side chain composed of at least one of the following formulas (1) to (5) It is preferable that the structure has

In the formula, Ar1 represents a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring,
Ar2 and Ar3 each independently represent a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring, or pyridine ring;
one of q1 and q2 is 1 and the other is 0,
Ar4 and Ar5 each independently represent a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring, or pyridine ring;
Y1-Y2 represents CH = CH, CH = N, N = CH or C≡C;
S1 to S3 each independently represents a single bond, a linear or branched alkylene having 1 to 18 carbon atoms, a cycloalkylene having 5 to 8 carbon atoms, phenylene or biphenylene, or a single bond, an ether bond or an ester bond. Represents one or more bonds selected from amide bonds, urea bonds, urethane bonds, amino bonds, carbonyls, or combinations thereof, or the number of carbon atoms through the one or more bonds. A structure in which 2 to 10 sites selected from 1 to 18 linear or branched alkylene, cycloalkylene having 5 to 8 carbon atoms, phenylene, biphenylene, or a combination thereof are bonded to each other. The group may have a structure in which a plurality of groups are connected via the bond,
R11 represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. 16 dialkylamino groups, wherein the benzene ring and / or naphthalene ring is substituted by one or more substituents selected from the same or different groups selected from halogen atoms, cyano groups, nitro groups, carboxyl groups and C2-11 alkoxycarbonyl groups. It may be. In this case, the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, or a combination thereof, and may be substituted with a halogen atom.

The photosensitive side chain acrylic polymer that exhibits liquid crystallinity within a predetermined temperature range as the component (A) of the present application can contain liquid crystal side chains.

  The mesogenic group possessed by the liquid crystalline side chain is a group that forms a mesogenic structure by hydrogen bonding between side chains, such as benzoic acid, even if it is a group that forms a mesogenic structure alone, such as biphenyl or phenylbenzoate. May be. As the mesogenic group possessed by the side chain, the following structure is preferable.

<< Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain acrylic polymer exhibiting liquid crystallinity in the above-mentioned predetermined temperature range is obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer. Can do.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
The photoreactive group possessed by the side chain is preferably a structure represented by the above formulas (1) to (5).

  More specific examples of the photoreactive side chain monomer include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide and norbornene. A structure having a polymerizable group composed of at least one selected from the group consisting of and a photosensitive side chain composed of at least one of the above formulas (1) to (5) is preferable.

[Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.

  More specific examples of liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and other radical polymerizable groups. A structure having a polymerizable group composed of at least one selected from the group and a side chain having at least one of the “mesogenic groups of the liquid crystalline side chain” is preferable.

  (A) A side chain type acrylic polymer can be obtained by the polymerization reaction of the above-mentioned photoreactive side chain monomer that exhibits liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl 8 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate. (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  The method for producing the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

  As a polymerization initiator for radical polymerization, a known radical polymerization initiator such as AIBN (azobisisobutyronitrile) or a known compound such as a reversible addition-cleavage chain transfer (RAFT) polymerization reagent should be used. Can do.

  The radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.

  The organic solvent used for the polymerization reaction of the photosensitive side chain acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range is not particularly limited as long as the produced polymer is soluble. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like can be mentioned.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.

  The polymerization temperature during radical polymerization can be selected from 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

  In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is It is preferable that it is 0.1 mol%-10 mol% with respect to the monomer to superpose | polymerize. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.

[Recovery of photosensitive side-chain acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

  The molecular weight of the photosensitive side-chain acrylic polymer that exhibits liquid crystallinity in the predetermined temperature range of the present invention (A) is the strength of the resulting coating film, workability during coating film formation, and coating film uniformity. Is considered, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2000 to 1000000, and more preferably 5000 to 100,000.

<(B) component>
The component (B) contained in the liquid crystal aligning agent of the present invention is a compound having an alkoxysilyl group and a urea structure substituted at both the 1-position and 3-position (hereinafter also referred to as compound B).
As long as the compound has one or more alkoxysilyl groups and one or more 1,3-disubstituted urea structures in the compound, other structures are not particularly limited. Therefore, a compound represented by the following formula (b) is one of preferred examples.

(In the formula, X ² is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, and R ² is a hydrogen atom. Or an alkyl group, and when n is 2 or more, R ² is alkylene together with other R ² , or when n is 1 to 6, it is also bonded to X ² to form a ring together with X ² May form a structure, L represents an alkylene having 2 to 20 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or (It is an alkynyl group having 2 to 4 carbon atoms, and q represents a natural number of 1 to 3.)

Examples of R ³ and R ⁴ in the formula (b) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec-butyl, respectively. From the viewpoint, methyl or ethyl is preferable.

  Examples of L in the formula (b) include alkylene having 2 to 20 carbon atoms, but trimethylene is preferable from the viewpoint of obtaining the raw material.

  As q in the formula (b), 2 or 3 is preferable, and 3 is particularly preferable.

  As n in Formula (b), 1, 2 or 3 is preferable, and 1 or 2 is particularly preferable.

One embodiment of the compound of component (B) is a compound in which X ² is a divalent organic group, R ² is a hydrogen atom, and L is trimethylene.

Such a compound represented by the formula (2-1) can be obtained by reacting diamine with 2.05 equivalent of trialkoxysilylpropyl isocyanate.

Examples of X in the compound represented by the formula (2-1) include structures selected from the above (Y-1) to (Y-118) which are partial structures of the diamine described in the component (A). Is preferably a structure selected from the following structural formulas.

One embodiment of the compound of component (B) is a compound in which X ² is a divalent organic group, R ² together forms an alkylene, and L is trimethylene.

Such a compound represented by the formula (2-2) can be obtained by reacting 2.05 equivalent of trialkoxysilylpropyl isocyanate with a cyclic compound containing two NH.

X in the compound represented by the formula (2-2) is preferably a structure selected from the following structural formulas. For convenience, the description includes a nitrogen atom in the ring.

In one embodiment of the compound of component (B), X ² is a divalent organic group, one of R ² is a hydrogen atom, and the other is bonded to X ² to form a ring, A compound in which L is trimethylene.

Such a compound represented by the formula (2-3) can be obtained by reacting diamine with 2.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-3) is preferably a structure selected from the following structural formulas. For convenience, the description includes a nitrogen atom in the ring.

One embodiment of the compound of component (B) is a compound in which X ² is a trivalent organic group, R ² is a hydrogen atom, and L is trimethylene.

Such a compound represented by the formula (2-4) can be obtained by reacting a triamine compound with 3.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-4) is preferably a structure selected from the following structural formulas.

One embodiment of the compound of component (B) is a compound in which X ² is a monovalent organic group, R ² is a hydrogen atom, and L is trimethylene.

Such a compound represented by the formula (2-5) can be obtained by reacting a monoamine compound with 1.05 equivalent of trialkoxysilylpropyl isocyanate.

X in the compound represented by the formula (2-5) is preferably a structure selected from the following structural formulas.

One embodiment of the compound of component (B) is a compound in which X ² is a monovalent organic group, R ² is bonded to X ² to form a ring, and L is trimethylene.

Such a compound represented by the formula (2-6) can be obtained by reacting 1.05 equivalent of trialkoxysilylpropyl isocyanate with a cyclic compound containing one NH.

X in the compound represented by the formula (2-6) is preferably a structure selected from the following structural formulas. For convenience, the description includes a nitrogen atom in the ring.

Incidentally, in the reaction of the amine and the isocyanate, the amount of the isocyanate compound, to NH or NH ₂ group 1 group, 0.98 Toryobai 1.2 may be reacted with equivalent times. More preferably, it is 1.0 equivalent times to 1.05 equivalent times.

  The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogen systems such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate Carboxylic acid esters such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and nitrogen-containing aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone; Contains dimethyl sulfoxide, sulfolane, etc. Yellow aprotic polar solvent; pyridine, pyridines picoline and the like. These solvents may be used alone or as a mixture of two or more thereof. Preferred are toluene, acetonitrile, ethyl acetate and tetrahydrofuran, and more preferred are acetonitrile and tetrahydrofuran.

  The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the solvent is used in an amount of 0.1 to 100 times the amount of the isocyanate compound. It may be used. Preferably it is 0.5-30 mass times, More preferably, it is 1-10 mass times.

  Although reaction temperature is not specifically limited, For example, it is -90-150 degreeC, Preferably it is -30-100 degreeC, More preferably, it is 0 to 80 degreeC.

  The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

  A catalyst may be added to shorten the reaction time. Examples thereof include dibutyltin dilaurate, dioctyltin bis (isooctyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dibutyltin diacetate, etc. Organotin compounds of: triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N, N-dimethylcyclohexylamine, pyridine, tetramethylbutanediamine, N-methylmorpholine, 1,4-diazabicyclo-2.2.2 -Amines such as octane, 1,8-diazabicyclo [5.4.0] undecene, 1,5-diazabicyclo [4.3.0] nonene-5; p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid, etc. Possession of Sulfonic acid; Inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid; Titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate; Bismuth compounds such as bismuth tris (2-ethylhexanoate); Quaternary ammonium Examples include salts. These catalysts may be used alone or in combination of two or more. These catalysts are preferably liquid or soluble in the reaction solvent.

  When the catalyst is added, the catalyst may be used in an amount of 0.005 wt% to 100 wt%, preferably 0.05 wt% to 10 wt%, based on the total use amount (mass) of the compound having an isocyanate group. Preferably it is 0.1 wt%-5 wt%. If an organotin compound, a titanium compound, or a bismuth compound is used as the catalyst, it is preferably 0.005 wt% to 0.1 wt%.

  This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.

Specific examples of the preferred component (B) include compounds represented by any of S1 to S4.

  When the amount of the component (B) compound is too large, the liquid crystal orientation and the pretilt angle are affected. When the amount is too small, the effects of the present invention cannot be obtained. Therefore, 0.1-20 mass% is preferable with respect to the polymer of (A) component, and, as for the addition amount of the compound of (B) component, 1-10 mass% is more preferable.

<Liquid crystal aligning agent>
The liquid crystal aligning agent used in the present invention includes the polyimide precursor as the component (A), an imidized polymer of the polyimide precursor, and a photosensitive side chain acrylic resin that exhibits liquid crystallinity within a predetermined temperature range. It has the form of a solution in which at least one polymer selected from the group consisting of a coal (hereinafter referred to as a polymer having a specific structure) and the compound of component (B) are dissolved in an organic solvent. The molecular weight of the specific structure polymer is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and still more preferably 10,000 to 200,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 100,000.

The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed, but it is 1 weight from the viewpoint of forming a uniform and defect-free coating film. % From the viewpoint of storage stability of the solution, and preferably 10% by weight or less.

The organic solvent contained in the liquid crystal aligning agent used for this invention will not be specifically limited if a specific structure polymer melt | dissolves uniformly.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used.
Furthermore, when the solubility of the polymer of the present invention in a solvent is high, it is preferable to use a solvent represented by the formula [D-1] to the formula [D-3].

It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 20 mass%-99 mass% of the whole solvent contained in a liquid crystal aligning agent. Especially, 20 mass%-90 mass% is preferable. More preferably, it is 30% by mass to 80% by mass.

  As long as the effects of the present invention are not impaired, the liquid crystal aligning agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied. it can. Although the specific example of a poor solvent is given to the following, it is not limited to these examples.

  For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate Tar, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, milk Methyl, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropion Ethyl acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, lactic acid Examples thereof include isoamyl esters and solvents represented by the above formulas [D-1] to [D-3].

  Among these, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

  It is preferable that these poor solvents are 1 mass%-80 mass% of the whole solvent contained in a liquid crystal aligning agent. Especially, 10 mass%-80 mass% are preferable. More preferably, it is 20 mass%-70 mass%.

  In the liquid crystal aligning agent of the present invention, in addition to the above, as long as the effects of the present invention are not impaired, a polymer other than the polymer described in the present invention, the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, etc. Dielectric or conductive material for changing characteristics, silane coupling agent for improving adhesion between liquid crystal alignment film and substrate, crosslinkability for increasing hardness and density of liquid crystal alignment film When firing the compound, and further, the coating film, an imidization accelerator for the purpose of efficiently proceeding imidization by heating of the polyimide precursor may be added.

<Liquid crystal alignment film>
<Method for producing liquid crystal alignment film>
The liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, drying and baking. The substrate on which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, an acrylic substrate, a polycarbonate substrate such as a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light, such as aluminum, can also be used.

  Examples of the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to fully remove the organic solvent contained, it is dried at 50 ° C. to 120 ° C. for 1 minute to 10 minutes and then baked at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes. Although the thickness of the coating film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is 5-300 nm, Preferably it is 10-200 nm.

  Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and a photo-alignment processing method.

The rubbing process can be performed using an existing rubbing apparatus. Examples of the material of the rubbing cloth at this time include cotton, nylon, and rayon. As conditions for the rubbing treatment, generally, conditions of a rotational speed of 300 to 2000 rpm, a feed speed of 5 to 100 mm / s, and an indentation amount of 0.1 to 1.0 mm are used. Thereafter, the residue generated by rubbing is removed by ultrasonic cleaning using pure water or alcohol.

As a specific example of the photo-alignment treatment method, there is a method in which the surface of the coating film is irradiated with radiation deflected in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. Can be mentioned. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 100 nm to 400 nm are preferable, and those having a wavelength of 200 nm to 400 nm are particularly preferable. Moreover, in order to improve liquid crystal orientation, you may irradiate a radiation, heating a coating-film board | substrate at 50-250 degreeC. Dose of the radiation is preferably ^{1~10,000mJ / cm 2, 100~5,000mJ / cm} 2 is particularly preferred. The liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.

A higher extinction ratio of polarized ultraviolet rays is preferable because higher anisotropy can be imparted. Specifically, the extinction ratio of linearly polarized ultraviolet light is preferably 10: 1 or more, and more preferably 20: 1 or more.

  In the above, the film irradiated with polarized radiation may then be contact-treated with a solvent containing at least one selected from water and an organic solvent.

  The solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves a decomposition product generated by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- Examples include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Two or more of these solvents may be used in combination.

In view of versatility and safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable. Water, 2-propanol, and a mixed solvent of water and 2-propanol are particularly preferable.

  In the present invention, the contact treatment between the film irradiated with polarized radiation and the solution containing the organic solvent is a treatment such that the film and the liquid are preferably sufficiently in contact with each other, such as immersion treatment or spraying treatment. Done. Especially, the method of immersing a film | membrane in the solution containing an organic solvent, Preferably it is 10 seconds-1 hour, More preferably, it is 1 to 30 minutes is preferable. The contact treatment may be performed at normal temperature or preferably at 10 to 80 ° C., more preferably at 20 to 50 ° C. Moreover, a means for enhancing contact such as ultrasonic waves can be applied as necessary.

  After the above contact treatment, for the purpose of removing the organic solvent in the used solution, either rinsing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, or drying, or both May be done.

Furthermore, the film subjected to the contact treatment with the solvent may be heated at 150 ° C. or higher for the purpose of drying the solvent and reorienting the molecular chains in the film.

The heating temperature is preferably 150 to 300 ° C. A higher temperature promotes reorientation of molecular chains. However, if the temperature is too high, molecular chains may be decomposed. Therefore, as heating temperature, 180-250 degreeC is more preferable, and 200-230 degreeC is especially preferable.

If the heating time is too short, the effect of reorienting the molecular chain may not be obtained, and if it is too long, the molecular chain may be decomposed. 10 minutes is more preferable.

  When a photosensitive side chain type acrylic polymer that exhibits liquid crystallinity in a predetermined temperature range is used as the component (A), it is obtained after forming a coating film and irradiating the obtained coating film with polarized ultraviolet rays. By heating the coated film in a temperature range (also referred to as a liquid crystal temperature range) in which the resin of component (A) exhibits liquid crystallinity, a liquid crystal alignment film having alignment control ability is obtained.

The heating temperature is preferably within a temperature range of a temperature at which the side chain acrylic polymer exhibits liquid crystallinity (hereinafter referred to as a liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a side-chain acrylic polymer that can exhibit liquid crystallinity is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the upper limit of the liquid crystal temperature range, with the temperature being 10 ° C. lower than the lower limit of the liquid crystal expression temperature of the side chain acrylic polymer used. It is preferable that the temperature is in a range where the temperature is the upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
The liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

<Liquid crystal display element>
The liquid crystal display element of this invention comprises the liquid crystal aligning film obtained by the manufacturing method of the said liquid crystal aligning film.

In the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method for producing a liquid crystal alignment film, a liquid crystal cell is produced by a known method, and a liquid crystal cell is used. This is a display element.

  As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Note that the liquid crystal display element may be an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display.

First, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of SiO ₂ —TiO ₂ formed by a sol-gel method.

Next, the liquid crystal alignment film of the present invention is formed on each substrate. Next, the other substrate is superposed on one substrate so that the alignment film surfaces face each other, and the periphery is bonded with a sealant. In order to control the substrate gap, a spacer is usually mixed in the sealing material. In addition, it is preferable that spacers for controlling the substrate gap are also sprayed on the in-plane portion where no sealing material is provided. A part of the sealing material is provided with an opening that can be filled with liquid crystal from the outside.

Next, a liquid crystal material is injected into a space surrounded by two substrates and the sealing material through an opening provided in the sealing material. Thereafter, the opening is sealed with an adhesive. For the injection, a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used. Next, a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer. By passing through the above process, the liquid crystal display element of this invention is obtained.

In the present invention, as the sealant, for example, a resin that is cured by ultraviolet irradiation or heating having a reactive group such as an epoxy group, an acryloyl group, a methacryloyl group, a hydroxyl group, an allyl group, or an acetyl group is used. In particular, it is preferable to use a cured resin system having reactive groups of both an epoxy group and a (meth) acryloyl group.

An inorganic filler may be blended in the sealing agent of the present invention for the purpose of improving adhesiveness and moisture resistance. The inorganic filler that can be used is not particularly limited. Specifically, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, Calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. Preferably, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide Beam, calcium silicate, aluminum silicate. Two or more of the above inorganic fillers may be mixed and used.

The following examples further illustrate the present invention. The present invention is not construed as being limited to these.
Abbreviations used in the examples are as follows.
<Additives>

<Synthesis Example of Compound 1 (S1)>

In a 200 mL four-necked flask, 7.00 g of 4-aminodiphenylamine and 75 g of acetonitrile were charged, and 9.40 g of triethoxysilylpropyl isocyanate was added dropwise over 10 minutes with stirring under ice cooling, followed by stirring at room temperature for 3 hours. Thereafter, the crystals precipitated in the reaction solution were filtered under reduced pressure and dried under reduced pressure to obtain 6.16 g of Compound 1 (S1) (yield: 38%, property: light purple solid).
¹ H-NMR (400 MHz) in CDCl ₃ : 7.25-7.22 ppm (m, 2H), 7.19-7.15 ppm (m, 2H), 7.06-7.01 ppm (m, 4H), 6.92 ppm (t, J = 7.2 Hz , 1H), 6.35ppm (s, 1H), 5.71ppm (s, 1H), 4.98-4.94ppm (m, 1H), 3.80ppm (q, J = 6.8Hz, 6H), 3.22ppm (q, J = 7.2Hz, 2H), 1.67-1.57ppm (m, 2H), 1.21ppm (t, J = 6.8Hz, 9H), 0.65-0.60ppm (m, 2H)
<Synthesis Example of Compound 2 (S2)>

In a 300 mL four-necked flask, 7.00 g of 1-methylpiperazine and 138 g of acetonitrile were charged, and 17.29 g of triethoxysilylpropyl isocyanate was added dropwise over 15 minutes while stirring with ice cooling, followed by stirring at room temperature for 5 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and the solvent was completely distilled off to obtain 22.9 g of Compound 2 (S2) (yield: 94%, property: yellow oil).
¹ H-NMR (400 MHz) in CDCl ₃ : 4.81-4.73 ppm (m, 1H), 3.82 ppm (q, J = 6.8 Hz, 6H), 3.40-3.36 ppm (m, 4H), 3.27-3.22 ppm (m , 2H), 2.40-2.37ppm (m, 4H), 2.30ppm (s, 3H), 1.68-1.59ppm (m, 2H), 1.23ppm (t, J = 6.8Hz, 9H),
0.67-0.62ppm (m, 2H)
<Synthesis of Compound 3 (S3)>

A 2 L four-necked flask was charged with 20.00 g of 4,4′-diaminodiphenylamine and 300 g of tetrahydrofuran, and a solution obtained by diluting 50.90 g of triethoxysilylpropyl isocyanate with 100 g of tetrahydrofuran was added dropwise over 30 minutes while stirring with ice. Thereafter, the mixture was stirred at room temperature for 18 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and about half of THF was distilled off. Next, 720 g of acetonitrile was added at room temperature, stirred for 30 minutes, and then stirred at 5 ° C. for a while. The crystals thus precipitated were filtered under reduced pressure and dried under reduced pressure to obtain 60.70 g of compound 3 (S3) (yield: 87%, property: white solid).
¹ H-NMR (400MHz) in d6-DMSO: 8.10ppm (s, 2H), 7.61ppm (s, 1H), 7.20ppm (d, J = 7.6Hz, 4H), 6.87ppm (d, J = 7.6Hz , 4H), 6.04-6.00ppm (m, 2H), 3.75ppm (q, J = 6.8Hz, 12H), 3.34ppm (s, 2H), 3.06-3.00ppm (m, 4H), 1.50-1.42ppm ( m, 4H), 1.14ppm (t, J = 6.8Hz, 18H), 0.58-0.52ppm (m, 4H)
<Synthesis of Compound 4 (S4)>

To a 300 mL four-necked flask, 4.00 g of 1,4-diaminobenzene and 60 g of tetrahydrofuran were charged, and a solution obtained by diluting 18.76 g of triethoxysilylpropyl isocyanate with 20 g of tetrahydrofuran was added dropwise over 1.5 hours with stirring under ice cooling. And then stirred at room temperature for 18 hours. Thereafter, the crystals precipitated in the reaction solution were filtered under reduced pressure, and transferred to another 300 mL four-necked flask. Next, 100 g of acetonitrile was added thereto, followed by stirring for a while at room temperature. The crystal slurry thus obtained was filtered under reduced pressure and dried under reduced pressure to obtain 18.98 g of compound 4 (S4) (yield: 85%, property: white solid).
¹ H-NMR (400 MHz) in CDCl ₃ : 7.60-7.47 ppm (br, 2H), 6.51 ppm (s, 4H), 6.46-6.30 ppm (br, 2H), 3.81 ppm (q, J = 6.8 Hz, 12H ), 3.24-3.10ppm (m, 4H), 1.70-1.57ppm (m, 4H), 1.22ppm (t, J = 6.8Hz, 18H), 0.67-0.62ppm (m, 4H)
<Methacrylic monomer>

MA1 was synthesized by a synthesis method described in a patent document (WO2011-084546).
MA2 was synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).
<Polymerization initiator>
AIBN: 2,2'-azobisisobutyronitrile

<Tetracarboxylic dianhydride>
PMDA: pyromellitic dianhydride
CBDA: 1,2,3,4-cyclobutanetetracarboxylic acid-1,2: 3,4-dianhydride <diamine>
BAPU: 1,3-bis (4-aminophenethyl) urea
Me-4PhA: N- (4-aminophenethyl) methylamine

<Organic solvent>
THF: tetrahydrofuran
NMP: N-methyl-2-pyrrolidone
BC: Butyl cellosolve

<Polymer polymerization example 1>
After MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were dissolved in THF (85.5 g) and deaerated with a diaphragm pump, AIBN (1.48 g, 3.0 mmol) was added and deaeration was performed again. Thereafter, the mixture was reacted at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder.
NMP (29.3 g) was added to the resulting methacrylate polymer powder (6.0 g) and dissolved by stirring at room temperature for 5 hours. NMP (24.7 g) and BC (40.0 g) were added to this solution and stirred to obtain a methacrylate polymer solution (PMA1).

<Example 1>
Additive (S1) (0.018 g) was added to the resulting methacrylate polymer solution (PMA1) (10.0 g) g, and the mixture was stirred at room temperature for 1 hour to obtain a liquid crystal aligning agent (TM1).

<Examples 2-4, Controls 1-3>
The liquid crystal aligning agent of Examples 2-4 was obtained using the method shown in Table 1 and the method similar to Example 1. FIG.
Controls 1 to 3 were also adjusted in the same manner.

<Production of liquid crystal cell>
The liquid crystal aligning agent (TM1) obtained in Example 1 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C. for 90 seconds, and a film thickness of 100 nm. A liquid crystal alignment film was formed. Next, the coating surface was irradiated with 313 nm ultraviolet rays through a polarizing plate at 15 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, a 6 μm spacer is set on the liquid crystal alignment film surface of one substrate, and the two substrates are combined so that the rubbing directions are parallel to each other. The periphery was sealed, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which liquid crystals were aligned in parallel.

Regarding the liquid crystal alignment materials (TM2 to TM4) obtained in Examples 2 to 4, liquid crystal cells were prepared using the same method as TM1.
Controls 1 to 3 (CM1 to CM3) produced liquid crystal cells in the same manner.

<VHR evaluation>
For the evaluation of VHR, a voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 70 ° C. for 60 μs, the voltage after 50 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica. The evaluation results are shown in Table 2.

<Polymer polymerization example 2>
As a tetracarboxylic dianhydride component, PMDA (4.88 g) was stirred in NMP (20.89 g) at room temperature for 1 hour to obtain a completely dissolved solution a1. Next, as a diamine component, BAPU (6.35 g) was stirred in NMP (68.33 g) at room temperature for 1 hour to completely dissolve it to obtain a solution a2. After the solution a2 was cooled to 10 ° C., the solution a1 was added and reacted at 60 ° C. for 8 hours to obtain an 11 wt% solution of polyamic acid. NMP (37.5 g) and BCS (45.83 g) were added to the obtained solution (100 g) and stirred at room temperature for 2 hours to obtain a polyamic acid solution A having a concentration of 6 wt%.
Then, as a tetracarboxylic dianhydride component, CBDA (6.82 g) was stirred in NMP (22.61 g) at room temperature for 1 hour to obtain a completely dissolved solution b1. Next, BAPU (5.73 g) and Me-4PhA (2.01 g) as diamine components were stirred in NMP (62.62 g) at room temperature for 1 hour, and completely dissolved to obtain a solution b2. After the solution b2 was cooled to 10 ° C., the solution b1 was added and reacted at room temperature for 2 hours to obtain a 14.6 wt% solution of polyamic acid. NMP (74.82 g) and BCS (33.75 g) were added to the obtained solution (100 g) and stirred at room temperature for 2 hours to obtain a polyamic acid solution B having a concentration of 7 wt%.
Next, polyamic acid solution B (50.0 g) was added to the obtained polyamic acid solution A (50.0 g), and the mixture was stirred at room temperature for 2 hours to obtain a polyamic acid solution (PAA1) having a concentration of 6.5 wt%. .

<Example 5>
Additive (S2) (0.020 g) was added to the resulting polyamic acid solution (PAA1) (10.0 g) g and stirred at room temperature for 1 hour to obtain a liquid crystal aligning agent (TPA1).

<Example 6, control 4>
The liquid crystal aligning agent of Example 6 was obtained using the same method as in Example 5 with the composition shown in Table 3.
For Control 4, the PAA1 solution was used as it was.

<Production of liquid crystal cell>
The liquid crystal aligning agent (TPA1) obtained in Example 5 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 80 seconds, and then at 230 ° C. The film was baked for 30 minutes to obtain a coating film having a thickness of 100 nm. This polyimide film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 50 mm / sec, pushing amount: 0.3 mm), and then subjected to ultrasonic irradiation for 1 minute in pure water and at 80 ° C. for 10 minutes. Dried. Two substrates with such a liquid crystal alignment film are prepared, a 6 μm spacer is set on the liquid crystal alignment film surface of one substrate, and the two substrates are combined so that the rubbing directions are parallel to each other. The periphery was sealed, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which liquid crystals were aligned in parallel.

For the liquid crystal alignment material (TPA2) obtained in Example 6, a liquid crystal cell was prepared using the same method as for TPA1.
In addition, a liquid crystal cell was prepared in the same manner for control 4 (CPA1).

<VHR evaluation>
VHR is evaluated by applying a voltage of 1V to the obtained liquid crystal cell at a temperature of 90 ° C. for 60 μs, measuring the voltage after 166.7 ms, and calculating the voltage holding ratio as the voltage holding ratio. did. The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technica. The evaluation results are shown in Table 4.

  From the above, it was found that the liquid crystal display element using the liquid crystal aligning agent of this example has a good charge retention rate.

Claims (10)

The liquid crystal aligning agent characterized by including the following (A) component, (B) component, and an organic solvent.
Component (A): at least one polymer selected from the group consisting of a polyimide precursor, an imidized polymer of the polyimide precursor, and a photosensitive side chain acrylic polymer that exhibits liquid crystallinity within a predetermined temperature range. .
Component (B): A compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted. The compound having the alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted is contained in an amount of 0.1 to 20% by mass with respect to the polymer. Liquid crystal aligning agent. The liquid crystal aligning agent according to claim 1 or 2, wherein the compound having an alkoxysilyl group and a urea structure in which both the 1-position and the 3-position are substituted is represented by the following formula (b).

(In the formula, X ² is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 1 to 6, and R ² is a hydrogen atom. Or an alkyl group, and when n is 2 or more, R ² is alkylene together with other R ² , or when n is 1 to 6, it is also bonded to X ² to form a ring together with X ² May form a structure, L represents an alkylene having 2 to 20 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or (It is an alkynyl group having 2 to 4 carbon atoms, and q represents a natural number of 1 to 3.) The liquid crystal aligning agent according to claim 1, wherein R ³ in the formula (b) is a methyl group or an ethyl group. N in Formula (b) is 2 or 1, The liquid crystal aligning agent in any one of Claims 1 thru | or 4 characterized by the above-mentioned. 6. The liquid crystal aligning agent according to claim 1, wherein q in the formula (b) is 3. The liquid crystal aligning film obtained by apply | coating and baking the liquid crystal aligning agent in any one of Claims 1 thru | or 6. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to claim 1 and irradiating polarized radiation. A liquid crystal display device comprising the liquid crystal alignment film according to claim 7. A lateral electric field drive type liquid crystal display device comprising the liquid crystal alignment film according to claim 7.