KR101824283B1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(X¹ 은 지방족 탄화수소기 또는 비방향족계 고리형 탄화수소기로 이루어지는 2 가의 유기기이고, X² 는 단결합, -O-, -NH-, -S-, -SO₂-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, 벤젠고리 또는 시클로헥산고리이고, X³ 은 하기 식 [1-1] ∼ [1-6] 에서 선택되는 적어도 1 종이다).
[화학식 2]

(W¹ 은 수소 원자 또는 벤젠고리를 나타낸다. W² 는 벤젠고리, 시클로헥산고리 및 복소고리로 이루어지는 군에서 선택되는 고리형기이고, W³ 은 탄소수 1 ∼ 18 을 갖는 알킬기, 불소 함유 알킬기, 알콕실기 또는 불소 함유 알콕실기이다)A liquid crystal alignment treatment agent capable of providing a liquid crystal alignment film in which scraped scrapes and scratches of a polymer film accompanied with rubbing treatment are not generated well and a voltage retention rate is suppressed after a long time of light irradiation and a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, Thereby providing a display element.
A liquid crystal alignment treatment agent comprising a compound (component (A)) represented by the following formula [1] and at least one polymer (component (B)) selected from the group consisting of a polyimide precursor and a polyimide.
[Chemical Formula 1]

(X ¹ is a divalent organic group comprising an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group, and X ² is a single bond, -O-, -NH-, -S-, -SO ₂ -, -COO-, OCO-, -CONH-, -NHCO-, -CO-, a benzene ring or a cyclohexane ring, and X ³ is at least one selected from the following formulas [1-1] to [1-6].
(2)

(W ¹ represents a hydrogen atom or a benzene ring, W ² represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, W ³ represents an alkyl group having 1 to 18 carbon atoms, a fluorine- A fluorine-containing alkoxyl group)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element,

The present invention relates to a liquid crystal alignment treatment agent used in producing a liquid crystal alignment film, a liquid crystal alignment film using the same, and a liquid crystal display element.

BACKGROUND ART [0002] Liquid crystal display devices are widely used today as display devices for realizing thin and light weight. In general, a liquid crystal alignment film is used in this liquid crystal display element to determine the alignment state of the liquid crystal. In addition, except for some vertically aligned liquid crystal display elements, most of the liquid crystal alignment film is produced by subjecting the surface of the polymer film formed on the electrode substrate to any alignment treatment.

A currently commonly used method for orienting a polymer film is a method in which the surface of the polymer film is subjected to so-called rubbing treatment in which a pressure is applied by a cloth made of rayon or the like and rubbed. As a method for solving the problem based on the scraped surface of the polymer film accompanied with the rubbing treatment, a liquid crystal alignment treatment agent containing a specific thermally crosslinkable compound is used in addition to at least one polymer of a polyamic acid or a polyimide A method of improving the rubbing resistance by using a curing agent such as a method (see, for example, Patent Document 1) or a method using a liquid crystal alignment treatment agent containing an epoxy group-containing compound (see, for example, Patent Document 2) have.

Japanese Patent Application Laid-Open No. 9-185065 Japanese Patent Application Laid-Open No. 9-146100

In recent years, for the purpose of shortening the manufacturing process time of the liquid crystal display element, the rubbing treatment is performed under a strong rubbing condition in a short time. For this reason, there is a problem that a lot of scratches accompanied by shavings and rubbing of the polymer film accompanying the rubbing treatment occur more than in the conventional art. Such an abnormality is one of the causes of deteriorating the characteristics of the liquid crystal display element and hence lowering the yield.

In recent years, liquid crystal display devices have been used for applications such as liquid crystal televisions and vehicle-mounted applications, for example, car navigation systems and meter panels, in accordance with the recent enhancement of performance of liquid crystal display devices. In such applications, a backlight having a large calorific value may be used in order to obtain high brightness. For this reason, the liquid crystal alignment film is further required to have high reliability from a separate standpoint, that is, high stability against light from the backlight. Particularly, when the voltage holding ratio, which is one of the electric characteristics of the liquid crystal display element, is lowered by light irradiation from the backlight, ghost failure (also referred to as line ghost), which is one display defect of the liquid crystal display element, The high liquid crystal display element can not be obtained. Therefore, in addition to good initial characteristics, it is demanded that the liquid crystal alignment film does not lower the voltage holding ratio even after exposure to light for a long time, for example.

An object of the present invention is to provide a liquid crystal alignment film having the above characteristics. That is, an object of the present invention is to provide a liquid crystal display device and a method of manufacturing the liquid crystal display device, which are capable of effectively preventing degradation of the voltage holding ratio even when exposed to light irradiation for a long time without causing scrapes or rubbing accompanying scraping or rubbing treatment A liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film, and a liquid crystal display element obtained from the liquid crystal alignment treatment agent.

As a result of intensive studies, the inventors of the present invention have found that a liquid crystal alignment treatment agent containing a compound having a specific structure is very effective for achieving the above object, and has completed the present invention.

That is, the present invention has the following points.

(1) A liquid crystal alignment treatment agent containing the following components (A) and (B).

Component (A): A compound represented by the following formula [1] (hereinafter also referred to as a specific amine compound)

Component (B): at least one kind of polymer selected from the group consisting of a polyimide precursor and polyimide (hereinafter also referred to as a specific polymer).

[Chemical Formula 1]

(X ¹ is a divalent organic group comprising an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group, and X ² is a single bond, -O-, -NH-, -S-, -SO ₂ -, -COO-, OCO-, -CONH-, -NHCO-, -CO-, a benzene ring or a cyclohexane ring, and X ³ is at least one group selected from the following formulas [1-1] to [1-6]

(2)

(W ¹ represents a hydrogen atom or a benzene ring, W ² represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, W ³ represents an alkyl group having 1 to 18 carbon atoms, a fluorine atom having 1 to 18 carbon atoms Containing alkyl group, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms)

(2) X ^{1 in the} formula [1] represents any -CH ₂ - not adjacent to the amino group of the bivalent organic group, -O-, -COO-, -OCO-, -CONH-, -NHCO- , -CO-, -S-, -S (O ) 2 -, -CF 2 -, -C (CF 3) 2 -, -C (CH 3) 2 -, -Si (CH 3) 2 -, - _{OSi (CH 3) 2 -,} -Si (CH 3) 2 O-, -OSi (CH 3) 2 O-, and may be substituted with a cyclic hydrocarbon group or a heterocyclic ring, a hydrogen atom bonded to any carbon atom Is substituted with a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic hydrocarbon group having 3 to 20 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom or a hydroxyl group The liquid crystal alignment treatment agent according to the above (1), which may be used.

(3) The liquid crystal alignment treating agent according to the above (1) or (2), wherein X ² in the formula [1] is a single bond, -OCO-, -NHCO-, a benzene ring or a cyclohexane ring.

(1) to (4), wherein X ³ in the formula [1] is a group of the structure represented by the formula [1-2], the formula [1-4], the formula [ (3) above.

(5) The positive resist composition as described in the above item (1), wherein the component (B) is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and a polyimide obtained by dehydrocondensing the polyamic acid The liquid crystal alignment treatment agent according to any one of (1) to (4) above.

(6) The liquid crystal alignment treatment agent according to (5), wherein the diamine component is a diamine compound represented by the following formula [2].

(3)

(Wherein Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-, Y ² is a single bond or CH _{2) b} - _(b is an integer in a) of 1 ~ 15, Y ³ is a single _{bond, - (CH 2) c -} (c is an integer of 1 ~ 15), -O-, -CH 2 O- , -COO- or OCO- Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom), or a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton device and, Y ⁵ is any of a hydrogen atom in the cyclic group (these cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, 1 to 3 carbon atoms Alkyl group, may be substituted 1 to 3 carbon atoms in the alkoxy group, fluorine-containing alkoxy group or a fluorine atom having a carbon number of 1 to 3 fluorine-containing alkyl group, having 1 to 3), n is an integer of 0 ~ 4. Y ⁶ is , An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and m is an integer of 1 to 4)

(7) The liquid crystal alignment treating agent according to (6), wherein the diamine compound represented by the formula [2] is contained in an amount of 5 to 80 mol% of the diamine component.

(8) The liquid crystal alignment treatment agent according to any one of (5) to (7), wherein the tetracarboxylic dianhydride component is a tetracarboxylic acid dianhydride represented by the following formula [3].

[Chemical Formula 4]

(Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms)

(9) The liquid crystal alignment treating agent according to (8), wherein Z ¹ in the formula [3] is a structure represented by the following formulas [3a] to [3j].

[Chemical Formula 5]

(Wherein Z ² to Z ⁵ are each a hydrogen atom, a methyl group, a chlorine atom or a benzene ring and may be the same or different), Z ⁶ and Z ⁷ are each a hydrogen atom or a methyl group,

(10) The liquid crystal alignment treatment agent according to any one of (1) to (9) above, wherein the polymer of component (B) is a polyimide obtained by dehydrating and ring closure of polyamic acid.

(11) The liquid crystal alignment treating agent according to any one of (1) to (10), wherein the amount of the component (A) is 0.1 to 50 parts by mass based on 100 parts by mass of the component (B).

(12) The liquid crystal alignment treatment agent according to any one of (1) to (11), wherein the liquid crystal alignment treatment agent contains an organic solvent and contains a poor solvent in an amount of 5 to 80 mass% of the total organic solvent.

(13) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of (1) to (12) above.

(14) A liquid crystal display element having the liquid crystal alignment layer according to (13) above.

(15) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound capable of polymerizing by at least one of an active energy ray and a heat is disposed between the pair of substrates (13), wherein the liquid crystal alignment layer is used for a liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(16) A liquid crystal display element having the liquid crystal alignment film according to (15) above.

(17) electrode and a liquid crystal alignment layer described in (13) or (15) above, and a liquid crystal layer is formed between the pair of substrates by at least one of active energy rays and heat A liquid crystal display element according to the above (16), wherein a liquid crystal composition containing a polymerizable compound to be polymerized is placed and a step of polymerizing the polymerizable compound while applying a voltage between the electrodes is performed.

(18) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, wherein a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of an active energy ray and a heat is disposed between the pair of substrates, The liquid crystal alignment film according to (13), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(19) A liquid crystal display element having the liquid crystal alignment film according to (18) above.

(20) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, wherein a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal display element according to (19), wherein the liquid crystal display element is manufactured through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

INDUSTRIAL APPLICABILITY The liquid crystal alignment treatment agent of the present invention does not cause scarring caused by scraped scraping or rubbing treatment of a polymer film accompanied by rubbing treatment during the production process of a liquid crystal display element, Can be obtained. Thus, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television having a large surface and a high definition.

The reason why the liquid crystal alignment treating agent of the present invention brings about the above-mentioned excellent properties for some reason is not necessarily clear, but it is considered as follows.

That is, in the liquid crystal alignment treatment agent of the present invention, the primary amino group in the specific amine compound may be a salt formed with a carboxyl group in a specific polymer, or may be an amide bond or a carboxyl group in a specific polymer, , Or it is considered that the imide group in the specific polymer is bonded to the imide group through a reaction accompanied by ring opening of the imide group. It is also believed that the primary amino group forming a salt with the carboxyl group in the specific polymer in the firing step in the production of the liquid crystal alignment film forms an amide bond by elimination of water. As a result, it is considered that the liquid crystal alignment treatment agent of the present invention is efficiently combined with a specific amine compound and a specific polymer among the obtained liquid crystal alignment films, although it is a simple means of mixing in an organic solvent.

It is also known that the double bond moieties of the formulas [1-1] to [1-6] as X ³ in the specific amine compound react by irradiation with heat or ultraviolet rays. Therefore, as described above, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in the firing step in the production of the liquid crystal alignment film and in the production of the liquid crystal display element The cross-linking reaction of the polymers occurs by the curing step of the sealant of the sealant, that is, the firing step or the ultraviolet light irradiation step, so that the physical stability is improved and furthermore, the resistance to heat and light becomes high.

In this way, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is superior to the liquid crystal alignment film containing no specific amine compound in comparison with the liquid crystal alignment film containing the specific amine compound, which is accompanied by scraping or rubbing treatment of the polymer film accompanied with the rubbing treatment in the liquid crystal display element production process It is possible to suppress the deterioration of the voltage holding ratio even when exposed to light irradiation for a long period of time.

In addition, since the specific amine compound in the present invention has only one primary amino group contained in the molecule, there is a possibility that problems such as precipitation of the polymer and gelation during the preparation of the liquid crystal alignment treatment agent and storage of the liquid crystal alignment treatment agent Can be avoided.

≪ Specific amine compound >

The specific amine compound of the present invention is a compound represented by the following formula [1].

[Chemical Formula 6]

(X ¹ is a divalent organic group comprising an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group, and X ² is a single bond, -O-, -NH-, -S-, -SO ₂ -, -COO-, OCO-, -CONH-, -NHCO-, -CO-, a benzene ring or a cyclohexane ring, and X ³ is at least one member selected from the groups represented by the following formulas [1-1] to [1-6] to be)

(7)

In the formula [1], X ¹ represents a divalent organic group consisting of an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group, in order that the primary amino group contained in the specific amine compound easily reacts with the specific polymer by salt formation or reaction. to be. Specifically, any -CH ₂ - which is an aliphatic hydrocarbon group or nonaromatic cyclic hydrocarbon group having 1 to 20 carbon atoms and is not adjacent to an amino group may be replaced by -O-, -COO-, -OCO-, -CONH- , -NHCO-, -CO-, -S-, -S (O) 2 -, -CF 2 -, -C (CF 3) 2 -, -C (CH 3) 2 -, -Si (CH 3) ₂ , -OSi (CH ₃ ) ₂ -, -Si (CH ₃ ) ₂ O-, -OSi (CH ₃ ) ₂ O-, a cyclic hydrocarbon group or a heterocyclic ring, The hydrogen atom is preferably a linear alkyl group of 1 to 20 carbon atoms, a branched alkyl group of 3 to 20 carbon atoms, a cyclic hydrocarbon group of 3 to 20 carbon atoms, a fluorine-containing alkyl group of 1 to 10 carbon atoms, a heterocyclic ring, Or may be substituted with a hydroxyl group.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a hydrocarbon group having an unsaturated bond. Among them, an alkylene group having 1 to 20 carbon atoms is preferable. More preferably an alkylene group having 1 to 15 carbon atoms, and still more preferably an alkylene group having 1 to 10 carbon atoms.

Specific examples of the non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctadecane ring, a tricyclohexane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, A tricyclodecanoic acid ring, a bicyclohexyl ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, or an adamantane ring. Among them, a ring having 3 to 20 carbon atoms is preferable. More preferably a ring having 3 to 15 carbon atoms, and more preferably a ring having 6 to 12 carbon atoms, which is a non-aromatic cyclic hydrocarbon group. Specifically, it is a cyclohexane ring or a bicyclohexyl ring.

In the formula [1], X ² represents a single bond, -O-, -NH-, -S-, -SO ₂ -, -COO-, -OCO-, -CONH-, -NHCO-, Or a cyclohexane ring. Among them, a single bond, -O-, -NH-, -COO-, -OCO-, -CONH-, -NHCO-, a benzene ring or a cyclohexane ring is preferable. More preferably a single bond, -OCO-, -NHCO-, a benzene ring or a cyclohexane ring.

In the formula [1], X ³ is at least one selected from the groups represented by the formulas [1-1] to [1-6].

In the formula [1-3], W ¹ represents a hydrogen atom or a benzene ring.

In the formula [1-6], W ² is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Among them, a benzene ring, a cyclohexane ring or a biphenyl ring is preferable.

In the formula [1-6], W ³ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms is preferable.

In the formula [1], X ³ is preferably a group represented by the formula [1-2], the formula [1-4], the formula [1-5] or the formula [1-6].

Preferred combinations of X ¹ , X ² and X ^{3 in} the formula [1] are as shown in Tables 1 and 2.

Among them, the specific amine compound is preferably an amine compound in combination of 1-1 to 1-7, 1-14 to 1-24, 1-33 to 1-40, or 1-46 to 1-48 . Particularly preferred are amine compounds in combination of 1-1 to 1-7 or 1-14 to 1-16.

≪ Specific polymer &

The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor having a structure represented by the following formula [A] and a polyimide in which the polyimide precursor is imidized.

[Chemical Formula 8]

(Wherein R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and n is a positive integer)

The specific polymer of the present invention is preferably a repeating unit represented by the following formula [D] because the specific polymer is relatively easily obtained by using the diamine component represented by the following formula [B] and the tetracarboxylic acid dianhydride component represented by the following formula [C] Or a polyimide obtained by imidizing the polyamic acid is preferable.

[Chemical Formula 9]

(R < ¹ > and R < ² > have the same meanings as defined in formula [A]

[Chemical formula 10]

(R ¹ , R ² and n have the same meanings as defined for formula [A]),

In the formula [A] and the equation [D], and R ¹ and R ² are even, each one kind, each having different R ¹ and R ² It may be a combination of plural kinds different as a repeating unit.

As the diamine component, it is preferable to use a diamine compound represented by the following formula [2] (hereinafter also referred to as a specific side chain type diamine compound).

(11)

In formula [2], Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-. Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or COO- is preferable because the side chain structure is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or COO-.

In formula [2], Y ² is a single bond or (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or (CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

In formula [2], Y ³ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-. Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- is preferable since it is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or OCO-.

In formula [2], Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ is an organic group having 12 to 25 carbon atoms and having a steroid skeleton. Among them, an organic group having 12 to 25 carbon atoms and having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable.

In the formula [2], Y ⁵ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

In the formula [2], n is an integer of 0 to 4. Preferably an integer of 0 to 2.

In the formula [2], Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In the formula [2], m is an integer of 1 to 4. Preferably an integer of 1.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , n and m in the formula [2] are as shown in Tables 3 to 32.

More specifically, it is, for example, a diamine compound represented by the following formulas [2-1] to [2-31].

[Chemical Formula 12]

(R ⁵ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ⁶ represents an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or fluorine Containing alkoxyl group)

[Chemical Formula 13]

(R ⁷ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ - R ⁸ is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group)

[Chemical Formula 14]

(R ⁹ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O - or -NH-, and R ¹⁰ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group)

[Chemical Formula 15]

(Wherein R ¹¹ is an alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer)

[Chemical Formula 16]

(R ¹² is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer)

[Chemical Formula 17]

(A ⁴ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ³ is a 1,4-cyclohexylene group or a 1,4-phenylene group, A ² is an oxygen atom or -COO- * , The bond number (bond) attached with "*" is bonded to A ³ ), A ¹ is an oxygen atom or -COO- * (provided that the bond number ("CH ₂ ) a _2" ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1)

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

Among them, the compound represented by the formula [2-1] to [2-6] or the compound represented by the formula [2-9] to the formula [2-31] is preferable as the specific side chain type diamine compound. Particularly preferably, the compound represented by the formula [2-1] to [2-6], the compound of the formula [2-9] to the compound of the formula [2-12] -22] or the compound represented by the formula [2-23] is preferable.

In the present invention, as long as the effect of the present invention is not impaired, other diamine compounds other than the specific side chain diamine compound (hereinafter also referred to as other diamine compounds) can be used as the diamine component. Specific examples thereof are illustrated below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, Phenylene bis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4- (4-aminophenoxy) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4- Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, Aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- Phenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis -Bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- , 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) amide, 3- ) Methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, , 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

In addition, as long as the effect of the present invention is not impaired, a diamine compound having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used.

Specifically, diamine compounds represented by the following formulas [DA1] to [DA12] can be exemplified.

(23)

(S ¹ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

≪ EMI ID =

(S ² represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or NH-, S ³ represents an alkyl group having 1 to 22 carbon atoms or fluorine Containing alkyl group)

(25)

(p is an integer of 1 to 10)

In addition to these, a diamine compound represented by the following formulas [DA13] to [DA20] may be used as long as the effect of the present invention is not impaired.

(26)

(m is an integer of 0 to 3, and n is an integer of 1 to 5)

In addition, as long as the effect of the present invention is not impaired, a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA25] may be used.

(27)

(m ₁ is an integer of 1 ~ ^4, S 4 represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) - , -O-, -CO-, -NH-, -N (CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH ₃ ) -, or N (CH ₃ ) CO-, m ₂ and m ₃ are each an integer of 0 to 4, and m ₂ + m ₃ is an integer of 1 to 4. m ₄ and m ₅ are S ⁵ is a linear or branched alkyl group having 1 to 5 carbon atoms and m ₆ is an integer of 1 to 5. S ⁶ is a single bond, -CH ₂ -, -C ₂ H ₄ - -C (CH ₃ ) ₂ -, -CF ₂ -, -C (CF ₃ ) -, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, _{-CH 2 O-, -OCH 2 -,} -COO-, -OCO-, -CON (CH 3) - or a N (CH ₃₎ CO-, ₇ m is an integer of 1-4.)

The above-mentioned specific side chain type diamine compound and other diamine compounds may be used alone or in combination of two or more kinds thereof in accordance with the properties such as liquid crystal alignability, voltage retention rate, and accumulated charge when used as a liquid crystal alignment film.

In order to obtain the specific polymer of the present invention, it is preferable to use a tetracarboxylic acid dianhydride (also referred to as a specific tetracarboxylic acid dianhydride) represented by the following formula [3] as a part of the starting material.

(28)

In the formula [3], Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.

Specifically, it is a group of a structure represented by the following formulas [3a] to [3j].

[Chemical Formula 29]

Formula [3a] of, Z ² ~ Z ⁵ are each independently a group in which hydrogen atom, methyl group, chlorine atom or selected from a benzene ring, a formula [3g] from, Z ⁶ and Z ⁷ are each independently a hydrogen atom or a methyl group to be.

Especially preferred structures of Z ^{1 in} the formula [3] are those of the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] ] to be.

In the present invention, other tetracarboxylic acid dianhydride (hereinafter also referred to as other tetracarboxylic acid dianhydride) other than the specific tetracarboxylic dianhydride may be used as long as the effect of the present invention is not impaired . Examples of other tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides of the following tetracarboxylic acids.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4- Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The above-mentioned specific tetracarboxylic dianhydrides and other tetracarboxylic dianhydrides may be used alone or in combination of two or more, depending on the properties of the liquid crystal alignment layer, such as liquid crystal aligning property, voltage holding ratio, and accumulated charge .

The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide, and the polyimide precursor has a structure represented by the formula [A].

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic dianhydride component. Generally, a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component composed of one or more kinds of diamine compounds. In order to obtain a polyamide acid alkyl ester, a method of converting a carboxyl group of a polyamic acid into an ester is used. In order to obtain a polyimide, a method of imidizing the polyamic acid or polyamide acid alkyl ester to form a polyimide is used.

The liquid crystal alignment film obtained by using the specific polymer of the present invention can increase the pretilt angle of the liquid crystal as the content ratio of the specific side chain type diamine compound in the diamine component increases. For the purpose of increasing this property, it is preferable that 5 to 80 mol% of the diamine component is a specific side chain type diamine compound. Among them, it is more preferable that 5 to 60 mol% of the diamine component is a specific side chain type diamine compound from the viewpoint of coating property of the liquid crystal alignment treatment agent and electrical characteristics as a liquid crystal alignment film.

Further, in order to obtain the specific polymer of the present invention, it is preferable to use a specific tetracarboxylic acid dianhydride as the tetracarboxylic acid dianhydride component. At this time, it is preferable that 1 mol% or more of the tetracarboxylic dianhydride component is a specific tetracarboxylic acid dianhydride, more preferably 5 mol% or more, further preferably 10 mol% or more. Further, 100 mol% of the tetracarboxylic dianhydride component may be a specific tetracarboxylic dianhydride.

The reaction of the diamine component and the tetracarboxylic dianhydride component is usually carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples thereof are illustrated below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve, ethyl cellosolve, methyl cellosolve, But are not limited to, sorbose, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene 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, diethyl Diethylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate 3-methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, propyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. Further, a solvent which does not dissolve the polyimide precursor may be used in combination with the solvent within a range in which the resulting polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic dianhydride component are reacted in the organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is dispersed or dissolved in the organic solvent as it is A method of adding a diamine component to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic dianhydride component and a diamine component, and the like , Any of these methods may be used. When a plurality of diamine components or tetracarboxylic dianhydride components are used to carry out the reaction, they may be reacted in a previously mixed state, or they may be sequentially reacted individually, and the individually reacted low molecular weight compounds are mixed and reacted A specific polymer may be used. The polymerization temperature at that time may be any temperature between -20 ° C and 150 ° C, preferably between -5 ° C and 100 ° C. If the concentration is too low, it becomes difficult to obtain a specific polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to perform uniform stirring. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the number of moles of the diamine component to the total number of moles of the tetracarboxylic dianhydride component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.

In the polyimide of the present invention, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

The temperature at which the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferred because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Of these, use of acetic anhydride is preferable since the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by controlling the amount of catalyst, the reaction temperature, and the reaction time.

In the case of recovering the polyimide precursor or polyimide produced from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and dried at room temperature or under reduced pressure or at normal pressure. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further increased, which is preferable.

The molecular weight of the specific polymer of the present invention is preferably 5,000 to 5,000 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography), considering the strength of the polymer film obtained therefrom, the workability in forming a polymer film, And more preferably 10,000 to 150,000.

≪ Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and contains a specific amine compound, a specific polymer and an organic solvent.

The content of the specific amine compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the specific polymer, and the crosslinking reaction proceeds to develop the desired film curability, More preferably from 0.1 to 100 parts by mass, and particularly preferably from 1 to 50 parts by mass.

The polymer component in the liquid crystal alignment treatment agent of the present invention may be all the specific polymer of the present invention, and the other polymer may be mixed with the specific polymer of the present invention. At this time, the content of other polymer in the polymer component is 0.5 to 15% by mass, preferably 1 to 10% by mass. Examples of the other polymer include a polyimide precursor or polyimide obtained from a tetracarboxylic acid dianhydride component not containing a specific side chain type diamine compound and a specific diamine component containing no tetracarboxylic dianhydride have. Further, polyimide precursors and polymers other than polyimide, specifically, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, and the like can be mentioned.

The organic solvent in the liquid crystal alignment treatment agent of the present invention preferably has an organic solvent content of 70 to 99 mass% from the viewpoint of forming a uniform polymer film by coating. The content can be appropriately changed depending on the intended thickness of the liquid crystal alignment film.

The organic solvent at this time is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer. More specifically, there may be mentioned N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, Dimethylol-imidazolidinone, ethylamylketone, methylmethylpyrrolidone, dimethylvinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone, Nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

The liquid crystal alignment treatment agent of the present invention may contain a crosslinkable compound having an epoxy group, an isocyanate group or an oxetane group, a compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group, A crosslinking compound having a polymerizable unsaturated bond, and the like.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylpentanoyloxyphenyl) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, 2- (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3- Oxy) phenyl) -1- (4- (1- (4 - (2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

(30)

Specifically, it is a crosslinkable compound represented by the following formulas [4a] to [4k].

(31)

(32)

(33)

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin and the like. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group, or a benzoguanamine derivative or glycoluril can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. They preferably have 3 to 6 methylol groups or alkoxymethyl groups per one triazine ring on average.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercial product, MW having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co., Ltd.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 253 and 254, butoxymethylated melamines such as Cymel 506 and 508, methoxymethylated isobutoxymethylated melamine containing carboxyl groups such as Cymel 1141, and methoxymethylated ethoxy compounds such as Cymel 1123, Methoxymethylated butoxymethylated benzoguanamine such as methylated benzoguanamine and Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, and carboxyl group-containing methoxymethylated methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80. Guanamine ( Manufactured by Mitsui Cyanamid Co., Ltd.), and the like. Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluril such as Cymel 1172 and methoxymethylolglycoluril such as Powderlink 1174, and the like.

Benzene having a hydroxyl group or an alkoxyl group, or a phenolic compound can also be exemplified as a crosslinking compound. For example, there can be mentioned 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) Dihydroxymethyl-p-tert-butylphenol and the like.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri ) Crosslinkable compounds having three polymerizable unsaturated groups such as acryloyloxyethoxy trimethylol propane and glycerin polyglycidyl ether poly (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylates such as di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, Two cross-linked compound having a polymerizable unsaturated group in the molecule, and the like; Hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- Ester, N-methylol (meth) acrylamide, and other crosslinkable compounds having one polymerizable unsaturated group in the molecule.

In addition, the compound represented by the following formula [5] can also be exemplified as a crosslinkable compound.

(34)

(E ¹ is a cyclohexane ring, a non-cyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, a monovalent is selected from anthracene ring or phenanthrene ring group, E ² is, Is a monovalent group selected from the following formulas [5a] and [5b], and n is an integer of 1 to 4)

(35)

The compound is an example of a crosslinkable compound, but is not limited thereto. The crosslinkable compound contained in the liquid crystal alignment treatment agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer component, and the crosslinking reaction proceeds to exhibit a desired effect, More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass.

It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the following formulas [M1] to [M156] as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge dropout of the liquid crystal cell using the liquid crystal alignment film. The amine compound may be directly added to a solution of a specific polymer, but it is preferable to add the amine compound in a suitable solvent at a concentration of 0.1 to 10 mass%, preferably 1 to 7 mass%. The solvent is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned specific polymer.

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

The liquid crystal alignment treatment agent of the present invention may contain an organic solvent (also referred to as a poor solvent) or a compound which improves the film thickness uniformity and surface smoothness of the polymer film when the liquid crystal alignment treatment agent is applied, ≪ / RTI > Further, it may contain a compound for improving the adhesion between the liquid crystal alignment film and the substrate.

Specific examples of the poor solvent for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, 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 monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid, methyl lactate, isobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy- , 1-phenoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, and lactic acid isoamyl ester.

These poor solvents may be used alone or in combination. When such a poor solvent is used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total amount of the organic solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EFTA EF301, EF303 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), FLORAD FC430 and FC431 manufactured by Sumitomo 3M ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment treatment agent.

Specific examples of the compound improving the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound for improving adhesion to a substrate is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain a crosslinkable compound, a poor solvent and a compound for improving the adhesion property, as long as the effect of the present invention is not impaired, Or a conductive material may be added.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In the reflection type liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side. As the electrode in this case, a material that reflects light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. As other coating methods, there are dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is coated on the substrate, the polymer film can be formed by evaporating the solvent at 50 to 300 ° C, preferably 80 to 250 ° C, by a heating means such as a hot plate. When the thickness of the polymer film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness of the polymer film is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 To 100 nm. When the liquid crystal is horizontally aligned or tilted, the polymer film after firing is subjected to rubbing, polarized ultraviolet irradiation, or the like.

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, and then manufacturing a liquid crystal cell by a known method to obtain a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate to make the liquid crystal alignment film surface inward, and the other substrate is bonded ), A method of injecting a liquid crystal under reduced pressure and sealing, or a method of dropping a liquid crystal on a liquid crystal alignment film surface on which a spacer is dispersed and then bonding and sealing the substrate.

Further, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat between a pair of substrates And then polymerizing the polymerizable compound by at least one of irradiation of an active energy ray and heating while applying a voltage between the electrodes is preferably used for the liquid crystal display device. Here, the active energy ray is preferably ultraviolet ray.

The liquid crystal display device controls the pretilt angle of the liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is incorporated into a liquid crystal material, a liquid crystal cell is assembled, and a predetermined voltage is applied to the liquid crystal layer, , And the size of the pretilt angle of the liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. Further, since the rubbing treatment is not required in the PSA system, it is suitable for forming a vertically aligned liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

That is, the liquid crystal display element of the present invention can be obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, then preparing a liquid crystal cell, The orientation of the liquid crystal molecules can be controlled.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on a liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inward, the other substrate is bonded, A method in which a liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is bonded and sealed.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays.

Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal can not be controlled. When the amount exceeds 10 parts by mass, unreacted polymerizable compounds increase, do.

After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of the liquid crystal molecules can be controlled.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with an electrode and containing a polymerizable group polymerizable by at least one of active energy rays and heat between the pair of substrates And then applying a voltage between the electrodes. The liquid crystal display device according to claim 1, Here, the active energy ray is preferably ultraviolet ray.

In order to obtain a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, a method of using a polymer component containing a polymerizable group Method. Examples of the polymerizable group include polymerizable unsaturated groups such as an acryl group, a methacryl group, a vinyl group, and a maleimide group.

Since the liquid crystal alignment treatment agent of the present invention contains a specific amine compound having a double bonding site which reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation with ultraviolet rays and heating have.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on a liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inward, the other substrate is bonded, A method in which a liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is bonded and sealed.

After the liquid crystal cell is manufactured, the alignment of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

As described above, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television having a large surface and a high definition.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

&Quot; Synthesis of polyimide precursor and polyimide &quot;

The abbreviations of the compounds used in the examples are as follows.

(Tetracarboxylic dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

TCA: tetracarboxylic acid dianhydride represented by the following formula

(42)

(Specific side chain type diamine compound)

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

PBCH5DAB: 1,3-Diamino-4- {trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

ColDAB-1: Specific side chain type diamine compound represented by the following formula

(43)

(Other diamine compound)

p-PDA: p-phenylenediamine

m-PDA: m-Phenylenediamine

DBA: 3,5-diaminobenzoic acid

(44)

(Specific amine compound)

A-1: Specific amine compound represented by the following formula

[Chemical Formula 45]

(Amine compound)

B-1: An amine compound represented by the following formula

(46)

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight of polyimide precursor and polyimide)

The molecular weight of the polyimide in Synthesis Example was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) , And measured by the following method.

Column temperature: 50 ° C

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

Flow rate: 1.0 ml / min

Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight about 12,000, 4,000,

(Measurement of imidization rate)

The imidization rate of the polyimide in the synthesis example was measured as follows. (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) (0.53 ml) was added to an NMR sample tube (NMR sampling tube standard, phi 5 ) Was added, and completely dissolved by applying ultrasonic waves. This solution was subjected to proton NMR measurement at 500 MHz using an NMR (nuclear magnetic resonance) analyzer (JNW-ECA500) (manufactured by Nippon Denshi Datum Co., Ltd.). A proton originating from a structure in which the structure did not change before and after imidization was defined as a reference proton and the proton peak integrated value derived from the NH group of the amide acid appearing in the vicinity of 9.5 to 10.0 ppm By using the following formula.

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

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid in the case of the polyamic acid (the imidization rate is 0% The ratio of the number of reference protons to one protopertone.

&Lt; Synthesis Example 1 &

BODA (5.61 g, 22.4 mmol), PCH7DAB (5.34 g, 14.0 mmol) and p-PDA (1.52 g, 14.0 mmol) were mixed in NMP (22.4 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (1.10 g, 5.60 mmol) and NMP (18.3 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (A) having a resin solid content concentration of 25.0 mass%. This polyamic acid had a number average molecular weight of 27,400 and a weight average molecular weight of 79,100.

&Lt; Synthesis Example 2 &

 NMP was added to the polyamic acid solution (A) (20.0 g) having a resin solid content concentration of 25.0 mass% obtained in Synthesis Example 1 to dilute to 6 mass%, acetic anhydride (2.51 g) and pyridine 1.90 g), and the mixture was reacted at 80 DEG C for 3.5 hours. The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The imidization ratio of the polyimide was 52%, the number average molecular weight was 23,100, and the weight average molecular weight was 56,200.

&Lt; Synthesis Example 3 &

BODA (5.72 g, 22.8 mmol), PBCH5DAB (3.71 g, 8.57 mmol) and DBA (3.04 g, 20.0 mmol) were mixed in NMP (22.4 g) and reacted at 80 ° C for 5 hours. Thereafter, CBDA (1.12 g, 5.74 mmol) and NMP (18.3 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

NMP was added to the obtained polyamic acid solution (20.2 g) to dilute to 6 mass%, acetic anhydride (4.55 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 90 ° C for 3 hours. The reaction solution was poured into methanol (400 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (C). The imidization ratio of the polyimide was 80%, the number average molecular weight was 20,700, and the weight average molecular weight was 51,300.

&Lt; Synthesis Example 4 &

BODA (5.87 g, 23.5 mmol), ColDAB-1 (2.17 g, 4.40 mmol) and DBA (3.79 g, 24.9 mmol) were mixed in NMP (21.4 g) and reacted at 80 ° C for 4 hours. Thereafter, CBDA (1.15 g, 5.80 mmol) and NMP (17.5 g) were added and reacted at 40 ° C for 5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (2.50 g) and pyridine (1.95 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (D). The imidization ratio of the polyimide was 54%, the number average molecular weight was 21,500, and the weight average molecular weight was 54,500.

&Lt; Synthesis Example 5 &

The reaction was carried out at 40 占 폚 for 6 hours to give a mixture of TCA (4.10 g, 18.3 mmol), PCH7DAB (3.48 g, 9.15 mmol) and p- PDA (0.99 g, 9.15 mmol) To obtain a polyamic acid solution (E) having a resin solid content concentration of 25.0 mass%. The number average molecular weight of this amic acid was 28,900 and the weight average molecular weight was 79,200.

&Lt; Synthesis Example 6 &

(1.80 g, 4.17 mmol) and m-PDA (1.05 g, 9.72 mmol) were mixed in NMP (17.8 g) and reacted at 40 ° C for 6 hours, To obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (2.50 g) and pyridine (1.95 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (F). The imidization rate of the polyimide was 55%, the number average molecular weight was 19,500, and the weight average molecular weight was 50,300.

Table 33 shows the polyamic acid and polyimide obtained in the above Synthesis Examples.

* 1: Polyamide acid.

&Quot; Production of liquid crystal alignment treatment agent &quot;

Examples 1 to 6 and Comparative Examples 1 to 4 show production examples of liquid crystal alignment treatment agents for evaluation. The results are shown in Tables 34 and 35.

Production of Liquid Crystal Alignment Film, Evaluation of Rubbing Treatment Resistance, Production of Liquid Crystal Cell (also commonly referred to as Cell), Production of Liquid Crystal Cell (PSA Cell), and Evaluation of Electrical Properties are as follows. The properties of the respective liquid crystal alignment treatment agents obtained in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Tables 36 to 38. Table 36 shows the results of the evaluation of the rubbing resistance, Table 37 shows the evaluation results of the electric characteristics using ordinary cells, and Table 38 shows the evaluation results of the electric characteristics using the PSA cells.

&Lt; Production of liquid crystal alignment film &

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of a substrate having a 30 mm x 40 mm ITO electrode formed thereon and heat-treated on a hot plate at 80 캜 for 5 minutes and at 220 캜 for 30 minutes in a heat- A substrate on which a 100 nm polyimide liquid crystal alignment film was formed was obtained.

&Quot; Evaluation of rubbing resistance &

The coating film surface of the substrate on which the liquid crystal alignment film obtained in the above &quot; Production of Liquid Crystal Alignment Film &quot; was formed was coated on the coated surface of the substrate with a rayon bath having a roll diameter of 120 mm using a Rayon spring at a roll rotation speed of 300 rpm, a roll progress speed of 20 mm / sec, Rubbing treatment. The surface of the liquid crystal alignment film in the vicinity of the center of the substrate after the rubbing treatment was randomly observed at five points by a laser microscope set at a magnification of 100 times and a rubbing scratch which was observed in a range of about 6.5 mm square, Adhesion amount) was evaluated. The evaluation criteria were as follows.

 (Evaluation standard)

A: Less than 20 crumbs scraped by rubbing or rubbing

B: 20 to 40 shavings scraped by rubbing scratches or rubbing

C: 40 ~ 60 pieces of scraped scraped by rubbing scratches or rubbing

D: More than 60 crumbs scraped by rubbing scratches or rubbing

&Quot; Production of liquid crystal cell (ordinary cell) &quot;

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of a substrate having a 30 mm x 40 mm ITO electrode formed thereon and heat-treated on a hot plate at 80 캜 for 5 minutes and at 220 캜 for 30 minutes in a heat- An ITO substrate on which a 100 nm polyimide liquid crystal alignment film was formed was obtained. The coating film surface of the ITO substrate was subjected to rubbing treatment using a rayon bath with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.1 mm.

Two sheets of the ITO substrates on which the obtained liquid crystal alignment films were formed were prepared, and 6 mu m spacers were interposed therebetween with the liquid crystal alignment film surface on the inner side, and the periphery was bonded with a sealer to prepare blank cells. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

Regarding the liquid crystal cell obtained in Examples and Comparative Examples, alignment uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. In all of the liquid crystal cells, there were no shrinkage and orientation defects accompanying the rubbing treatment, and the liquid crystal was uniformly oriented.

&Quot; Production of liquid crystal cell (PSA cell) &quot;

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of a substrate on which an ITO electrode with a pattern interval of 20 占 퐉 of 10 mm 占 10 mm was formed and a substrate on which a 10 mm 占 40 mm ITO electrode was formed at the center, For 5 minutes at 220 DEG C for 30 minutes in a thermocycling type clean oven to obtain a polyimide coating film having a thickness of 100 nm. The coating film surface was cleaned with pure water and then subjected to heat treatment at 100 DEG C for 15 minutes in a thermocycling type clean oven to obtain a substrate having a liquid crystal alignment film formed thereon.

The substrate on which this liquid crystal alignment film was formed was assembled by interposing a spacer of 6 mu m with the liquid crystal alignment film surface inward and bonding the periphery with a sealant to prepare an empty cell. The polymerizable compound (1) represented by the following formula was mixed with MLC-6608 (manufactured by Merck Japan) in a vacuum cell by vacuum impregnation, and 0.3% by mass of a polymerizable compound was mixed with 100% by mass of MLC-6608 Liquid crystal was injected and the injection port was sealed to obtain a liquid crystal cell.

(47)

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while applying a voltage of 5 V alternating current to the obtained liquid crystal cell and irradiated with ultraviolet rays of 20 J / cm 2 in terms of 365 nm Thus, a liquid crystal cell (PSA cell) in which the alignment direction of the liquid crystal was controlled was obtained. The temperature in the irradiator when the liquid crystal cell was irradiated with ultraviolet rays was 50 占 폚.

The response speeds of the liquid crystal cell before and after ultraviolet irradiation were measured. The response speed was measured from T90 to T10 at a transmittance of 90% and a transmittance of 10%. The PSA cells obtained in Examples and Comparative Examples were found to have controlled the alignment direction of the liquid crystal in that the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before the ultraviolet irradiation.

Further, in all the liquid crystal cells, it was confirmed by the polarization microscope observation that the liquid crystal was uniformly oriented.

&Quot; Evaluation of electric characteristics &

A voltage of 1 V was applied at 60 占 퐉 under a temperature of 80 占 폚 to the liquid crystal cell obtained in the above-mentioned "production of a liquid crystal cell (normal cell)" and "production of a liquid crystal cell (PSA cell) The voltage at the end was measured, and the degree of voltage maintenance was calculated as the voltage holding ratio. The measurement was conducted using a VHR-1 voltage maintenance ratio measuring device (manufactured by Toyota Technica) with a voltage of ± 1 V, a pulse width of 60 μs, and a flame period of 16.67 ms or 50 ms.

After the measurement of the voltage holding ratio was completed, ultraviolet rays of 50 J / cm 2 in terms of 365 nm were irradiated to the liquid crystal cell, and VHR was measured under the same conditions. The ultraviolet irradiation was performed using a table-top UV curing apparatus (HCT3B28HEX-1) (manufactured by Sen Light Corporation).

&Lt; Example 1 >

NMP (5.83 g) and NMP solution (2.50 g) of A-1 (5.0% by mass of NMP (A-1) were added to a polyamic acid solution (A) (10.0 g) having a resin solid content concentration of 25.0% Solution) and BCS (23.5 g) were added, and the mixture was stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treating agent (1). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (1), evaluation of the rubbing resistance with the above-described conditions and evaluation of the electric characteristics of the ordinary cell were carried out.

&Lt; Example 2 >

NMP (12.6 g) was added to the polyimide powder (B) (2.51 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 占 폚 for 24 hours. An NMP solution (2.51 g) of A-1 (5.0% by mass of NMP solution), NMP (7.27 g) and BCS (19.7 g) were added to this solution and stirred at 50 占 폚 for 15 hours To obtain a liquid crystal alignment treatment agent (2). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (2), the rubbing treatment resistance was evaluated under the above-described conditions, and the electric characteristics of the normal cell and the PSA cell were evaluated.

&Lt; Example 3 >

NMP (11.8 g) was added to the polyimide powder (C) (2.48 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added an NMP solution (3.47 g) of A-1 (NMP solution of 5.0 mass% of A-1), 8.70 g of NMP and 17.5 g of BCS, and the mixture was stirred at 50 캜 for 15 hours To obtain a liquid crystal alignment treatment agent (3). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (3), evaluation of the rubbing resistance and ordinary electric characteristics of the cell were carried out under the above-described conditions.

<Example 4>

NMP (14.2 g) was added to the polyimide powder (D) (2.50 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, an NMP solution (2.50 g) of A-1 (5.0 wt% of NMP solution of A-1), NMP (13.30 g) and BCS (11.8 g) were added and stirred at 50 캜 for 15 hours To obtain a liquid crystal alignment treatment agent (4). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (4), the rubbing treatment resistance was evaluated under the above-described conditions, and the electric characteristics of a typical cell were evaluated.

&Lt; Example 5 >

NMP (7.73 g) and NMP solution (2.50 g) of A-1 (5.0% by mass of NMP (A-1)) were added to a polyamic acid solution (E) (10.0 g) having a resin solid content concentration of 25.0% Solution) and BCS (21.5 g) were added, and the mixture was stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (5), the rubbing treatment resistance was evaluated under the above-described conditions, and the electric characteristics of the cell were evaluated.

&Lt; Example 6 >

NMP (16.7 g) was added to the polyimide powder (F) (2.51 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. An NMP solution (5.02 g) of A-1 (5.0% by mass of NMP solution), NMP (8.28 g) and BCS (11.8 g) of A-1 were added to this solution and stirred at 50 占 폚 for 15 hours To obtain a liquid crystal alignment treatment agent (6). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (6), the rubbing treatment resistance was evaluated under the above-described conditions, and the electric characteristics of the cell were evaluated.

&Lt; Comparative Example 1 &

NMP (8.20 g) and BCS (23.5 g) were added to the polyamide acid solution (A) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (7), the rubbing resistance was evaluated under the above-described conditions, and the electric characteristics of a typical cell were evaluated.

&Lt; Comparative Example 2 &

NMP (14.8 g) was added to the polyimide powder (B) (2.51 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 占 폚 for 24 hours. NMP (7.40 g) and BCS (19.6 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treating agent (8). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (8), the rubbing treatment resistance was evaluated under the above-described conditions, and the electric characteristics of the normal cell and the PSA cell were evaluated.

&Lt; Comparative Example 3 &

NMP (6.10 g) and NMP solution (2.63 g) of B-1 (B-1 is 5.0% by mass of NMP (2)) were added to a polyamic acid solution (A) (10.5 g) having a resin solid content concentration of 25.0% Solution) and BCS (24.7 g) were added, and the mixture was stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (9), the rubbing treatment resistance was evaluated under the above-described conditions, and the electric characteristics of the cell were evaluated.

&Lt; Comparative Example 4 &

NMP (13.2 g) was added to the polyimide powder (B) (2.50 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, an NMP solution (2.50 g) of B-1 (5.0 mass% of NMP solution of B-1), NMP (6.58 g) and BCS (19.6 g) was added and stirred at 50 占 폚 for 15 hours To obtain a liquid crystal alignment treatment agent (10). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the liquid was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 10, the rubbing resistance of the cell and the PSA cell were evaluated under the above-described conditions.

From the above results, it was found that the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention had less scraping off by rubbing treatment and, after exposure to ultraviolet rays, The decrease in the retention ratio was small.

Comparative Example 3 and Comparative Example 4 using the amine compound (B-1) having no double bond site and Comparative Example 1 and Comparative Example 2 which did not contain a specific amine compound were largely scraped off by rubbing treatment, In addition, the voltage holding ratio after the exposure to ultraviolet rays for a long time also decreased greatly.

Industrial availability

The liquid crystal alignment treatment agent of the present invention does not cause scarring caused by scraped scraping or rubbing of the polymer film accompanied by the rubbing treatment during the production process of the liquid crystal display element, and even when exposed to light irradiation for a long time, A liquid crystal alignment film capable of suppressing the deterioration of the liquid crystal alignment film can be obtained. The liquid crystal display element having the liquid crystal alignment film of the present invention is excellent in reliability and is preferably used for a liquid crystal television of a large size and a large size and is also useful as a TN device, an STN device, a TFT liquid crystal device, Do.

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be used for manufacturing a liquid crystal display element having a step of irradiating ultraviolet rays while applying a voltage between the electrodes.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-158783 filed on July 13, 2010 are hereby incorporated herein by reference as the disclosure of the present invention.

Claims (18)

A liquid crystal alignment treatment agent comprising the following components (A) and (B).
Component (A): A compound represented by the following formula [1].
Component (B): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide.

(Wherein X ¹ is an alkylene group having 1 to 10 carbon atoms, X ² is a single bond, a benzene ring or a cyclohexane ring, and X ³ is a group represented by the following formula [1-4]

The method according to claim 1,
Wherein the component (B) is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and a polyimide obtained by dehydrocondylating the polyamic acid, . 3. The method of claim 2,
Wherein the diamine component is a diamine compound represented by the following formula [2].

(Formula [2], Y ¹ is a single bond, - (CH _{2) a} - a (a is an integer of 1 ~ 15), -O-, -CH 2 O-, -COO- or OCO-, Y ² is a single bond or (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15) , -CH ₂ O-, -COO- or OCO-, Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be substituted with 1 to 3 An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom) is a divalent organic group selected from, Y ⁵ is a benzene ring, a cyclohexane ring and the cyclic group is selected from the group consisting of heterocyclic ring (any of the hydrogen atoms on these cyclic group, carbon An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or fluorine atoms), and n is an integer of 0 to 4 Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and m is an integer of 1 to 4) The method of claim 3,
The diamine compound represented by the formula [2] is contained in an amount of 5 to 80 mol% of the diamine component. 3. The method of claim 2,
Wherein the tetracarboxylic acid dianhydride is a tetracarboxylic acid dianhydride represented by the following formula [3].

(In the formula [3], Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms) 6. The method of claim 5,
A liquid crystal alignment treating agent wherein Z ¹ in the formula [3] is a structure represented by the following formulas [3a] to [3j].

(Formula [3a] of, Z ² ~ Z ⁵ is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, respectively, are the same or different. In the formula [3g] from, Z ⁶ and Z ⁷ represents a hydrogen atom or a methyl group, Each may be the same or different) The method according to claim 1,
A liquid crystal alignment treatment agent wherein the polymer of component (B) is a polyimide obtained by dehydration ring closure of polyamic acid. The method according to claim 1,
Wherein the component (A) is 0.1 part by mass to 50 parts by mass relative to 100 parts by mass of the component (B). The method according to claim 1,
A liquid crystal alignment treatment agent wherein the liquid crystal alignment treatment agent contains an organic solvent and contains 5 to 80 mass% of a poor solvent as a whole of the organic solvent. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 9. A liquid crystal display element having the liquid crystal alignment film according to claim 10. 11. The method of claim 10,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, And the polymerizable compound is polymerized while applying a voltage between the liquid crystal alignment layer and the liquid crystal alignment layer. A liquid crystal display device comprising a liquid crystal alignment layer between a liquid crystal alignment film and a pair of substrates provided with an electrode according to claim 10 and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat between the pair of substrates A liquid crystal display element produced by placing a liquid crystal composition and polymerizing the polymerizable compound while applying a voltage between the electrodes. 11. The method of claim 10,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, And the polymerizable group is polymerized while applying a voltage to the liquid crystal alignment layer. A liquid crystal alignment film according to claim 10, which has a liquid crystal layer between a pair of substrates provided with electrodes and contains a polymerizable group polymerizable by at least one of active energy rays and heat between the pair of substrates And polymerizing the polymerizable group while applying a voltage between the electrodes.
delete delete delete