KR20160003120A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal alignment treatment agent capable of enhancing adhesion between a sealant and a liquid crystal alignment film and suppressing the occurrence of display irregularities near the frame of the device under high temperature and high humidity conditions and forming a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio do. (B) containing at least one polymer selected from the group consisting of a component (A) containing a compound represented by the formula [1], a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimide ) Component. ≪ / RTI > (X ¹ : a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms and having a benzene ring or a cyclohexane ring, X ² : 5] (W ¹ : a hydrogen atom or a benzene ring)

Description

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

The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

A film made of an organic material such as a polymer material has attracted attention for ease of formation and insulation performance and is widely used as an interlayer insulating film and a protective film in the field of electronic devices. Among them, in a liquid crystal display element well known as a display device, an organic film made of polyimide is used as a liquid crystal alignment film.

The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. In recent years, there has been a demand for suppressing display defects due to contrast or a long-term use of a liquid crystal display element as the liquid crystal display element becomes finer and finer.

For such a problem, in the case of using polyimide as the liquid crystal alignment film, there has been proposed a method for increasing the liquid crystal alignability and preventing display defects from being generated in the periphery of the liquid crystal display screen, which is formed by using a liquid crystal alignment treatment agent containing an alkoxysilane compound A liquid crystal alignment film has been proposed (for example, see Patent Document 1 or 2).

Japanese Patent Application Laid-Open No. 61-171762 Japanese Patent Application Laid-Open No. 11-119226

Recently, liquid crystal display devices have been used for mobile applications such as smart phones and mobile phones. In these applications, in order to secure as much display surface as possible, it is necessary to make the width of the sealant used for bonding between the substrates of the liquid crystal display element smaller than the conventional one. For the reasons described above, it is also required to position the sealing agent at the position where the sealant is in contact with the end portion of the liquid crystal alignment film having poor adhesiveness to the sealant or the liquid crystal alignment film. In such a case, water is easily mixed into the liquid crystal display element between the sealant and the liquid crystal alignment film by use under high temperature and high humidity conditions, and display irregularity occurs near the frame of the liquid crystal display element.

In addition, when water is mixed in the liquid crystal display element, the voltage holding ratio, which is one of the electric characteristics of the liquid crystal display element, is significantly lowered, and ghost failure (also called line ghost), which is one of display defects of the liquid crystal display element, A liquid crystal display element with high reliability can not be obtained.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a liquid crystal display device capable of enhancing adhesion between a sealant and a liquid crystal alignment film and suppressing occurrence of display irregularities in the vicinity of a frame of a liquid crystal display element under high temperature and high humidity conditions, A liquid crystal alignment treatment agent capable of providing a liquid crystal alignment film capable of suppressing the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent containing at least one kind of polymer selected from the group consisting of a compound having a specific structure and a polyimide precursor and a polyimide is very effective The present invention has been completed.

That is, the present invention has the following points.

(1) A liquid crystal alignment treatment agent characterized by containing 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 obtained by reacting a diamine component and a tetracarboxylic acid component.

[Chemical Formula 1]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring and X ² represents a group represented by the following formulas [ Represents a structure selected from the formula [1-5]

(2)

(W < ¹ > represents a hydrogen atom or a benzene ring)

(2) The liquid crystal alignment treating agent according to (1), wherein X ^{1 in} the formula (1) is an alkylene group having 1 to 10 carbon atoms.

(3) The liquid crystal alignment treatment agent according to (1) or (2), wherein the X ² of the formula [1] is a structure selected from the formulas [1-1], [1-2] and [ .

(4) The liquid crystal composition according to any one of (1) to (3), wherein the diamine component in the polymer of the component (B) contains at least one diamine compound having a structure represented by the following formula [2] Orientation treatment agent.

(3)

(Y represents a substituent of a structure selected from the following formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

[Chemical Formula 4]

(a represents an integer of 0 to 4, and b represents an integer of 0 to 4).

Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-, Y ² represents 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), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 and having a steroid skeleton, Any hydrogen atom on the cyclic group may be substituted with 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a substituent, 3 alkyl group, carbon atoms and may be substituted with one to three of an alkoxy group, fluorine-containing alkyl group, fluorine-containing C 1 -C 3 alkoxy group or a fluorine atom of 1 to 3 carbon atoms, n is an integer of 0 ~ 4, Y ⁶ Represents 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 fluoro-containing alkoxyl group having 1 to 18 carbon atoms,

Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group of 1 to 12 carbon atoms and Y ¹¹ represents an alkyl group of 1 to 5 carbon atoms.

(5) The liquid crystal alignment treatment agent according to any one of (1) to (4), wherein the tetracarboxylic acid component in the polymer of the component (B) contains a compound represented by the following formula [3].

[Chemical Formula 5]

(Z < ¹ > is a group of a structure selected from the following formulas [3a] to [3j]

[Chemical Formula 6]

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

(6) The liquid crystal alignment treatment agent according to any one of (1) to (5), wherein the polymer of the component (B) is a polyimide obtained by dehydrating and cyclizing a polyamic acid.

(7) The liquid crystal alignment treating agent according to any one of (1) to (6), wherein the amount of the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (B).

(8) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (7).

(9) A liquid crystal alignment film obtained by the ink jet method using the liquid crystal alignment treatment agent according to any one of (1) to (7).

(10) A liquid crystal display element having the liquid crystal alignment film according to (8) or (9) above.

(11) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound polymerizable by at least one of an active energy ray and heat between the pair of substrates, The liquid crystal alignment film according to (8) or (9) above, which is used for a liquid crystal display device produced by polymerizing the polymerizable compound while applying a voltage between electrodes.

(12) A liquid crystal display element having the liquid crystal alignment film according to (11) above.

(13) A liquid crystal alignment film having 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, The liquid crystal alignment film according to (8) or (9), which is used for a liquid crystal display device produced by polymerizing the polymerizable group while applying a voltage between them.

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

According to the present invention, a liquid crystal alignment treatment agent containing a compound having a specific structure and at least one polymer selected from the group consisting of a polyimide precursor and a polyimide improves the adhesion between the sealing agent and the liquid crystal alignment film, It is possible to form a liquid crystal alignment film capable of suppressing the occurrence of display irregularities in the vicinity of the frame of the liquid crystal display element and suppressing a decrease in the voltage holding ratio. That is, 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 screen and a high definition.

The present invention relates to a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and further, a liquid crystal display device having the liquid crystal alignment film.

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

Component (B): at least one polymer (also referred to as a specific polymer) selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

(7)

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring and X ² represents a group represented by the following formulas [ Represents a structure selected from the formula [1-5]

[Chemical Formula 8]

(W < ¹ > represents a hydrogen atom or a benzene ring).

In the liquid crystal alignment treatment agent of the present invention, the O = C = N group (also referred to as an isocyanate group) in a specific compound can be obtained by heating at the time of producing the liquid crystal alignment treatment agent or by baking at the time of producing the liquid crystal alignment film, Is believed to be chemically bonded to the carboxyl group in the specific polymer. Therefore, it is considered that the liquid crystal alignment treatment agent of the present invention is efficiently bound to a specific compound and a specific polymer in a liquid crystal alignment film obtained therefrom, despite the simple means of mixing in an organic solvent.

It is also known that the double bond sites of the formulas [1-1] to [1-5] as X ² in a specific compound react by irradiation with heat or ultraviolet rays. These double bond sites are also contained in the compound contained in the sealant.

Therefore, when the liquid crystal alignment treatment agent of the present invention is used, the double bond sites in the liquid crystal alignment film and the compound in the sealant can be prevented by the curing step of the sealant during the production of the liquid crystal display element, And the sealant and the liquid crystal alignment film are chemically bonded to each other, thereby enhancing their adhesiveness.

In view of the above, the liquid crystal alignment treatment agent containing the specific compound of the present invention and a specific polymer has high adhesiveness to the sealant, suppresses occurrence of display irregularities in the vicinity of the frame of the liquid crystal display element even under high temperature and high humidity conditions, It is possible to form a liquid crystal alignment film capable of suppressing lowering of the voltage holding ratio.

<Specific compound>

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

[Chemical Formula 9]

(X ¹ and X ² have the same meanings as defined above, and X ² represents a structure selected from the following formulas [1-1] to [1-5]

[Chemical formula 10]

(W &lt; ¹ &gt; represents a hydrogen atom or a benzene ring)

In the formula [1], X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring. Among them, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable from the viewpoint of the availability of the compound and production.

In the formula [1], X ² is a structure selected from the formulas [1-1] to [1-5].

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

In the formula [1], X ² is preferably a structure represented by the formula [1-1], the formula [1-2] or the formula [1-4] from the viewpoint of reactivity by irradiation with heat or ultraviolet rays.

More specifically, the structure represented by the following formulas [1a] to [1d] can be mentioned.

(11)

(X ³ represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring, and X ⁴ represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring)

[Chemical Formula 12]

(X ⁵ represents an alkylene group, a benzene ring or a cyclohexane ring having 1 to 5 carbon atoms, X ⁶ represents an alkylene group, a benzene ring or a cyclohexane ring having a carbon number of 1 to 5)

&Lt; Specific polymer &

The specific polymer as the component (B) of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The polyimide precursor has a structure represented by the following formula [A].

[Chemical Formula 13]

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² may be the represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, respectively, be the same or different, A ³ and A ⁴ Each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, which may be the same or different and n is a positive integer)

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule. As the tetracarboxylic acid component, a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound , A tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.

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

[Chemical Formula 14]

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

[Chemical Formula 15]

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

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

&Lt; Diamine component >

As the diamine component for producing the specific polymer which is the component (B), a known diamine compound can be used.

Among them, it is preferable to use at least one kind of diamine compound (also referred to as a specific diamine compound) having a structure represented by the following formula [2].

[Chemical Formula 16]

(Y represents a substituent of a structure selected from the following formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

[Chemical Formula 17]

In the formula [2-1], a represents an integer of 0 to 4. Among them, 0 or 1 is preferable from the viewpoint of availability of raw materials and easiness of synthesis.

In the formula [2-2], b represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

In formula [2-3], Y ¹ represents 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 in view of availability of raw materials and ease of synthesis. desirable. 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 the formula [2-3], Y ² represents 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 [2-3], Y ³ represents 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- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [2-3], Y ⁴ is a bivalent cyclic group selected from 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, 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 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton. Among them, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable from the viewpoint of ease of synthesis.

In formula [2-3], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom in these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, 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. Among them, a benzene ring or a cyclohexane ring is preferable.

In the formula [2-3], n represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials and easiness of synthesis, 0 to 3 is preferable. More preferred is 0 to 2.

In the formula [2-3], Y ⁶ represents 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. And particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-3] for constituting the substituent Y in the formula [2] (2-1) to (2-629) listed in Tables 6 to 47 of Pages 13 to 34 of Japanese Patent Application No. 132751 (published on October 27, 2011). In addition, Y1 ~ Y6 in the respective tables of the International Patent Publication, and by reading the change Y ¹ ~ Y ⁶ of the present invention.

In the formula [2-4], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-. Among them, -O-, -CH ₂ O-, -COO- or -CONH- is preferable. More preferably -O-, -COO- or -CONH-.

In the formula [2-4], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

In the formula [2-5], Y ⁹ and Y ¹⁰ independently represent a hydrocarbon group of 1 to 12 carbon atoms.

In the formula [2-6], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

The method for producing the specific diamine compound represented by the formula [2] is not particularly limited, but preferable examples include the following.

As an example, the specific diamine compound represented by the formula [2] is obtained by synthesizing a dinitro compound represented by the following formula [2-A], reducing the nitro group and converting it into an amino group.

[Chemical Formula 18]

(Y represents a substituent of the structure selected from the above formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

The method for reducing the dinitro group of the dinitro compound represented by the formula [2-A] is not particularly limited, and a palladium- Hydrazine or hydrogen chloride using carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon or the like as a catalyst.

The specific structure of the specific diamine compound represented by the formula [2] is shown below, but it is not limited to these examples.

Specific diamine compounds include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,4- 2-7] to [2-47] in addition to 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol and 4,6-diaminoresorcinol. ] Can be mentioned.

[Chemical Formula 19]

(A &lt; ¹ &gt; represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(Wherein R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ² represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine- Containing alkoxy group)

(32)

(R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, and R ⁴ represents an alkyl group having 1 to 22 carbon atoms , An alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

(33)

(R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - or -O-, R ⁶ 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)

(34)

(R ⁷ represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is preferably a trans isomer).

(35)

(R ⁸ represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is preferably a trans isomer).

(36)

(B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, B ² represents an oxygen atom or -COO- * It represents (provided that the combined hand provided with an "*" in combination with B ^3), B ¹ is a bond hand provided with an oxygen atom or -COO- * (where, "*" is combined with the (CH ^₂₎ a ₂ A ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.)

Of the specific diamine compounds represented by the above-mentioned formula [2], liquid crystal alignment layers are formed by using a liquid crystal alignment treatment agent obtained from a specific polymer wherein the substituent Y in the formula [2] is a diamine compound having a structure represented by the formula [2-3] , The pretilt angle of the liquid crystal can be increased. Among the above diamine compounds, it is preferable to use the diamine compounds represented by the formulas [2-25] to [2-40] or the formulas [2-43] to [2-47] in order to increase the pretilt angle. More preferred are the diamine compounds represented by the formulas [2-29] to [2-40] or the formulas [2-43] to [2-47].

The amount of the diamine compound used for increasing the pretilt angle is preferably from 5 mol% to 80 mol% of the entire diamine component. More preferably, it is from 5 mol% to 60 mol% of the total diamine component in view of coating properties of the liquid crystal alignment treatment agent and electric characteristics as a liquid crystal alignment film.

The specific diamine compound represented by the formula [2] may be one or two kinds (one to two kinds) depending on the solubility and coating properties of a specific polymer to a solvent, the orientation of liquid crystals in the case of a liquid crystal alignment film, Or more can be mixed and used.

As the diamine component for producing a specific polymer, a diamine compound other than the specific diamine compound represented by the formula [2] (also referred to as another diamine compound) may be used as the diamine component. Specific examples of the other diamine compounds are shown below, but the diamines are not limited to these examples.

For example, there may be mentioned m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'- 3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, 3,3'- Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldi aniline, 3,3'-sulfo Bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl- , Dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenyl Amine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl -Methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-di Diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminobenzophenone, Diaminonaphthalene, 2,6-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4- Aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5- Di (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, Benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, Phenylenebis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 3,4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, 3,3' - [1,3 Phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4- 4-phenylenebis (3- Aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminobenzoate), bis Bis (4-aminophenyl) isophthalate, N, N '- (1,4-phenylene) bis (4-aminobenzamide), N, N (1,3-phenylene) bis (4-aminobenzamide), N, N '- N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) terephthalamide, N, N'- Bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ 2 ' -bis (4-aminophe ), Hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis Bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4- Bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, Bis (4-aminophenoxy) heptane, 1,7-bis (4-aminophenoxy) heptane, 1,7- Bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1, Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like.

As other diamine compounds, those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, and those having a polycyclic substituent composed of these groups may also be cited. Specifically, the diamine compounds represented by the following formulas [DA1] to [DA7] can be exemplified.

(37)

(38)

[Chemical Formula 39]

(Wherein A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² represents a linear chain having 1 to 22 carbon atoms Branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms)

(40)

(p represents an integer of 1 to 10)

As other diamine compounds, diamine compounds represented by the following formulas [DA8] to [DA13] may be used as long as they do not impair the effect of the present invention.

(41)

(42)

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

The diamine compounds represented by the following formulas [DA14] to [DA17] may be used as long as they do not impair the effect of the present invention.

(43)

(A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C (CH ₃ ) ₂ -, -CF ₂ -, -C (CF ₃ ) ₂ -, -O-, _{-NH-, -N (CH 3) -} , -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3) - or -N ( CH ₃ ) CO-, m ¹ and m ² each represent an integer of 0 to 4, m ¹ + m ² represents an integer of 1 to 4, and m ³ and m ⁴ in the formula [DA15] A ² is a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ is an integer of 1 to 5, A ³ is a single bond, -CH _{2 -, -C 2 H 4 -} , -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH 3 ) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3) - or -N (CH ₃₎ represents a CO-, m ⁶ represents an integer of 1 to 4)

As other diamine compounds, diamine compounds represented by the following formulas [DA18] and [DA19] may also be used.

(44)

Further, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA20] may be used.

[Chemical Formula 45]

(A ¹ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) ₃ ) CO-, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, A ³ is a single bond, -O-, _{-NH-, -N (CH 3) -} , -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- , and -O (CH ₂ ) _m - (wherein m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4)

The above other diamine compounds may be used alone or in combination of two or more types depending on the solubility of the specific polymer in a solvent, the application property of the liquid crystal alignment treatment agent, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage retention rate, May be used in combination.

&Lt; Tetracarboxylic acid component >

Examples of the tetracarboxylic acid component for producing the specific polymer which is the component (B) of the present invention include tetracarboxylic acid dianhydride represented by the following formula [3], tetracarboxylic acid derivatives thereof, tetracarboxylic acid, tetra It is preferable to use a carboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound (all of them collectively referred to as a specific tetracarboxylic acid component).

(46)

In the formula [3], Z ¹ is a group of a structure selected from the following formulas [3a] to [3j].

(47)

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ each represent a hydrogen atom or a methyl group, and may be the same or different.

Among the structures represented by the formula [3], which is the specific tetracarboxylic acid component, Z ¹ is preferably a tetracarboxylic acid component represented by the formula [3a], the formula [3c], and the formula [3b], from the viewpoints of ease of synthesis and ease of polymerization reaction in the production of the polymer. The structure represented by the formula [3d], the formula [3e], the formula [3f] or the formula [3g] is preferable. More preferred is the structure represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g]. Particularly preferred are the formula [3e], the formula [3f] or the formula [3g].

The specific tetracarboxylic acid component is preferably at least 1 mol% of the total tetracarboxylic acid component. More preferably, it is at least 5 mol%, particularly preferably at least 10 mol%. Among them, 15 to 100 mol% is more preferable.

When a specific tetracarboxylic acid component having the structure of the formula [3e], the formula [3f] or the formula [3g] is used, the amount of the tetracarboxylic acid component is preferably 20 mol% or more based on the total amount of the tetracarboxylic acid component . More preferably, it is at least 30 mol%. Further, the tetracarboxylic acid component may all be a tetracarboxylic acid component having the structure of the formula [3e], the formula [3f] or the formula [3g].

In the specific polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used as long as the effect of the present invention is not impaired.

Examples of the other tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds .

That is, other tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,6- Naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2- 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'-diphenylsulfonetetracarboxylic acid, , 10-perylene tetracarboxylic acid or 1,3-diep Nyl-1, 2,3,4-cyclobutane tetracarboxylic acid.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component can be suitably selected depending on the solubility of the specific polymer of the present invention in a solvent, the application property of the liquid crystal alignment treatment agent, the orientation of the liquid crystal in the case of a liquid crystal alignment film, Depending on the characteristics of charge, etc., one kind or two or more kinds may be mixed and used.

&Lt; Process for producing specific polymer &

The method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid 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. Specifically, there are the following methods.

(1) A method of polycondensation of a tetracarboxylic acid dianhydride and a primary or secondary diamine compound to obtain a polyamic acid.

(2) A method of obtaining a polyamic acid by dehydration polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound.

(3) A method of polycondensation of a tetracarboxylic acid dihalide with a primary or secondary diamine compound to obtain a polyamic acid.

In order to obtain a polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid in which a carboxylic acid group is dialkyl esterified with a primary or secondary diamine compound, a method in which a carboxylic acid group is dialkyl esterified and a tetracarboxylic acid dihalide And a primary or secondary diamine compound, or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain the polyimide, a method of converting the polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent containing a diamine component and a tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples of the organic solvent used in the reaction are shown below, but the present invention is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-imidazolidinone.

When the solvent solubility of the polyimide precursor is high, it is preferable to use methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D- D-3] can be used.

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(D ¹ is an alkyl group having 1 to 3 carbon atoms, D ² is an alkyl group having 1 to 3 carbon atoms, and D ³ is an alkyl group having 1 to 4 carbon atoms)

These may be used alone or in combination. In addition, a solvent that does not dissolve the polyimide precursor may be used in combination with the solvent insofar as the resultant polyimide precursor does not precipitate. In addition, the moisture in the organic solvent inhibits the polymerization reaction and, furthermore, causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, the following method may be used, but any method may be used.

(1) a method in which a solution obtained by dispersing or dissolving a diamine component in an organic solvent is stirred to add the tetracarboxylic acid component as it is or after dispersed or dissolved in an organic solvent.

(2) In contrast, a method in which a diamine component is added to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent.

(3) A method of alternately adding a diamine component and a tetracarboxylic acid component.

When a plurality of diamine components or tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a preliminarily mixed state. Alternatively, the reaction may be carried out individually or sequentially, and the low molecular weight compounds reacted individually may be mixed and reacted You can. The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a 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 total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the conventional 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 ring closure of the above polyimide precursor. In this polyimide, the closed rate (also referred to as imidization rate) of the amide acid group does not necessarily have to be 100% Can be adjusted arbitrarily.

Examples of the method for imidizing the polyimide precursor include a heat imidization for directly heating the solution of the polyimide precursor or a 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 the polyimide precursor solution 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. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When recovering the resulting polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be introduced into a solvent and precipitated. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent, and the operation of re-precipitation 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 improved, which is preferable.

The molecular weight of the specific polymer is preferably 5,000 to 1,000,000 in terms of weight average molecular weight measured by gel permeation chromatography (GPC) in consideration of the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of forming the liquid crystal alignment film, And more preferably from 10,000 to 150,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and is a coating solution for forming a liquid crystal alignment film containing a specific compound, a specific polymer and a solvent.

The content of the specific compound in the liquid crystal alignment treatment agent is 0.1 to 30 parts by mass based on 100 parts by mass of the specific polymer. Among them, the amount is preferably 0.5 to 30 parts by mass, particularly preferably 1 to 20 parts by mass.

All the polymer components in the liquid crystal alignment treatment agent may be all the specific polymers of the present invention, or may be mixed with other polymers. At that time, the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the specific polymer of the present invention. Examples of the other polymer include a polyimide polymer not using the diamine compound represented by the formula [2] and the specific tetracarboxylic acid component. Further, examples of the other polymer include cellulose polymer, acrylic polymer, methacrylic polymer, polystyrene, polyamide, polysiloxane, and the like.

The content of the solvent in the liquid crystal alignment treatment agent is preferably 70 to 99.9 mass%, more preferably 80 to 99 mass%, from the viewpoint that a solvent in the liquid crystal alignment treatment agent forms a uniform liquid crystal alignment film by coating. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film.

The solvent used in the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent (also referred to as a good solvent) for dissolving a specific compound and a specific polymer. Specific examples of the two solvents are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. Further, when the solubility of the specific compound and the specific polymer in the solvent is high, it is preferable to use the solvent represented by the formula [D-1] to [D-3].

It is preferable that the both solvents in the liquid crystal alignment treatment agent are 10 to 100% by mass of the total solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferable. More preferred is 30 to 80 mass%.

As the liquid crystal alignment treatment agent, a solvent (also referred to as a poor solvent) for improving the film property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied may be used as long as the effect of the present invention is not impaired. Specific examples of the poor solvent include, but are not limited to, the following examples.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl Propylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- , Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol mono Ethylene glycol monoacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethyleneglycol monomethyl ether, triethyleneglycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, Propylene glycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, butylpropyleneglycol monoethylether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3-methoxypropyl D-1] to [D-3], and the like can be given, for example, as a solvent, such as methyl ethyl lactate, methyl lactate methyl lactate, ethyl lactate lactate, n-propyl lactate, n-butyl lactate, have.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, It is preferable to use a solvent represented by the formula [D-3].

These poor solvents are preferably 1 to 70% by mass of the total solvent contained in the liquid crystal alignment treatment agent. In particular, it is preferably 1 to 60% by mass. And more preferably 5 to 60% by mass.

As long as the effect of the present invention is not impaired, the liquid crystal alignment treatment agent may contain at least one selected from the group consisting of a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group , And further compounds having a polymerizable unsaturated bond (collectively referred to as a crosslinkable compound) may also be introduced. These substituent groups and polymerizable unsaturated bonds need to have two or more in the crosslinkable compound.

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- Phenoxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxy) phenyl) -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].

(49)

Specific examples thereof include crosslinkable compounds represented by the formulas [4a] to [4k] shown on pages 58 to 59 of International Publication No. WO2011 / 132751 (published on October 22, 2011).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

(50)

Specific examples thereof include crosslinkable compounds represented by the formulas [5-1] to [5-42] listed on pages 76 to 82 of International Publication WO2012 / 014898 (published on February 22, 2012).

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. These groups preferably have 3 to 6 on average of methylol groups or alkoxymethyl groups per one triazine ring.

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.) or methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 , 254 and the like, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, and methoxymethylated ethoxymethylated melamines such as Cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as benzoguanamine, Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, And anamine (manufactured by Mitsui Cyanamid Co., Ltd.). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluryl such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174, and the like.

Examples of the benzene or phenolic compound having a hydroxyl group or alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48] listed on pages 62 to 66 of WO2011 / 132751 (published on October 27, 2011) can be mentioned.

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, hydroxypivalic acid di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid neopentyl glycol di 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- A crosslinkable compound having one polymerizable unsaturated group such as ester or N-methylol (meth) acrylamide in the molecule; And the like.

The compound represented by the following formula [7] may also be used.

(51)

(E ₁ has to have a cyclohexane ring, a non-cyclohexane ring, represents a group selected from a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene group consisting of a ring, anthracene ring and phenanthrene ring, E ₂ (7a) and (7b), and n represents an integer of 1 to 4,

(52)

The compound is an example of a crosslinking compound, but is not limited thereto. The crosslinkable compound used 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 is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components, in order for the crosslinking reaction to proceed to exhibit the intended effect.

As long as the effect of the present invention is not impaired, the liquid crystal alignment treatment agent can use a compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness when the liquid crystal alignment treatment agent is applied.

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

More specifically, for example, EF Top 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 (Trade names, manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants 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 all the polymer components contained in the liquid crystal alignment treatment agent.

The liquid crystal alignment treatment agent includes a compound represented by the formula [M1] shown on pages 69 to 73 of WO2011 / 132751 (published on October 22, 2011) as a compound which promotes charge transfer in the liquid crystal alignment film to promote charge- A nitrogen-containing heterocyclic amine compound represented by the formula [M156] may also be added. The amine compound may be directly added to the liquid crystal alignment treatment agent, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent to be used is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer.

The liquid crystal alignment treatment agent may contain, in addition to a compound that improves the uniformity of film thickness or surface smoothness of the poor solvent, the crosslinkable compound, the resinous coating or the liquid crystal alignment film, and the compound that accelerates charge dropout, , A dielectric material or a conductive material may be added for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

<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. In the case of the 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 simplification of 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 element, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side, and 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 screen printing, offset printing, flexographic printing, inkjet printing, and the like are generally used industrially. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it is heated at 30 to 300 占 폚, preferably at 30 to 300 占 폚, depending on the solvent used for the liquid crystal alignment treatment agent, by heating means such as a hot plate, a heat circulation type oven and an IR The liquid crystal alignment layer can be formed by evaporating the solvent at a temperature of 30 to 250 ° C. When the thickness of the liquid crystal alignment film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may be deteriorated. 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 fired liquid crystal alignment film is subjected to rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate having a liquid crystal alignment film attached thereto from the liquid crystal alignment treatment agent of the present invention is obtained by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, a pair of substrates having a liquid crystal alignment film formed thereon is prepared, a spacer is scattered on the liquid crystal alignment film of the substrate of one substrate, and the substrates of the other substrate are bonded A method in which a liquid crystal is injected under reduced pressure and sealed, 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 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 polymerizable by at least one of active energy rays and heat between a pair of substrates And a liquid crystal display device produced by polymerizing a polymerizable compound by irradiation of an active energy ray and heating, while applying a voltage between electrodes. Here, as the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

The above liquid crystal display element controls the pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed into a liquid crystal material, and a liquid crystal cell is assembled. Then, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt angle of the liquid crystal molecules by the produced polymer. That is, 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. The PSA system is suitable for forming a vertically aligned liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment since no rubbing treatment is required.

The liquid crystal display element of the present invention can be obtained by obtaining a substrate on which a liquid crystal alignment film is adhered from a liquid crystal alignment treatment agent by the above-mentioned technique, preparing a liquid crystal cell, and polymerizing the polymerizable compound by at least one of irradiation with ultraviolet rays and heating , 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 the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which the liquid crystal is injected under reduced pressure and sealed, a method in which a liquid crystal is dropped on the liquid crystal alignment film surface on which the 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 compounds having at least one polymerizable unsaturated group such as an acrylate group and 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 is larger than 10 parts by mass, the number of unreacted polymerizable compounds increases, .

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 which is polymerized by at least one of active energy rays and heat between the pair of substrates And a liquid crystal display device manufactured by a process of applying a voltage between the electrodes. Here, as the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group which polymerizes in at least one of an active energy ray and a 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 .

Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that 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.

The liquid crystal cell having the liquid crystal alignment layer containing such a polymerizable group and the alignment of the liquid crystal molecules after the production of the liquid crystal cell are controlled in the same manner as the above-described liquid crystal cell of the PSA system.

The liquid crystal display element having a liquid crystal alignment film produced 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 screen 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 to these examples.

&Quot; Abbreviations of the compounds used in Synthesis Examples, Examples and Comparative Examples &quot;

<Specific compound>

P1: a compound represented by the following formula [P1]

P2: a compound represented by the following formula [P2]

P3: a compound represented by the following formula [P3]

(53)

&Lt; Monomer for producing polyimide polymer (specific polymer) >

(Specific diamine compound)

A1: 3,5-diaminobenzoic acid

A2: A diamine compound represented by the following formula [A2]

A3: 1,3-Diamino-4-octadecyloxybenzene

A4: 1,3-Diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

A5: 1,3-Diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl]

A6: 1,3-Diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

A7: A diamine compound represented by the following formula [A7]

(54)

(55)

(56)

(Other diamine compounds)

B1: p-phenylenediamine

B2: m-phenylenediamine

(57)

(Specific tetracarboxylic acid component)

C1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

C2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

C3: tetracarboxylic acid dianhydride represented by the following formula [C3]

C4: tetracarboxylic acid dianhydride represented by the following formula [C4]

(58)

<Solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

ECS: ethylene glycol monoethyl ether

EC: diethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

&Quot; Method for measuring molecular weight of polyimide polymer &quot;

The molecular weights of the polyimide precursor and polyimide were 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 as follows.

Column temperature: 50 ° C

Eluent: 30 mmol / l (liter) of lithium bromide-hydrate (LiBr 占₂ 2O) and 30 mmol / l (phosphoric acid anhydride crystal) , Tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard samples for preparing calibration curves: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000 manufactured by Polymer Laboratories).

&Quot; Method for measuring imidization rate of polyimide &quot;

(DMSO-d6, 0.05 mass% TMS (tetramethylsilane)) mixture was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, Product) (0.53 ml) was added, and completely dissolved by ultrasonic wave. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Denshoku Co., Ltd.). A proton originating from a structure which does not change before and after imidization is 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 when the polyamide acid (imidization ratio is 0% The ratio of the number of reference protons to one protopertone.

&Lt; Synthesis Example 1 &

The mixture of C1 (3.45 g, 17.6 mmol), A2 (0.73 g, 3.57 mmol) and B1 (1.54 g, 14.3 mmol) were mixed in NMP (17.2 g) and reacted at 40 ° C for 8 hours to obtain resin solid concentration To obtain a 25 mass% polyamic acid solution (1). The polyamic acid had a number average molecular weight of 26,600 and a weight average molecular weight of 85,200.

&Lt; Synthesis Example 2 &

C2 (3.83 g, 15.3 mmol), A2 (0.93 g, 4.59 mmol) and B2 (2.81 g, 26.0 mmol) were mixed in NEP (21.0 g) and reacted at 50 ° C for 2 hours. Thereafter, C1 (2.91 g, 14.8 mmol) and NEP (10.5 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. This polyamic acid had a number average molecular weight of 24,500 and a weight average molecular weight of 71,100.

&Lt; Synthesis Example 3 &

To polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2, NEP was added and diluted to 6% by mass, acetic anhydride (3.95 g) and pyridine (2.45 g) were added as an imidation catalyst, The reaction was carried out at 70 ° C for 3 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (3). The imidization ratio of the polyimide was 70%, the number average molecular weight was 22,100, and the weight average molecular weight was 60,100.

&Lt; Synthesis Example 4 &

(4.47 g, 17.9 mmol), A1 (1.95 g, 12.8 mmol) and A4 (4.85 g, 12.8 mmol) were mixed in NEP (25.4 g) and reacted at 80 ° C for 5 hours. Thereafter, C1 (1.43 g, 7.30 mmol) and NEP (12.7 g) were added and reacted at 40 占 폚 for 8 hours to obtain a polyamic acid solution (4) having a resin solid content concentration of 25 mass%. The polyamic acid had a number average molecular weight of 23,500 and a weight average molecular weight of 68,600.

&Lt; Synthesis Example 5 &

NEP was added to the polyamic acid solution (4) (4) (4) obtained in Synthesis Example 4 to dilute to 6 mass%, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as an imidation catalyst, The reaction was carried out at 70 DEG C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained 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 (5). The imidization ratio of the polyimide was 61%, the number average molecular weight was 19,900, and the weight average molecular weight was 57,100.

&Lt; Synthesis Example 6 &

A mixture of C2 (5.10 g, 20.4 mmol), A1 (1.94 g, 12.8 mmol), A2 (0.52 g, 2.55 mmol) and A5 (4.02 g, 10.2 mmol) in NMP (25.0 g) Lt; 0 &gt; C for 5 hours. Thereafter, C1 (0.93 g, 4.80 mmol) and NMP (12.5 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

To the resulting polyamic acid solution (30.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.54 g) and pyridine (3.33 g) were added as an imidation catalyst and reacted at 80 ° C for 3.5 hours . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of the polyimide was 85%, the number average molecular weight was 16,800, and the weight average molecular weight was 50,100.

&Lt; Synthesis Example 7 &

A mixture of C2 (2.42 g, 9.69 mmol), Al (2.58 g, 17.0 mmol) and A6 (3.14 g, 7.27 mmol) in NEP (21.9 g) 2.79 g, 14.2 mmol) and NEP (10.9 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NEP was added to the resulting polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.40 g) and pyridine (3.25 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 81%, the number average molecular weight was 17,400, and the weight average molecular weight was 52,800.

&Lt; Synthesis Example 8 &

C2 (4.32 g, 17.3 mmol), A1 (3.00 g, 19.7 mmol) and A7 (2.43 g, 4.93 mmol) were mixed in NMP (22.2 g) and reacted at 80 ° C for 5 hours. Thereafter, C1 (1.37 g, 7.00 mmol) and NMP (11.1 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resulting polyamidic acid solution (30.5 g) to dilute to 6 mass%, acetic anhydride (3.90 g) and pyridine (2.55 g) were added as imidation catalysts and reacted at 60 ° C for 3 hours . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The polyimide had an imidization rate of 53%, a number average molecular weight of 16,500 and a weight average molecular weight of 51,800.

&Lt; Synthesis Example 9 &

A mixture of C3 (5.40 g, 24.1 mmol), A1 (2.43 g, 15.9 mmol), A2 (0.50 g, 2.45 mmol) and A7 (3.02 g, 6.13 mmol) in NMP (34.1 g) C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.05 g) and pyridine (2.50 g) were added as an imidization catalyst and reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 55%, the number average molecular weight was 16,100, and the weight average molecular weight was 48,100.

&Lt; Synthesis Example 10 &

A mixture of C3 (5.38 g, 24.0 mmol), A1 (2.22 g, 14.6 mmol) and A5 (3.84 g, 9.72 mmol) in NMP (34.3 g) Of 25% by mass was obtained.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as imidation catalysts and reacted at 70 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained 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 (10). The imidization ratio of the polyimide was 61%, the number average molecular weight was 17,300, and the weight average molecular weight was 51,100.

&Lt; Synthesis Example 11 &

C4 (3.48 g, 11.6 mmol), A1 (1.06 g, 6.95 mmol), A2 (0.94 g, 4.63 mmol) and A3 (4.36 g, 11.6 mmol) were mixed in NEP (24.1 g) Lt; 0 &gt; C for 6 hours. Thereafter, C1 (2.20 g, 11.2 mmol) and NEP (12.0 g) were added and reacted at 25 占 폚 for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (7.20 g) and pyridine (2.30 g) were added as imidation catalysts and reacted at 40 ° C for 1.5 hours . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (11). The imidization ratio of the polyimide was 70%, the number average molecular weight was 17,500, and the weight average molecular weight was 40,100.

The polyimide-based polymers are summarized in Table 1.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

The liquid crystal alignment treatment agent was pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉 to evaluate the inkjet application property. For the ink-jet applicator, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was carried out on an ITO (indium tin oxide) -evaporated substrate cleaned with pure water and IPA (isopropyl alcohol) with a coating area of 70 x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 Mm / sec, the time from application to drying was 60 seconds, and drying was carried out on a hot plate at 70 DEG C for 5 minutes.

The film-like property of the obtained substrate on which the liquid crystal alignment film was adhered was confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence of pinholes. As a result, in the liquid crystal alignment film obtained in all the examples, no pinhole was observed on the coating film, and a liquid crystal alignment film excellent in coating film property was obtained.

Evaluation of display non-uniformity characteristics in the vicinity of a frame of a liquid crystal cell after high-temperature, high-humidity storage (normal cell) &quot;

The liquid crystal alignment treatment agent was pressure filtered through a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell (ordinary cell). This solution was spin-coated on an ITO surface of a substrate (100 mm long × 100 mm wide, 0.7 mm thick) with a 100 × 100 mm ITO electrode cleaned with pure water and IPA, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained by performing heat treatment at 230 DEG C for 30 minutes in a thermocycling type clean oven. The coated surface of the ITO substrate was subjected to rubbing treatment under the condition that the number of roll revolutions was 1000 rpm, the roll advancing speed was 50 mm / sec, and the amount of indentation was 0.1 mm using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm.

Two pieces of the ITO substrates with the obtained liquid crystal alignment films were prepared, and spacers having a size of 6 mu m were dispersed on the liquid crystal alignment film surface of the substrate on which the one liquid crystal alignment film was adhered. Thereafter, an ultraviolet curable sealant was drawn around the substrate, and liquid crystal was injected by an ODF (One Drop Filling) method to obtain a liquid crystal cell. Thereafter, in order to cure the ultraviolet curable sealant, a wavelength of 310 nm or less was cut into the liquid crystal cell using a metal halide lamp having an illuminance of 60 mW, ultraviolet rays of 5 J / cm 2 in terms of 365 nm were irradiated Respectively. Thereafter, heat treatment was performed in a heat-cycling type clean oven at 120 DEG C for 60 minutes to obtain a liquid crystal cell (ordinary cell).

The liquid crystal cells using the liquid crystal alignment treatment agents (1) to (3) obtained in Examples 1 to 3 and the liquid crystal alignment treatment agents (21) to (22) obtained in Comparative Examples 1 and 2 were each supplied with nematic liquid crystal MLC-2003) (manufactured by Merck Japan) was used.

The liquid crystal alignment treatment agents (4) to (6) obtained in Examples 4 to 6, the liquid crystal alignment treatment agent (8) obtained in Example 8, the liquid crystal alignment treatment agent (9) obtained in Example 9, The obtained liquid crystal alignment treatment agents (11) to (15), the liquid crystal alignment treatment agents (17) to (20) obtained in Examples 17 to 20 and the liquid crystal alignment treatment agents (23) to (24) obtained in Comparative Examples 3 and 4 For the liquid crystal cell, nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was used as a liquid crystal.

The obtained liquid crystal cell (ordinary cell) was subjected to evaluation of the liquid crystal alignability near the sealant using a polarizing plate and a backlight and visually observed, and as a result, uniform liquid crystal alignability was exhibited in all of the liquid crystal cells obtained in Examples and Comparative Examples.

Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity bath having a temperature of 80 캜 and a humidity of 90% RH for 36 hours, and the liquid crystal alignability in the vicinity of the sealing agent was evaluated under the same conditions as above. Specifically, the more the disturbance of liquid crystal alignability is not observed in the vicinity of the sealant, the better the evaluation is.

In Table 5 to Table 7, those in which no disturbance of liquid crystal alignability was observed were indicated as &quot; &quot;, and those in which disturbance in liquid crystal alignability was seen as &quot; x &quot;.

&Quot; Evaluation of voltage holding ratio after storage at high temperature and high humidity (normal cell) &quot;

The liquid crystal alignment treatment agent was pressure filtered through a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell (ordinary cell). This solution was spin-coated on an ITO surface of a substrate (40 mm long × 30 mm wide, 0.7 mm thick) with a 30 × 40 mm ITO electrode cleaned with pure water and IPA, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained by performing heat treatment at 230 DEG C for 30 minutes in a thermocycling type clean oven. The coated surface of the ITO substrate was subjected to rubbing treatment under the condition that the number of roll revolutions was 1000 rpm, the roll advancing speed was 50 mm / sec, and the amount of indentation was 0.1 mm using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm.

Two sheets of the ITO substrates to which the obtained liquid crystal alignment films were adhered were prepared, and the liquid crystal alignment film faces were inwardly put together with spacers of 6 mu m interposed therebetween to print an ultraviolet curable sealant. Subsequently, the other substrate and the liquid crystal alignment film were faced with each other facing each other, and then a process for curing the ultraviolet curable sealant was performed to obtain an empty cell. Specifically, a wavelength of 310 nm or less was cut using a metal halide lamp having an illuminance of 60 mW, irradiated with ultraviolet rays of 5 J / cm 2 in terms of 365 nm, and then irradiated at 120 ° C Heat treatment was performed for 60 minutes to obtain empty cells. A liquid crystal was injected into the empty cell by a low pressure injection method and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

The liquid crystal used in the production of the liquid crystal cell of each of the examples and the comparative example was the same as that of the evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage.

A voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 80 占 폚 for 60 占 퐏 and a voltage was measured after 50 占 하여 to calculate the voltage holding ratio (also referred to as VHR). The measurement was carried out by setting the voltage: ± 1 V, the pulse width: 60 μs, and the flame period: 50 ms using a voltage sustaining rate measuring apparatus (VHR-1) (manufactured by Toyota Corporation).

The liquid crystal cell in which the voltage holding ratio was measured was stored in a high-temperature and high-humidity bath having a temperature of 80 캜 and a humidity of 90% RH for 48 hours, and then the voltage holding ratio was measured under the same conditions as above.

The evaluation was made such that the decrease in the value of the voltage holding ratio after storage in the high temperature and high humidity bath was smaller with respect to the voltage holding ratio immediately after the liquid crystal cell was manufactured (Tables 5 to 7).

&Quot; Production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) &quot;

The liquid crystal alignment treatment agent was pressure-filtered with a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell and evaluate the liquid crystal alignment property (PSA cell). This solution was immersed in a substrate (40 mm long × 30 mm wide, 0.7 mm thick) on which ITO electrodes with a pattern interval of 20 μm were attached (10 × 10 mm) centered on pure water and IPA and a 10 × 40 mm ITO The ITO surface of the substrate (40 mm long x 30 mm wide, 0.7 mm thick) on which the electrode was attached was spin-coated, and the substrate was heat-treated on a hot plate at 100 DEG C for 5 minutes and at a temperature of 230 DEG C for 30 minutes in a heat- A polyimide coating film having a film thickness of 100 nm was obtained.

The substrate to which the liquid crystal alignment film was adhered was placed in a space of 6 mu m with the liquid crystal alignment film face inward, and bonded together with a sealant to prepare an empty cell. The polymeric compound (1) represented by the following formula was mixed in a vacuum of 0.3% by mass with respect to 100% by mass of a nematic liquid crystal (MLC-6608, manufactured by Merck Japan) And the injection port was sealed to obtain a liquid crystal cell.

[Chemical Formula 59]

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

The response speeds of the liquid crystal cell before and after ultraviolet irradiation were measured. The response speed was measured from T90 to T10 from a transmittance of 90% to a transmittance of 10%.

It was confirmed that the PSA cell obtained in the Examples had a higher response speed of the liquid crystal cell after ultraviolet irradiation than in the liquid crystal cell before the ultraviolet irradiation, and thus the alignment direction of the liquid crystal was controlled. In all of the liquid crystal cells, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (Nikon Corporation) that the liquid crystal was uniformly oriented.

&Lt; Example 1 >

NMP (19.9 g) and BCS (11.8 g) were added to polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 1 and stirred at 25 占 폚 for 2 hours. Then, P2 (0.25 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent .

&Lt; Example 2 >

NEP (18.9 g) and PB (14.4 g) were added to polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 hours. Then, P2 (0.18 g) was added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal orientation treating agent (2). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature, high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 2 .

&Lt; Example 3 >

NEP (17.0 g) and PB (7.30 g) were added to the polyimide powder (3) (1.55 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P2 (0.11 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were carried out using the obtained liquid crystal alignment treatment agent 3 .

<Example 4>

NEP (19.8 g) and PB (15.1 g) were added to polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4 and stirred at 25 占 폚 for 2 hours. Thereafter, P2 (0.19 g) was added and stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) were performed using the obtained liquid crystal alignment treatment agent 4 .

&Lt; Example 5 >

NEP (17.6 g), EC (4.30 g) and PB (12.9 g) were added to polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4, Lt; / RTI &gt; Thereafter, P1 (0.41 g) was added and stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; .

&Lt; Example 6 >

NEP (15.3 g) and PB (8.20 g) were added to the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P2 (0.11 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "(evaluation of voltage holding ratio after normal high-humidity storage (normal cell) (PSA cell) &quot;.

&Lt; Example 7 >

NEP (23.1 g) and PB (12.4 g) were added to the polyimide powder (5) (1.10 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P2 (0.077 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (7), &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

&Lt; Example 8 >

NMP (13.4 g), EC (2.40 g) and BCS (8.50 g) were added to the polyimide powder (5) (1.55 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P3 (0.23 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; .

&Lt; Example 9 >

NEP (15.5 g) and PB (8.30 g) were added to the polyimide powder (6) (1.52 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P1 (0.26 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage "," evaluation of the voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 10 >

NEP (22.1 g) and PB (11.9 g) were added to the polyimide powder (6) (1.05 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. Thereafter, P1 (0.18 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 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 solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 10, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

&Lt; Example 11 >

NEP (9.40 g),? -BL (4.70 g) and BCS (9.40 g) were added to the polyimide powder (7) (1.50 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P2 (0.075 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent 11. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 11 .

&Lt; Example 12 >

NMP (14.1 g), ECS (2.40 g) and BCS (7.10 g) were added to the polyimide powder (7) (1.50 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, P1 (0.075 g) and P2 (0.15 g) were added to this solution and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were carried out using the obtained liquid crystal alignment treatment agent 12 .

&Lt; Example 13 >

NEP (15.5 g) and PB (8.30 g) were added to the polyimide powder (8) (1.52 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. Thereafter, P2 (0.15 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage "," evaluation of the voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 14 >

NEP (15.3 g) and PB (8.20 g) were added to the polyimide powder (8) (1.50 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. Thereafter, P1 (0.045 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 14. [ No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) &quot; .

&Lt; Example 15 >

NEP (11.8 g),? -BL (2.40 g) and PB (9.40 g) were added to the polyimide powder (9) (1.50 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P3 (0.15 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 15. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) were performed using the obtained liquid crystal alignment treatment agent 15 .

&Lt; Example 16 >

NEP (16.2 g),? -BL (3.20 g) and PB (12.9 g) were added to the polyimide powder (9) (1.00 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C for 24 hours. Then, P3 (0.10 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 16. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 16, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

&Lt; Example 17 >

NMP (15.8 g) and PB (8.50 g) were added to the polyimide powder (10) (1.55 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, P1 (0.23 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 17. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) were performed using the obtained liquid crystal alignment treatment agent 17 .

&Lt; Example 18 >

NEP (15.8 g) and PB (8.50 g) were added to the polyimide powder (10) (1.55 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, P1 (0.11 g) and P2 (0.11 g) were added to this solution and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 18. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "," evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 19 >

Γ-BL (12.9 g), EC (2.40 g) and BCS (8.20 g) were added to the polyimide powder (11) (1.50 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 ° C. for 24 hours. Then, P3 (0.15 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 19. [ No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after normal high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 19 .

&Lt; Example 20 >

NMP (14.1 g), ECS (2.40 g) and BCS (7.10 g) were added to the polyimide powder (11) (1.50 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, P1 (0.075 g) and P2 (0.075 g) were added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent 20. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) were performed using the obtained liquid crystal alignment treatment agent 20 .

&Lt; Comparative Example 1 &

NEP (18.9 g) and PB (14.4 g) were added to polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 hours, A treating agent 21 was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) near the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature, high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 21 .

&Lt; Comparative Example 2 &

NEP (17.0 g) and PB (7.30 g) were added to the polyimide powder (3) (1.55 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 캜 for 24 hours to obtain a liquid crystal alignment treatment agent 22 . No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) were performed using the obtained liquid crystal alignment treatment agent 22 .

&Lt; Comparative Example 3 &

NEP (19.8 g) and PB (15.1 g) were added to polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4 and stirred at 25 캜 for 2 hours, A treating agent 23 was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) near the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 23 .

&Lt; Comparative Example 4 &

NEP (15.3 g) and PB (8.20 g) were added to the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 캜 for 24 hours to obtain a liquid crystal alignment treating agent 24 . No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 24 .

As can be seen from the above results, the liquid crystal alignment treatment agent of the examples showed better stability than the liquid crystal alignment treatment agent of the comparative example in that the liquid crystal alignment property near the sealant of the liquid crystal cell was not disturbed even when the liquid crystal cell was stored for a long time in a high- A liquid crystal alignment film was obtained. Further, even when the liquid crystal cell is stored for a long time in a high-temperature and high-humidity bath, a liquid crystal alignment film capable of suppressing a decrease in the voltage holding ratio can be obtained. That is, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment film capable of suppressing occurrence of display irregularities near the frame of the liquid crystal display element and lowering of the voltage holding ratio under high temperature and high humidity conditions.

Specifically, it is a comparison of Example 2 and Comparative Example 1, Example 3 and Comparative Example 2, Example 4 and Comparative Example 3, and Example 6 and Comparative Example 4, and the same Example (B) This is a comparison with a comparative example using a specific polymer and not containing a specific compound as the component (A). In the case of using the liquid crystal alignment treatment agent of the comparative example, when the liquid crystal cell was stored for a long period of time in a high-temperature and high-humidity bath, disturbance of liquid crystal orientation occurred near the sealant of the liquid crystal cell and the voltage retention rate was greatly lowered.

Industrial availability

The liquid crystal display element having a liquid crystal alignment film formed by using the liquid crystal alignment treatment agent of the present invention can be preferably used for a liquid crystal display which is excellent in reliability and is large in size and is large in size and is suitably used for a TN device, And is useful as a vertically aligned liquid crystal display element.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-96470, filed on May 1, 2013, are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims (14)

A liquid crystal alignment treatment agent characterized by containing 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 obtained by reacting a diamine component and a tetracarboxylic acid component.
[Chemical Formula 1]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring and X ² represents a group represented by the following formulas [ Represents a structure selected from the formula [1-5]
(2)

(W &lt; ¹ &gt; represents a hydrogen atom or a benzene ring) The method according to claim 1,
Wherein X ^{1 in} the formula [1] is an alkylene group having 1 to 10 carbon atoms. 3. The method according to claim 1 or 2,
Wherein the X ² of the formula [1] is a structure selected from the formulas [1-1], [1-2] and [1-4]. 4. The method according to any one of claims 1 to 3,
Wherein the diamine component in the polymer of the component (B) contains at least one diamine compound having a structure represented by the following formula [2].
(3)

(Y represents a substituent of a structure selected from the following formulas [2-1] to [2-6], and m represents an integer of 1 to 4)
[Chemical Formula 4]

(a represents an integer of 0 to 4, and b represents an integer of 0 to 4).
Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-, Y ² represents 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), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 and having a steroid skeleton, Any hydrogen atom on the cyclic group may be substituted with 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a substituent, 3 alkyl group, carbon atoms and may be substituted with one to three of an alkoxy group, fluorine-containing alkyl group, fluorine-containing C 1 -C 3 alkoxy group or a fluorine atom of 1 to 3 carbon atoms, n is an integer of 0 ~ 4, Y ⁶ Represents 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 fluoro-containing alkoxyl group having 1 to 18 carbon atoms,
Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.
Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group of 1 to 12 carbon atoms and Y ¹¹ represents an alkyl group of 1 to 5 carbon atoms. 5. The method according to any one of claims 1 to 4,
A liquid crystal alignment treatment agent containing a compound represented by the following formula [3] in a tetracarboxylic acid component in the polymer of the component (B).
[Chemical Formula 5]

(Z &lt; ¹ &gt; is a group of a structure selected from the following formulas [3a] to [3j]
[Chemical Formula 6]

(Wherein Z ² to Z ^{5 each} represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring and may be the same or different, and Z ⁶ and Z ⁷ each represent a hydrogen atom or a methyl group, 6. The method according to any one of claims 1 to 5,
Wherein the polymer of component (B) is a polyimide obtained by dehydrating and ring closure of polyamic acid. 7. The method according to any one of claims 1 to 6,
Wherein the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (B). A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 7. A liquid crystal alignment film obtained by the ink jet method using the liquid crystal alignment treatment agent according to any one of claims 1 to 7. A liquid crystal display element having the liquid crystal alignment film according to claim 8 or 9. 10. The method according to claim 8 or 9,
A liquid crystal composition having 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, A liquid crystal alignment film used in a liquid crystal display device produced by polymerizing the polymerizable compound while applying a voltage. A liquid crystal display element having the liquid crystal alignment film according to claim 11. 10. The method according to claim 8 or 9,
A liquid crystal alignment film having 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 then polymerizing the polymerizable group while applying the polymerizable group to the liquid crystal alignment layer. A liquid crystal display element having the liquid crystal alignment film according to claim 13.