KR20190125992A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent in which a liquid crystal aligning film is obtained in which the ability to align the liquid crystals vertically even when exposed to excessive heating is obtained, and even when any foreign matter comes into contact with the film, scratches occur. It provides the liquid crystal aligning agent from which the liquid crystal aligning film which does not fall the ability to orientate vertically is obtained.
The invention, of the diamine (formula (1) represented by the formula (1), X represents a divalent group, such as a single bond or -O-, Y represents a group represented by the formula [1-1]. Y ¹ ~ Y ⁶ represents a specific group described in the specification), and a liquid crystal alignment containing at least one polymer selected from a polyimide precursor which is a reactant with a tetracarboxylic acid component and a polyimide thereof. Offer

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

This invention relates to the liquid crystal aligning agent, the liquid crystal aligning film, and the liquid crystal display element which were excellent in the ability to orientate a liquid crystal perpendicularly.

The process of irradiating an ultraviolet-ray, applying a voltage to liquid crystal molecules in the manufacturing process in the liquid crystal display element of the system (also called a vertical orientation (VA) system) which makes a liquid crystal molecule orientate perpendicular to a board | substrate respond with an electric field. There is to include.

In the liquid crystal display element of such a vertical alignment system, a photopolymerizable compound is previously added to a liquid crystal composition, and also the response of a liquid crystal is made by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal cell using a vertical alignment film, such as a polyimide-type, etc. The technique which speeds up speed (PSA (Polymer Sustained Alignment) system element, for example, refer patent document 1 and nonpatent literature 1) is known.

As a liquid crystal aligning agent used for such a PSA system element, the liquid crystal aligning agent using the side chain which has a specific ring structure is proposed (refer patent document 2). This specific ring structure had high ability to orientate a liquid crystal vertically, and the liquid crystal display element of the vertical alignment system using this liquid crystal aligning agent was favorable in display characteristics.

Japanese Laid-Open Patent Publication 2003-307720 WO2006 / 070819

 K. Hanaoka, SID 04 DIGEST, P.1200-1202

However, in the recent liquid crystal display elements of the vertical alignment system, due to the influence of thinning and increasing the size of the substrate to be used, a temperature difference occurs between different portions in the same substrate at the time of firing, and the liquid crystal alignment film of the excessively heated portion is a liquid crystal. The ability to orientate vertically falls, and as a result, the problem which a liquid crystal display element obtained causes partial display defects arises.

Moreover, also in a liquid crystal panel manufacturing process, when a liquid crystal aligning film and a column spacer contact and a flaw generate | occur | produces in a liquid crystal aligning film, it is also a problem that an orientation defect (bright point) arises in the part.

This invention provides the liquid crystal aligning agent from which the liquid crystal aligning film which does not fall even if the ability to orientate a liquid crystal perpendicularly even when exposed to excessive heating is provided.

Moreover, even when a foreign material contacts a film | membrane and a flaw generate | occur | produces, it is providing the liquid crystal aligning agent from which the liquid crystal aligning film which does not fall the ability to orientate a liquid crystal perpendicularly | vertically is obtained.

The inventors found that the object can be achieved by the liquid crystal aligning agent having the following constitution, and completed the present invention.

That is, the structure of this invention is as follows.

1. Liquid crystal aligning containing the diamine component containing the diamine shown by following formula [1], and the at least 1 sort (s) of polymer chosen from the polyimide which is a polyimide precursor which is a reaction material with a tetracarboxylic-acid component, and its imide. My.

[Formula 1]

Formula [1], X is a single _{bond, -O-, -C (CH 3)} 2 -, -NH-, -CO-, -NHCO-, -COO-, - (CH 2) m -, - The divalent organic group which consists of SO <_2> -and these arbitrary combinations is shown, m shows the integer of 1-8.

Y each independently represents the structure of following formula [1-1].

Formula [1-1] in, Y ¹ and Y ³ are, each independently, a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -CH 2 O-, - At least 1 sort (s) chosen from the group which consists of CONH-, -NHCO-, -COO-, and -OCO- is shown.

Y ² represents a single bond or - (CH _{2) b} - represents a (b is an integer of 1 to 15.) (where, Y ¹ or Y ³ is only bond, - (CH _{2) a} - if, Y ² is Y ¹ is at least one member selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and / or Y ³ is- In the case of at least one member selected from the group consisting of O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, Y ² is a single bond or-(CH ₂ ) _b- ( Provided that when Y ¹ is -CONH-, Y ² and Y ³ are a single bond).

Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton; The arbitrary hydrogen atoms of the phase may be substituted with a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom.

Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms. The group, C1-C3 fluorine-containing alkyl group, C1-C3 fluorine-containing alkoxy group, or a fluorine atom may be substituted.

Y <^6> is group which consists of a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, and a C1-C18 fluorine-containing alkoxy group At least 1 sort (s) chosen from is shown. n represents the integer of 0-4.

According to this invention, even when exposed to excessive heating, the liquid crystal aligning agent from which the ability to orientate a liquid crystal perpendicularly | vertically does not fall can be provided.

In addition, the present invention provides a liquid crystal aligning agent in which a liquid crystal aligning film is obtained in which the ability to orient the liquid crystals vertically does not decrease even when any foreign matter contacts the film in addition to the above or in addition to the above effects and a scratch occurs. can do.

Furthermore, by this invention, the method of obtaining a liquid crystal aligning film using the liquid crystal aligning film obtained from the said liquid crystal aligning agent, and the said liquid crystal aligning agent can be provided.

The liquid crystal aligning agent of this invention is a diamine component containing the diamine represented by the said Formula [1] (Hereinafter, "diamine represented by the said Formula [1] may be abbreviated as" specific diamine. "), And tetracarr At least 1 sort (s) of polymer (Hereinafter, it may abbreviate as a "specific polymer") contains from the polyimide precursor which is a reactant with an acidic component, and the polyimide which is an imide.

Although a specific polymer contains specific diamine, you may have diamines other than a specific diamine.

The amount of the specific diamine and the other diamine is such that the amount of the specific diamine in the specific polymer is 5 mol% to 70 mol%, preferably 10 mol% to 50 mol%, and more preferably 10 mol% to 40 mol%. It is preferable to have a specific diamine.

Moreover, the liquid crystal aligning agent of this invention may contain "polyimide which is a polyimide precursor and / or its imide," other than a specific polymer.

Hereinafter, "specific diamine" is described, and then diamines other than "specific diamine" are described.

<Specific diamine>

The specific diamine used for the liquid crystal aligning agent of this invention is shown by following formula [1].

[Formula 2]

Formula [1], X is a single _{bond, -O-, -C (CH 3)} 2 -, -NH-, -CO-, -NHCO-, -COO-, - (CH 2) m -, - The divalent organic group which consists of SO <_2> -and these arbitrary combinations is shown, m shows the integer of 1-8.

"Any combination of them", -O- (CH ₂ ) _m -O-, -OC (CH ₃ ) _2- , -CO- (CH ₂ ) _m- , -NH- (CH ₂ ) _m- , -SO _2- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m -NHCO-, -COO- (CH ₂ ) _m -OCO- and the like. It is not limited to.

X is preferably a single bond, -O-, -NH-, -O- (CH ₂ ) _m -O-.

In formula [1], although Y may be a meta position or an ortho position from the position of X, Preferably it is an ortho position. That is, it is preferable that formula [1] is the following formula [1 '].

[Formula 3]

Location of the "-NH _2" in the formula (1), as shown in formula (1), which position even but, preferably the formula [1] -a1, [1] -a2, [1 It is preferable that it is a position represented by] -a3, More preferably, it is [1] -a1.

[Formula 4]

From said formula [1] -a1-formula [1] -a3 and said formula [1 '], it is preferable that said formula [1] is any structure chosen from the following formula, Preferably it is Formula [1]- It is preferable that it is a structure represented by a1-1.

[Formula 5]

Y each independently represents the structure of following formula [1-1].

[Formula 6]

Formula [1-1] in, Y ¹ and Y ³ are, each independently, a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -CH 2 O-, - At least 1 sort (s) chosen from the group which consists of CONH-, -NHCO-, -COO-, and -OCO- is shown.

Y ² represents a single bond or - (CH _{2) b} - represents a (b is an integer of 1 to 15.) (where, Y ¹ or Y ³ is only bond, - (CH _{2) a} - if, Y ² is Y ¹ is at least one member selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and / or Y ³ is- In the case of at least one member selected from the group consisting of O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, Y ² is a single bond or-(CH ₂ ) _b- ( Provided that when Y ¹ is -CONH-, Y ² and Y ³ are a single bond).

Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton; The arbitrary hydrogen atoms of the phase may be substituted with a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom.

Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms. The group, C1-C3 fluorine-containing alkyl group, C1-C3 fluorine-containing alkoxy group, or a fluorine atom may be substituted.

Y <^6> is group which consists of a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, and a C1-C18 fluorine-containing alkoxy group At least 1 sort (s) chosen from is shown. n represents the integer of 0-4.

Although the following groups [1-1] -1 to [1-1] -22 are mentioned as group represented by said Formula [1-1], It is not limited to these. Among these, it is preferable that they are [1-1] -1-[1-1] -4, [1-1] -8, and [1-1] -10. In addition, * represents the position which couple | bonds with the phenyl group in the said Formula [1], the said Formula [1 '], and the said Formula [1] -a1-the said Formula [1] -a3. m represents the integer of 1-15, n represents the integer of 0-18.

[Formula 7]

<Side chain of photoreactivity>

The polymer contained in the liquid crystal aligning agent of this invention may have a photoreactive side chain.

As for the photoreactive side chain, the "specific polymer" may have, and the "polyimide precursor and / or the polyimide which is the imide" which are polymers other than a "specific polymer" may have.

<Diamine containing photoreactive side chain>

To introduce photoreactive side chains into polymers other than "specific polymers" and / or "specific polymers", it is preferable to use diamines having photoreactive side chains as part of the diamine component. Examples of the diamine having a photoreactive side chain include, but are not limited to, diamines having a side chain represented by formula [VII] or a formula [VII].

[Formula 8]

Formula [Ⅷ], coupled position of the two amino groups (-NH ₂₎ of the formula [Ⅸ] is not limited. Specifically, 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, 5 positions on the benzene ring Can be mentioned. Especially, the position of 2, 4, the position of 2, 5, or the position of 3, 5 are preferable from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid. If the ease in synthesizing a diamine is also taken into consideration, the position of 2, 4 or the position of 3, 5 is more preferable.

The definition of R <^8> , R <^9> and R < ¹⁰ > in formula [VII] is as follows.

That is, R ⁸ is a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ ) -, -CON (CH ₃ )-, or -N (CH ₃ ) CO-. In particular, R ⁸ is preferably a single bond, -O-, -COO-, -NHCO-, or -CONH-.

R ⁹ represents a C1-C20 alkylene group which may be substituted with a single bond or a fluorine atom, and -CH ₂ -of the alkylene group may be optionally substituted with -CF ₂ -or -CH = CH- When either group does not mutually adjoin each other, you may substitute by these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring or a hetero ring.

In addition, although the following can be illustrated specifically, the said divalent carbon ring or heterocyclic ring is not limited to these.

[Formula 9]

R ⁹ can be formed by a conventional organic synthetic method, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.

R ¹⁰ represents a photoreactive group selected from the following formula.

[Formula 10]

In view of photoreactivity, R ¹⁰ is preferably a methacryl group, an acryl group or a vinyl group.

In addition, the definition of Y <_1> , Y <_2> , Y <_3> , Y <_4> , Y <_5> , and Y < ₆ > in a formula [VII] is as follows.

That is, Y ₁ represents -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-.

Y <_2> is a C1-C30 alkylene group, a bivalent carbon ring, or a heterocyclic ring, One or some hydrogen atoms of this alkylene group, a bivalent carbon ring, or a heterocyclic ring may be substituted by the fluorine atom or the organic group. . Y ₂ may be substituted with -CH ₂ -when these groups are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.

Y ₃ represents -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond.

Y ₄ represents a cinnamoyl group. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring or a hetero ring, and one or a plurality of hydrogen atoms of the alkylene group, the divalent carbon ring or a hetero ring are substituted with a fluorine atom or an organic group You may be.

Y ₅ may be substituted with -CH ₂ -when these groups are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.

Y ₆ represents a photopolymerizable group which is an acrylic group or a methacryl group.

Although the following are mentioned specifically, the diamine which has a photoreactive side chain is not limited to this. In the following formulae, X ⁹ and X ¹⁰ each independently represent a single bond, -O-, -COO-, -NHCO-, or a -NH--bonding group, and Y has 1 to 20 carbon atoms which may be substituted with a fluorine atom. An alkylene group is shown.

[Formula 11]

Moreover, as a diamine which has a photoreactive side chain, the diamine which has in a side chain the group which produces the photodimerization reaction represented by a following formula, and the group which produces a photopolymerization reaction is also mentioned.

[Formula 12]

In said formula, Y <_1> -Y <_6> is the same as the said definition.

The diamine which has the said photoreactive side chain is one kind according to the liquid crystal aligning property, the pretilt angle, the voltage holding characteristic, the accumulation charge, etc., the response speed of the liquid crystal at the time of making it a liquid crystal display element, etc. when it is set as a liquid crystal aligning film. Or two or more types can be mixed and used.

Moreover, as for the diamine which has a photoreactive side chain, it is preferable to use 10-70 mol% of the diamine component used for the synthesis | combination of a polyamic acid, More preferably, it is 20-60 mol%, Especially preferably, it is 30- 50 mol%.

Moreover, as a diamine which has a photoreactive side chain, the diamine which has in the side chain the site | part which has a radical generating structure which decomposes by ultraviolet irradiation and generate | occur | produces a radical is mentioned.

[Formula 13]

Have the Ar, R _1, R _2, T _1, T _2, S and Q are defined below in the formula (1).

That is, Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom.

R ₁ and R ₂ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group.

T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )- , -CON (CH ₃ )-, -N (CH ₃ ) CO-.

S is an alkylene group having 1 to 20 carbon atoms substituted with a single bond or unsubstituted or fluorine atom. However, —CH ₂ — or —CF ₂ — of the alkylene group may be optionally substituted with —CH═CH—, or when any of the following groups do not adjoin each other, they may be substituted with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent hetero ring.

Q represents a structure selected from the following (In the structural formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents —CH ₂ —, —NR—, —O—, or —S—. ).

[Formula 14]

In the above formula (I), Ar bonded to carbonyl is involved in the absorption wavelength of ultraviolet rays. Therefore, in the case of long wavelength, a long conjugated structure such as naphthylene and biphenylene is preferable. In addition, a substituent may be substituted by Ar, and such a substituent is preferably an electron donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, an amino group or the like.

In Formula (I), when Ar becomes a structure like naphthylene and biphenylene, solubility will worsen and the difficulty of synthesis will also become high. Since sufficient characteristics are obtained even if it is a phenyl group as long as the wavelength of an ultraviolet-ray is 250 nm-380 nm, a phenyl group is the most preferable.

Moreover, R <_1> , R <_2> is respectively independently a C1-C10 alkyl group, an alkoxy group, a benzyl group, or a phenethyl group, In the case of an alkyl group or an alkoxy group, even if it forms the ring by R <_1> , R <_2> . do.

In Formula (I), Q is preferably an electron donating organic group, and the above group is preferable.

In the case where Q is an amino derivative, there is a possibility that a problem such as formation of a salt of the carboxylic acid group and an amino group generated during polymerization of the polyamic acid, which is a precursor of the polyimide, may occur, and more preferably, a hydroxyl group or an alkoxy. It is a practical skill.

The diamino benzene in the formula (1) may be any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but m-phenylene in terms of reactivity with acid dianhydride Diamine or p-phenylenediamine is preferred.

Specifically, a structure represented by the following formula is most preferable in view of ease of synthesis, high versatility, characteristics, and the like. In addition, n is an integer of 2-8 in a formula.

[Formula 15]

<Other diamine>

As another diamine component for obtaining a specific polymer, you may contain diamines (henceforth other diamine) other than the specific diamine shown by the said Formula [1]. Such diamine is represented by the following general formula [2]. Other diamine may use together 1 type (s) or 2 or more types.

[Formula 16]

In said formula [2], A <_1> and A <_2> are respectively independently a hydrogen atom or a C1-C5 alkyl group, a C2-C5 alkenyl group, or a C2-C5 alkynyl group. From the viewpoint of the reactivity of the monomer, A ₁ and A ₂ are preferably a hydrogen atom or a methyl group. The structure of Y <_1> is as follows.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

In formula, unless otherwise specified, n is an integer of 1-6. In the following formulae, Boc represents a tert-butoxycarbonyl group.

[Formula 35]

Although the other diamine component used for the liquid crystal aligning agent of this invention is not specifically limited, From a viewpoint of applicability | paintability, voltage retention characteristic, residual DC voltage characteristic, etc., it is (Y-7), (Y-8), (Y -16), (Y-17), (Y-21), (Y-22), (Y-28), (Y-37), (Y-38), (Y-60), (Y-67 ), (Y-68), (Y-71) to (Y-73), it is particularly preferable to use a diamine selected from (Y-160) to (Y-180) to use in combination.

(Tetracarboxylic acid component)

As a tetracarboxylic-acid component for obtaining a specific polymer, tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl ester dihalide is mentioned. In addition, in this invention, these are named generically also as a tetracarboxylic-acid component.

As a tetracarboxylic-acid component, tetracarboxylic dianhydride, the derivative which is tetracarboxylic acid, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl ester dihalide (these are generically And 1st tetracarboxylic acid component.) May be used.

<Tetracarboxylic dianhydride>

As tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, the thing of the group of the following [1]-[5], etc. are mentioned, respectively.

[1] as aliphatic tetracarboxylic dianhydride, for example 1,2,3,4-butanetetracarboxylic dianhydride;

[2] As alicyclic tetracarboxylic dianhydride, for example, acid dianhydrides such as the following formulas (X1-1) to (X1-13);

[Formula 36]

In formulas (X1-1) to (X1-4), each of R ₃ to R ₂₃ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a carbon having 2 to 6 carbon atoms. It is an alkynyl group, a C1-C6 monovalent organic group containing a fluorine atom, or a phenyl group, and may be same or different,

In the formula, R _M is a hydrogen atom or a methyl group,

Xa is a tetravalent organic group represented by following formula (Xa-1) (Xa-7).

[Formula 37]

[3] 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 3,5,6-tricarboxy 2-carboxymethylnorbornane-2: 3,5: 6--2 anhydride, 4,9-dioxatricyclo [5.3.1.02,6] undecane-3,5,8,10-tetraone, etc .;

[4] As aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenylsulfone Tetracarboxylic dianhydride, acid dianhydride represented by the following formulas (Xb-1) to (Xb-10); and

[Formula 38]

[5] Furthermore, acid dianhydrides represented by formulas (X1-44) to (X1-52) and tetracarboxylic dianhydride described in JP 2010-97188 A may be mentioned.

[Formula 39]

In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

Although the tetracarboxylic dianhydride component used for the liquid crystal aligning agent of this invention is not specifically limited, From a viewpoint of applicability | paintability, voltage retention characteristic, residual DC voltage characteristic, etc., it is (X1-1), (X1-2) , (X1-3), (X1-6), (X1-7), (X1-8), (X1-9), (Xa-2), pyromellitic anhydride, 3,3 ', 4,4 It is preferable to select and use tetracarboxylic dianhydride selected from '-diphenylsulfontetracarboxylic dianhydride, (Xb-6), and (Xb-9).

<Production Method of Polymer>

The method for producing these polymers is usually obtained by reacting a diamine component with a tetracarboxylic acid component. The polyamic acid is reacted by reacting at least one kind of tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and derivatives of the tetracarboxylic acid with a diamine component composed of one or a plurality of diamines. The method of obtaining is mentioned. Specifically, a method of polycondensing tetracarboxylic dianhydride and primary or secondary diamine to obtain a polyamic acid is used.

In order to obtain a polyamic-acid alkylester, the method of polycondensing the tetracarboxylic acid which dialkyl-esterified the carboxylic acid group, and the primary or secondary diamine, the tetracarboxylic-acid dihalide which halogenated the carboxylic acid group, and primary or The method of polycondensing a secondary diamine or the method of converting the carboxy group of a polyamic acid into ester is used.

In order to obtain a polyimide, the method of ring-closing said polyamic acid or polyamic-acid alkylester to make polyimide is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent. It will not specifically limit, if the produced polyimide precursor melt | dissolves as a solvent used at that time. Although the specific example of the solvent used for reaction is given below, it is not limited to these examples.

For example N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1, 3- dimethyl- imidazolidinone is mentioned. Moreover, when solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl- 2-pentanone, or following formula [D-1]-a formula [D -3] can be used.

[Formula 40]

Of the formula ^[D-1], D 1 represents an alkyl group having a carbon number of 1 to 3, wherein ^[D-2], D 2 represents an alkyl group having a carbon number of 1 to 3, formula ^[D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms.

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

When reacting a diamine component and a tetracarboxylic-acid component in a solvent, the solution which disperse | distributed or melt | dissolved the diamine component in the solvent is stirred, and the method of disperse | distributing or dissolving the tetracarboxylic-acid component as it is or in a solvent, on the contrary, tetra The method of adding a diamine component to the solution which disperse | distributed or melt | dissolved the carboxylic acid component in the solvent, the method of adding the diamine component and the tetracarboxylic acid component alternately, etc. are mentioned, You may use any of these methods. Moreover, when making it react using two or more types of diamine components or tetracarboxylic acid components, it may be made to react in the state mixed previously, may be made to react individually one by one, and the low molecular weight reacted individually may be mixed and polymerized You may make it.

Although the temperature which polycondenses a diamine component and the tetracarboxylic-acid component can select arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. The reaction initial stage can be performed in high concentration | density, and can add a solvent after that.

In the polymerization reaction of a polyimide precursor, it is preferable that ratio of the total mole number of a diamine component and the total mole number of a tetracarboxylic-acid component is 0.8-1.2. As in the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyimide precursor to be produced.

The polyimide is a polyimide obtained by ring closing the above polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily need to be 100%, depending on the use and purpose. I can adjust it.

As a method of imidating a polyimide precursor, thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature at the time of thermally imidating a polyimide precursor in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC, The method of implementing while removing the water produced | generated by the imidation reaction outside system is preferable. Catalyst imidation of a polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the solution of a polyimide precursor, and stirring at -20-250 degreeC, Preferably it is 0-180 degreeC.

The amount of a basic catalyst is 0.5-30 mol times of amic acid groups, Preferably it is 2-20 mol times, and the quantity of an acid anhydride is 1-50 mol times of amic acid groups, Preferably it is 3-30 mol times.

Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In particular, the use of acetic anhydride is preferred because purification after completion of the reaction becomes easy.

The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the reaction solution of a polyimide precursor or a polyimide, the reaction solution may be added to a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer precipitated by being poured into a solvent can be dried by normal temperature or heating under normal pressure or reduced pressure after filtration and recovery. Moreover, if the polymer which precipitated and collect | recovered is re-dissolved in a solvent and repeats the operation which reprecipitates and recovers 2 to 10 times, impurities in a polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like. It is preferable to use three or more kinds of solvents selected from these because the efficiency of purification further increases.

The more specific method for manufacturing the polyamic-acid alkylester of this invention is shown to following (1)-(3).

(1) Method of producing by esterification of polyamic acid

A polyamic acid is produced from a diamine component and a tetracarboxylic acid component, and a carboxyl group (COOH group) is subjected to a chemical reaction, that is, an esterification reaction, to produce a polyamic acid alkyl ester.

The esterification reaction allows a polyamic acid and an esterifying agent to react for 30 minutes to 24 hours (preferably 1 to 4 hours) at -20 to 150 ° C (preferably 0 to 50 ° C) in the presence of a solvent. to be.

As said esterification agent, what can be easily removed after esterification reaction is preferable, and N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide di Propyl Acetal, N, N-DimethylformamideDynepentylbutylacetal, N, N-Dimethylformamidedi-t-butylacetal, 1-Methyl-3-p-tolyltriacene, 1-ethyl-3-p- Tolyltriazene, 1-propyl-3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like Can be. As for the usage-amount of an esterification agent, 2-6 molar equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid. Especially, 2-4 molar equivalent is preferable.

As a solvent used for the said esterification reaction, the solvent used for reaction of the said diamine component and the tetracarboxylic-acid component is mentioned from the viewpoint of the solubility to the solvent of polyamic acid. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are preferable. You may use these solvent 1 type or in mixture of 2 or more types.

As for the density | concentration of the polyamic acid in the solvent in the said esterification reaction, 1-30 mass% is preferable at the point which precipitation of a polyamic acid hardly occurs. Especially, 5-20 mass% is preferable.

(2) Method of producing by reaction of diamine component and tetracarboxylic acid diester dichloride

Specifically, the diamine component and tetracarboxylic acid diester dichloride are -30 to 150 ° C (preferably 0 to 50 ° C) in the presence of a base and a solvent for 30 minutes to 24 hours (preferably 1 To 4 hours).

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. Especially, pyridine is preferable because reaction advances mildly. The amount of base to be used is preferably an amount that can be easily removed after the reaction, and preferably 2 to 4 times molar relative to tetracarboxylic acid diester dichloride. Especially, 2-3 times mole is more preferable.

As a solvent, the solvent used for reaction of the said diamine component and the tetracarboxylic-acid component is mentioned from the viewpoint of the solubility to the solvent of the polymer obtained, ie, the polyamic-acid alkylester. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are preferable. You may use these solvent 1 type or in mixture of 2 or more types.

As for the density | concentration of the polyamic-acid alkylester in the solvent in reaction, 1-30 mass% is preferable at the point which precipitation of a polyamic-acid alkylester does not occur easily. Especially, 5-20 mass% is preferable. Moreover, in order to prevent the hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for preparation of a polyamic-acid alkylester is dehydrated as much as possible. In addition, it is preferable to perform reaction in nitrogen atmosphere and to prevent mixing of external air.

(3) Method to prepare by reaction of diamine component and tetracarboxylic acid diester

Specifically, the diamine component and the tetracarboxylic acid diester are 30 minutes to 24 hours (preferably 3 at 0 to 150 ° C (preferably 0 to 100 ° C) in the presence of a condensing agent, a base and a solvent. To 15 hours) polycondensation reaction.

Examples of condensing agents include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1, 3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluroniumtetrafluoroborate, O- (benzotriazole-1 -Yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl) phosphonic acid diphenyl and the like can be used have. 2-3 times mole is preferable with respect to tetracarboxylic-acid diester, and, as for the usage-amount of a condensing agent, 2-2.5 times mole is especially preferable.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount which can be easily removed after a polycondensation reaction is preferable, as for the usage-amount of a base, 2-4 times mole is preferable with respect to a diamine component, and 2-3 times mole is more preferable.

The solvent used for a polycondensation reaction can mention the solvent used for reaction of the said diamine component and the tetracarboxylic-acid component from the viewpoint of the solubility to the solvent of the polymer obtained, ie, the polyamic-acid alkylester. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are preferable. You may use these solvent 1 type, or 2 or more types.

Moreover, in a polycondensation reaction, reaction advances efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. As for the usage-amount of Lewis acid, 0.1-10 times mole is preferable with respect to a diamine component. Especially, 2.0-3.0 times mole is preferable.

When recovering a polyamic-acid alkylester from the solution of the polyamic-acid alkylester obtained by the method of said (1)-(3), what is necessary is just to throw a reaction solution into a solvent and to precipitate. Examples of the solvent used for precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like. It is preferable to perform the washing | cleaning operation in multiple times with the said solvent for the purpose of removing the additive and catalysts used above which the polymer thrown into the solvent and precipitated. After washing, filtration and recovery, the polymer can be dried by normal temperature or heating under normal pressure or reduced pressure. Moreover, the impurity in a polymer can be reduced by re-dissolving the polymer which precipitated and collect | recovered in a solvent and repeating the operation of reprecipitation recovery 2 to 10 times.

As for polyamic-acid alkylester, the manufacturing method of said (2) or (3) is preferable.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains the specific polymer mentioned above, Preferably it is preferable that it is a solution for forming a liquid crystal aligning film. 2-10 mass% is preferable in a liquid crystal aligning agent, and, as for content of the polymer in a liquid crystal aligning agent, 3-8 mass% is more preferable.

As for all the polymer components in the liquid crystal aligning agent of this invention, all may be the specific polymer of this invention, and the other polymer other than that may be mixed. As a polymer other than that, a cellulose polymer, an acrylic polymer, a methacryl polymer, polystyrene, a polyamide, a polysiloxane etc. are mentioned in addition to a polyimide and a polyimide precursor. 1-90 mass% is preferable in the resin component contained in a liquid crystal aligning agent, and, as for content of another polymer other than that, 30-80 mass% is more preferable.

The good solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if the specific polymer of this invention melt | dissolves. Although the specific example of the solvent used for a liquid crystal aligning agent is given below, it is not limited to these examples.

For example N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1, 3- dimethyl- imidazolidinone is mentioned.

Moreover, when solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl- 2-pentanone, or the said formula [D-1]-a formula [D -3] can also be used.

The said good solvent may be used by one type, and may be used in more suitable combinations and ratios according to a coating method, etc.

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

The liquid crystal aligning agent of this invention can use the solvent (also called poor solvent) which improves the coating-film property and surface smoothness of the liquid crystal aligning film at the time of apply | coating a liquid crystal aligning agent. The specific example is given to the following.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether , Dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-part Ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methylethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3 -Pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1- Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol mono Methyl ether acetate, di Propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate , Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy Ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol Noethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid , 3-methoxy propionate, 3-methoxy butyl propionate, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, the above formula [D-1] to [ D-3], etc. are mentioned.

Especially, as a preferable solvent combination, N-methyl- 2-pyrrolidone, ethylene glycol monobutyl ether, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, ethylene glycol monobutyl ether, N- Methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyro Lactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and 2,6-dimethyl- 4-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol Monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, and the like. As for these poor solvents, 1-80 mass% of the whole solvent contained in a liquid crystal aligning agent is preferable, 10-80 mass% is more preferable, 20-70 mass% is especially preferable. The kind and content of such a solvent are suitably selected according to the coating device of a liquid crystal aligning agent, application | coating conditions, application environment, etc.

In addition to the above, in the liquid crystal aligning agent of this invention, the polymer other than the polymer described in this invention, the silane coupler for the purpose of improving the adhesiveness of the dielectric for the purpose of changing electrical characteristics, such as dielectric constant and electroconductivity of a liquid crystal aligning film, a liquid crystal aligning film, and a board | substrate. A crosslinking compound for the purpose of increasing the hardness and the density of the film in the case of using a ring agent, a liquid crystal alignment film, and an imidation accelerator for the purpose of efficiently advancing the imidization by heating the polyimide precursor when firing the coating film. You can also do it.

As a compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, a functional silane containing compound and an epoxy group containing compound are mentioned, For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxy Silyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxy Silyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol di Glycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-te Raglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Cyclohexane or N, N, N ', N'- tetraglycidyl-4,4'- diamino diphenylmethane etc. are mentioned.

Moreover, in order to raise the mechanical strength of a liquid crystal aligning film, you may add the following additives to the liquid crystal aligning agent of this invention.

[Formula 41]

It is preferable that said additive is 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a liquid crystal aligning agent. If it is less than 0.1 mass part, an effect cannot be expected, and when it exceeds 30 mass parts, since the orientation of a liquid crystal is reduced, More preferably, it is 0.5-20 mass parts.

<Liquid crystal aligning film and liquid crystal display element>

The liquid crystal aligning film of this invention can be formed by apply | coating and baking the liquid crystal aligning agent of this invention on a board | substrate.

For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, you may dry as needed, and you may use the cured film obtained by baking, as a liquid crystal aligning film as it is. Moreover, it is also possible to rub this cured film, irradiate light of a polarization or a specific wavelength, etc., process ion beams, etc., or irradiate UV in the state which applied the voltage to the liquid crystal display element after liquid crystal charge as an alignment film for PSA. Do. In particular, it is useful to use it as an oriented film for PSA.

At this time, as a board | substrate to be used, if it is a board | substrate with high transparency, it will not specifically limit, A glass plate, a polycarbonate, a poly (meth) acrylate, a polyether sulfone, a polyarylate, a polyurethane, a polysulfone, a polyether, a polyether Plastic substrates such as ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose and the like can be used. Moreover, it is preferable to use the board | substrate with which the ITO electrode etc. for liquid crystal drive were formed from a viewpoint of the simplification of a process. Moreover, in the reflective liquid crystal display element, only an opaque one, such as a silicon wafer, can be used if it is only a board | substrate on one side, and the electrode in this case can also use the material which reflects light, such as aluminum.

The coating method of a liquid crystal aligning agent is not specifically limited, Printing methods, such as screen printing, offset printing, and flexographic printing, an inkjet method, a spray method, a roll coating method, a dip, a roll coater, a slit coater, a spinner, etc. are mentioned. have. In terms of productivity, the transfer printing method is widely used industrially, and is also preferably used in the present invention.

The coating film formed by apply | coating a liquid crystal aligning agent by the said method can be baked, and it can be set as a cured film. Although the process of drying after apply | coating a liquid crystal aligning agent is not necessarily required, when the time from application | coating to baking is not constant for every board | substrate, or when it does not bake immediately after application | coating, it is preferable to perform a drying process. The solvent should just be removed to such an extent that a coating-film shape does not deform | transform by conveyance of a board | substrate etc., and this drying is not specifically limited about the drying means. For example, the method of drying for 0.5 minutes-30 minutes, Preferably 1 minute-5 minutes is mentioned on the hotplate of temperature 40 degreeC-150 degreeC, Preferably 60 degreeC-100 degreeC.

The baking temperature of the coating film formed by apply | coating a liquid crystal aligning agent is not limited, For example, it is 100-350 degreeC, Preferably it is 120-350 degreeC, More preferably, it is 150 degreeC-330 degreeC. The firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 10 minutes to 30 minutes. Heating can be normally performed by a well-known method, for example, a hotplate, a hot air circulation furnace, an infrared furnace, etc.

Moreover, although the thickness of the liquid crystal aligning film obtained by baking is not specifically limited, Preferably it is 5-300 nm, More preferably, it is 20-200 nm.

The liquid crystal display element can produce a liquid crystal cell by a well-known method, after forming a liquid crystal aligning film in a board | substrate by said method. Specific examples of the liquid crystal display device include a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer formed between the substrates, and the liquid crystal alignment film formed between the substrate and the liquid crystal layer and formed by a liquid crystal alignment agent. It is a liquid crystal display element of a vertical alignment system. Specifically, a liquid crystal aligning film is formed by coating and baking a liquid crystal aligning agent on two board | substrates, two board | substrates are arrange | positioned so that this liquid crystal aligning film may oppose, and the liquid crystal layer comprised of liquid crystal is clamped between these two board | substrates. It is a liquid crystal display element of the vertical alignment system provided with the liquid crystal cell produced.

Vertical alignment capability is remarkable by using the liquid crystal aligning film formed by the liquid crystal aligning agent containing the specific polymer of this invention, and irradiating an ultraviolet-ray and reacting the polymeric compound contained in a liquid crystal, applying a voltage to a liquid crystal aligning film and a liquid crystal layer, and It becomes an excellent PSA system liquid crystal display element.

Although it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate of a liquid crystal display element, Usually, it is a board | substrate with a transparent electrode for driving a liquid crystal on the board | substrate. As a specific example, the thing similar to the board | substrate described by the said liquid crystal aligning film is mentioned. Although the board | substrate with which the conventional electrode pattern and the projection pattern were formed may be used, in the PSA system liquid crystal display element, since the liquid crystal aligning agent containing the polyimide-type polymer of this invention is used, it is one to one board | substrate, for example. It can operate also in the structure which forms the line / slit electrode pattern of 10 micrometers, and does not form a slit pattern and a projection pattern in the opposing board | substrate, The process at the time of manufacture can be simplified by the liquid crystal display element of this structure, High transmittance can be obtained.

Moreover, in the high functional element like a TFT type element, the thing in which an element like a transistor was formed between the electrode for liquid crystal drive, and a board | substrate is used.

In the case of a transmissive liquid crystal display element, it is common to use the above-mentioned board | substrate, but in a reflective liquid crystal display element, it is possible to use opaque board | substrates, such as a silicon wafer, only if it is a board | substrate of one side. In that case, the material like aluminum which reflects light can also be used for the electrode formed in the board | substrate.

The liquid crystal material which comprises the liquid crystal layer of a liquid crystal display element is not specifically limited, The liquid crystal material used by the conventional vertical alignment system, for example, negatives, such as MLC-6608, MLC-6609, and MLC-3023 by Merck, Inc. Type liquid crystals can be used. Moreover, in the PSA system liquid crystal display element, the liquid crystal containing a polymeric compound represented by a following formula can be used, for example.

[Formula 42]

A well-known method is mentioned as a method of clamping a liquid crystal layer between two board | substrates. For example, a pair of board | substrates with which the liquid crystal aligning film was formed is prepared, the spacer, such as a beads, is spread | dispersed on the liquid crystal aligning film of one board | substrate, and the other board | substrate is bonded together so that the surface of the side in which the liquid crystal aligning film was formed may be inward. And a method of injecting and sealing the liquid crystal under reduced pressure. Moreover, a pair of board | substrate with which the liquid crystal aligning film was formed is prepared, after spreading spacers, such as a beads, on the liquid crystal aligning film of one board | substrate, a liquid crystal is dripped, and after that, the surface of the side in which the liquid crystal aligning film was formed is made into another inside, A liquid crystal cell can also be produced by the method of bonding one board | substrate together and sealing. The thickness of the said spacer becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

The process of manufacturing a liquid crystal cell by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal aligning film and a liquid crystal layer, for example, applies an electric field to a liquid crystal aligning film and a liquid crystal layer by applying a voltage between the electrodes provided on the board | substrate, And a method of irradiating ultraviolet rays while maintaining an electric field. Here, as a voltage applied between electrodes, it is 5-30 Vp-p, Preferably it is 5-20 Vp-p. The irradiation amount of the ultraviolet ray is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of the ultraviolet ray can suppress the decrease in reliability caused by the destruction of the member constituting the liquid crystal display element, and the ultraviolet ray It is preferable because the production efficiency is increased by reducing the irradiation time.

As described above, when ultraviolet rays are applied while applying voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the response of the liquid crystal display device obtained by storing the direction in which the liquid crystal molecules are inclined by the polymer is stored. You can speed it up. Moreover, when ultraviolet-ray is irradiated, applying a voltage to a liquid crystal aligning film and a liquid crystal layer, the polyimide obtained by imidating the side chain which orientates a liquid crystal perpendicularly, the polyimide precursor which has a photoreactive side chain, and this polyimide precursor Since the photoreactive side chains which the at least 1 sort (s) of polymer chosen from and the photoreactive side chain which a polymer has, and a polymeric compound react, the response speed of the liquid crystal display element obtained can be made quick.

Example

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is limited to these and is not interpreted. The abbreviation of the used compound is as follows.

(Liquid crystal)

MLC-3023 (manufactured by Merck, negatively polymerizable compound-containing liquid crystal)

(Specific Side Chain Diamine Component)

W-A1: the compound represented by a formula [W-A1]

W-A2: Compound represented by formula [W-A2]

W-A3: Compound represented by formula [W-A3]

W-A4: Compound represented by formula [W-A4]

W-A5: Compound represented by formula [W-A5]

W-A6: Compound represented by formula [W-A6]

W-A7: Compound represented by formula [W-A7]

W-A8: Compound represented by formula [W-A8]

W-A9: Compound represented by formula [W-A9]

W-A10: Compound represented by formula [W-A10]

[Formula 43]

(Other Side Chain Diamine Compound)

A1: the compound represented by formula [A1]

A2: the compound represented by formula [A2]

A3: the compound represented by formula [A3]

[Formula 44]

(Other diamine compound)

C1: compound represented by formula [C1]

C2: Compound represented by formula [C2]

C3: Compound represented by formula [C3]

C4: Compound represented by formula [C4]

C5: Compound represented by formula [C5]

C6: compound represented by formula [C6]

C7: compound represented by formula [C7]

C8: compound represented by formula [C8]

C9: Compound represented by formula [C9]

C10: compound represented by formula [C10]

[Formula 45]

(Tetracarboxylic acid component)

D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

D3: pyromellitic dianhydride

D4: 2,3,5-tricarboxycyclopentyl acetic acid anhydride

D5: 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride

[Formula 46]

(menstruum)

NMP: N-methyl-2-pyrrolidone

BCS: Ethylene Glycol Monobutyl Ether

NEP: N-ethyl-2-pyrrolidone

(Bridge)

E1: Crosslinking agent represented by following formula (E1)

(additive)

E2: 3-picolylamine

[Formula 47]

(Molecular weight measurement)

The molecular weight of a polyimide precursor and a polyimide is using the normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (made by Showa Denko), and a column (KD-803, KD-805) (made by Shodex) It measured as follows.

Column temperature: 50 ℃

Eluent: N, N'-dimethylformamide (as additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol / L (liter), phosphoric acid and anhydrous crystals (o-phosphate) is 30 mmol / L, tetra Hydrofuran (THF) 10 ml / L)

Flow rate: 1.0 ml / min

Standard samples for calibration curve preparation: 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).

(Measurement of the imidation ratio of polyimide)

20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ 5 (manufactured by Kusano Scientific Co., Ltd.)) and mixed with deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) Product) (0.53 mL) was added, and ultrasonic wave was added to dissolve completely. 500 MHz of proton NMR was measured for this solution by the NMR measuring machine (JNW-ECA500) (made by Nippon Electron Datum). The imidation ratio determines the proton derived from the structure which does not change before and after imidation as a reference proton, and uses the peak integrated value of this proton and the proton peak integrated value derived from the NH group of the amic acid appearing around 9.5-10.0 ppm. It calculated | required by the following formula.

Imidation ratio (%) = (1-alpha-x / y) x100

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

(Viscosity measurement)

In the synthesis example or the comparative synthesis example, the viscosity of the polyimide-based polymer was 1.1 mL of sample volume and cone rotor TE-1 (1 ° 34 ', R24) using an E-type viscometer TVE-22H (manufactured by Toki Industries Co., Ltd.). It measured at 25 degreeC of temperature.

W-A1-W-A3 and W-A4-W-A10 are unpublished novel compounds, such as a literature, and the synthesis method is explained in full detail below.

The products described in Synthesis Examples 1 to 3 and Synthesis Examples 4 to 10 were identified by ¹ H-NMR analysis (analysis conditions are as follows).

Device: Varian NMR System 400 NB (400 MHz).

Determination solvent: CDCl ₃ , DMSO-d ₆ .

Reference Material: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H).

<< synthesis of synthesis example 1 W-A1 >>

[Formula 48]

<Synthesis of Compound [1] and Compound [2]>

In tetrahydrofuran (165.6 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (41.1 g, 135 mmol) and triethylamine (31.5 g) were injected and Methanesulfonyl chloride (33.2g) was dripped under nitrogen atmosphere ice-cooling conditions, and the compound [1] was obtained by making it react for 1 hour. Subsequently, p- (trans-4-heptylcyclohexyl) phenol (77.8 g) dissolved in tetrahydrofuran (246.6 g) was added, and the hydroxide dissolved in pure water (233 g) after stirring at 40 ° C for 1 hour. Potassium (41.0 g) was added at the same temperature and reacted for 21 hours. After completion of the reaction, 1.0 M aqueous hydrochloric acid solution (311 ml) and pure water (1050 g) were added to precipitate a crude product, and the crude product was recovered by filtration. The obtained crude substance was heated and dissolved in tetrahydrofuran (574 g) at 50 degreeC, methanol (328g) was added, the crystal | crystallization was precipitated, and filtration and drying were obtained, and compound [2] was obtained (amount: 97.9 g, yield: 89%). ).

<Synthesis of W-A1>

In tetrahydrofuran (1783 g), compound [2] (74.3 g, 90.9 mmol) and 3% platinum carbon (5.94 g) were injected and reacted under a hydrogen atmosphere at room temperature. After completion | finish of reaction, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure to make internal gross weight 145g. Subsequently, methanol (297g) was added to the concentrated solution, ice-cooled stirring, filtration and drying were performed to obtain W-A1 (amount: 59.2 g, yield: 86%).

<< synthesis of synthesis example 2 W-A2 >>

[Formula 49]

<Synthesis of Compound [3]>

4,4'-dinitro-2,2'-diphenic acid (40.9 g, 123 mmol) and p- (trans-4-heptylcyclohexyl) phenol (72.1 g) in tetrahydrofuran (327.2 g), 4 -Dimethylaminopyridine (1.50 g) was injected, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (56.6 g) was added under a nitrogen atmosphere at room temperature to react for 3 hours. After completion of the reaction, the reaction solution was poured into pure water (1226 g) to precipitate a crude product, which was recovered by filtration. Subsequently, the slurry was filtered after slurry washing with methanol (245 g), and the obtained crude substance was dissolved in tetrahydrofuran (245 g) by heating at 60 ° C. After removing the insoluble matter by filtration, the total weight was 232 g by concentration under reduced pressure, and then methanol (163 g) was added to precipitate the crystals, followed by stirring under ice-cooling conditions, followed by filtration and drying to give Compound [3]. Obtained (amount: 73.9 g, yield: 71%).

<Synthesis of W-A2>

Compound [3] (73.9 g, 87.4 mmol) and 5% palladium carbon (8.80 g) were injected in tetrahydrofuran (443 g) and methanol (73.9 g), and the mixture was reacted under a hydrogen atmosphere at room temperature. After completion | finish of reaction, palladium carbon was removed by filtration and the internal gross weight was 171g by concentration under reduced pressure. Subsequently, methanol (222 g) was added to the concentrated solution to precipitate crystals, ice-cooled stirring, filtration and drying to obtain W-A2 (amount: 66.6 g, yield: 97%).

<< synthesis of synthesis example 3 W-A3 >>

[Formula 50]

<Synthesis of Compound [4] and Compound [5]>

4- (trans-4-heptylcyclohexyl) -benzoic acid (73.1 g, 242 mmol) and N, N-dimethylformamide (0.73 g) were injected in toluene (366 g), and the mixture was cooled under nitrogen atmosphere at 50 ° C. Thionyl (35.9 g) was added dropwise. After dripping and reacting at the same temperature for 1 hour, compound [4] was obtained by concentrating a reaction solution under reduced pressure. Subsequently, in tetrahydrofuran (210 g), 4,4'-dinitro-1,1'-biphenyl-2,2'- dimethanol (35.0 g, 115 mmol) and triethylamine (26.8 g) Was injected, and compound [4] dissolved in tetrahydrofuran (73.1 g) was added dropwise under nitrogen atmosphere ice-cooling conditions. After completion of the dropwise addition, the reaction temperature was brought to room temperature and reacted for 18 hours. After completion | finish of reaction, after triethylamine hydrochloride was removed by filtration, the oily compound was obtained by concentration under reduced pressure. The obtained oily compound was added to pure water (1015 g) to precipitate crystals, and the crude product was recovered by filtration. Subsequently, the obtained crude product was washed with room temperature slurry with methanol (291 g), room temperature slurry with ethyl acetate (175 g), filtered and dried to obtain compound [5] (amount: 92.7 g, yield: 92%).

<Synthesis of W-A3>

In tetrahydrofuran (484 g) and methanol (161 g), compound [5] (80.5 g, 92.2 mmol) and 3% platinum carbon (6.44 g) were injected and reacted under a hydrogen atmosphere at room temperature. After completion of the reaction, the platinum total carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure, so that the total internal weight was 96.6 g. Subsequently, methanol (322 g) was added to the concentrated solution to precipitate crystals, ice-cooled stirring and filtration to obtain a crude product. Subsequently, the obtained crude product was heated and dissolved at 60 ° C. with ethyl acetate (322 g), methanol (700 g) was added, crystals were precipitated under ice-cooled conditions, filtered, and dried to obtain W-A3 (amount: 67.9 g) , Yield: 91%).

<< synthesis of synthesis example 4 W-A4 >>

[Formula 51]

<Synthesis of Compound [6] and Compound [7]>

In toluene (134 g), trans, trans-4'-amylbicyclohexyl-4-carboxylic acid (26.7 g, 95.1 mmol) and N, N-dimethylformamide (0.401 g) are charged, and a nitrogen atmosphere 50 Thionyl chloride (13.6 g, 114 mmol) was dripped under the conditions of ° C. After dripping and reacting at the same temperature for 1 hour, compound [6] was obtained by concentrating a reaction solution under reduced pressure. Subsequently, in tetrahydrofuran (63.0 g), 4,4'-dinitro-1,1'-biphenyl-2,2'- dimethanol (12.6 g, 41.4 mmol) and triethylamine (10.9 g, 108 mmol) was injected, and compound [6] dissolved in tetrahydrofuran (12.6 g) was added dropwise under nitrogen atmosphere ice-cooling conditions. After completion of the dropwise addition, the reaction temperature was maintained at room temperature and allowed to react for 17 hours. After completion of the reaction, crystals were precipitated by adding the reaction solution in pure water (731 g), and then the crude product was recovered after filtration, pure water washing and methanol washing. Subsequently, the obtained crude product was dissolved in toluene (56.0 g) by heating, hexane (112 g) was added to precipitate crystals, and the mixture was stirred under room temperature, filtered and dried to obtain compound [7] (amount: 17.0 g). , 20.6 mmol, yield: 50%).

<Synthesis of W-A4>

Compound [7] (17.0 g, 20.6 mmol) and 3% platinum carbon (1.36 g) were injected in tetrahydrofuran (136 g) and methanol (34.0 g), and the mixture was reacted for about 41 hours under a hydrogen atmosphere at room temperature. After completion | finish of reaction, internal gross weight was 40 g by filtration and concentration under reduced pressure. Subsequently, methanol (68.0 g) was added to precipitate crystals, which was then filtered and dried to obtain W-A4 (amount: 15.2 g, 19.9 mmol, yield: 97%).

<< synthesis of synthesis example 5 W-A5 >>

[Formula 52]

<Synthesis of Compound [8]>

Trans-1-bromo-4- (4-heptylcyclohexyl) benzene (45.4 g, 135 mmol) and lithium bis (trimethylsilyl) amide (about 26% tetrahydrofuran solution, about 1.30 in toluene (227 g) mol / L, 218 ml), tri-tert-butylphosphoniumtetrafluoroborate (1.58 g, 5.44 mmol), bis (dibenzylideneacetone) palladium (0) (3.14 g, 5.46 mmol) were injected and nitrogen It was made to react for 17 hours under atmospheric room temperature conditions. After the completion of the reaction, 5.7 mol / L aqueous hydrochloric acid solution (80.0 ml) was added to precipitate crystals, and the hydrochloride salt of compound [8] was recovered by filtration. The hydrochloride obtained was dispersed in a mixed solution of toluene (300 g), ethyl acetate (200 g) and tetrahydrofuran (100 g), separated with 3.0 mol / L aqueous sodium hydroxide solution (200 g), and the organic phase was further saturated brine. Washed with. Subsequently, activated carbon (item: special egret, 2.27 g) was added to the organic phase and stirred, and then activated carbon was removed by filtration. The obtained filtrate was concentrated under reduced pressure to obtain an oily compound. The oily compound was dispersed in hexane (100 g), and crystals were precipitated under dry ice / ethanol cooling conditions to obtain compound [8] (amount: 27.5 g, 101 mmol, yield: 75%).

<Synthesis of Compound [9]>

4,4'-dinitro-2,2'-diphenic acid (14.9 g, 45.0 mmol) in tetrahydrofuran (120 g) and methylene chloride (60.0 g) with compound [8] (25.8 g, 94.3 mmol) , 4-dimethylaminopyridine (0.550 g, 4.50 mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (20.0 g, 104 mmol) were injected and reacted for 14 hours under nitrogen atmosphere at room temperature. I was. After the completion of the reaction, the mixture was diluted with ethyl acetate (375 g), washed three times with pure water (149 g), and the obtained organic phase was treated with magnesium sulfate dehydration. Then, the organic phase was concentrated under reduced pressure, the internal gross weight was 112 g, and methanol (120 g) was added to precipitate crystals, filtered and dried to obtain compound [9] (amount: 28.0 g, 33.2 mmol, yield). : 74%)

<Synthesis of W-A5>

Compound [9] (28.0 g, 33.2 mmol) and 5% palladium carbon (2.10 g) were injected in tetrahydrofuran (140 g) and methanol (56.0 g) and reacted for about 3 days under hydrogen atmosphere room temperature conditions. After completion | finish of reaction, palladium carbon was removed by filtration and the internal gross weight was 122 g by concentrating under reduced pressure. Methanol (168g) was added to the obtained solution to precipitate crystals, and filtration and drying were carried out to obtain W-A5 (amount: 23.8 g, 30.4 mmol, yield: 92%).

<< synthesis of synthesis example 6 W-A6 >>

[Formula 53]

<Synthesis of Compound [10]>

4,4'-dinitro-2,2'-diphenic acid (25.0 g, 75.4 mmol) and cholesterol (61.7 g, 160 mmol), 4- in tetrahydrofuran (113 g) and methylene chloride (113 g) Dimethylaminopyridine (0.919 g, 7.54 mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (33.6 g, 175 mmol) were injected and reacted under nitrogen atmosphere at room temperature for 18 hours. After completion of the reaction, methylene chloride (375 g) was added to the reaction solution, and the organic phase was washed three times with saturated brine (200 g), and then the organic phase was dehydrated with magnesium sulfate. Subsequently, the obtained solution was concentrated under reduced pressure to obtain a brown oily compound, and a mixed solution of ethyl acetate (200 g) and isopropyl alcohol (200 g) was added to precipitate crystals and filtered to obtain a crude product. The obtained crude product was recrystallized twice from a mixed solution of chloroform (500 g) and methanol (600 g), filtered and dried to obtain Compound [10] (amount: 41.8 g, 39.1 mmol, yield: 52%).

<Synthesis of W-A6>

Compound [10] (40.4 g, 37.8 mmol) and 5% palladium carbon (3.03 g) were injected in tetrahydrofuran (320 g) and methanol (80.8 g), and reacted for about 3 days under hydrogen atmosphere room temperature conditions. After completion | finish of reaction, the palladium carbon was removed by filtration and the internal gross weight was 112 g by concentrating under reduced pressure. Methanol (160 g) was added to the obtained solution to precipitate crystals, which was filtered and dried to obtain W-A6 (amount: 35.0 g, 34.7 mmol, yield: 92%).

<< synthesis of synthesis example 7 W-A7 >>

[Formula 54]

<Synthesis of Compound [11] and Compound [12]>

4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (40.0 g, 132 mmol) and triethylamine (36.6 g, 362 mmol) in tetrahydrofuran (152 g) Was injected, and ethanesulfonyl chloride (44.4 g, 345 mmol) was added dropwise under ice-cooled conditions under a nitrogen atmosphere. After completion of dropwise addition, the compound [11] was obtained by stirring the reaction temperature at 40 ° C for 3 hours. Subsequently, p- (trans-4-propylcyclohexyl) phenol (63.1 g, 289 mmol) dissolved in tetrahydrofuran (240 g) and potassium hydroxide (85.0% product, 45.1 g) dissolved in pure water (228 g). , 683 mmol) was added to a reaction solution of compound [11], heated to 50 ° C. and reacted for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (1500 g), and the crude product was precipitated, followed by filtration and pure water washing. Subsequently, slurry washing was performed with a pure water (378 g) and methanol (378 g) mixed solution, followed by filtration and washing with methanol. The obtained crystal crude product was melt | dissolved in tetrahydrofuran (600g) at 60 degreeC, methanol (400g) is added, and a crystal | crystallization is precipitated, the compound [12] was obtained by filtering, drying after stirring under room temperature conditions (amount: 77.7 g, 110 mmol, yield: 83%).

<Synthesis of W-A7>

Compound [12] (77.7 g, 110 mmol) and 3% platinum carbon (6.22 g) were injected into tetrahydrofuran (741 g) and methanol (155 g), and reacted for about 2 days at room temperature under hydrogen atmosphere. . After completion of the reaction, the platinum resin was removed by filtration, and the filtrate was concentrated under reduced pressure. Tetrahydrofuran (122g) was added to the obtained concentrated crude substance, it melt | dissolved at 60 degreeC, acetonitrile (159g) was added, the crystal | crystallization was precipitated, and it stirred under room temperature conditions, filtered, and dried, and obtained W-A7 ( Yield: 58.6 g, 88.1 mmol, yield: 80%).

<< synthesis of synthesis example 8 W-A8 >>

[Formula 55]

<Synthesis of Compound [11] and Compound [13]>

4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (39.2 g, 129 mmol) and triethylamine (35.0 g, 346 mmol) in tetrahydrofuran (156 g) Was injected, and ethanesulfonyl chloride (34.8 g, 271 mmol) was added dropwise under ice-cooled conditions under a nitrogen atmosphere. After dripping, the reaction temperature was stirred at 40 degreeC for 3 hours, and compound [11] was obtained. Subsequently, 4-cyclohexylphenol (50.0 g, 284 mmol) dissolved in tetrahydrofuran (230 g) and potassium hydroxide (85.0% product, 47.1 g, 714 mmol) dissolved in pure water (231 g) were prepared. 11], and it heated at 50 degreeC and made it react for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (660 g), and liquid separation and extraction were performed with chloroform (588 g x 4 times). The recovered organic phase was concentrated under reduced pressure, and the crude solution was dissolved in tetrahydrofuran (118 g) by heating at 60 ° C, methanol (235 g) was added to precipitate crystals, and the mixture was stirred at room temperature and filtered. The crystals were cake-washed with pure water / methanol = 1/1 mixed solvent (118 g) and methanol (118 g × 2 times) and dried to obtain Compound [13] (amount: 67.6 g, 120 mmol, yield: 93%). ).

<Synthesis of W-A8>

Compound [13] (65.0 g, 105 mmol) and 3% platinum carbon (5.20 g) were injected in tetrahydrofuran (325 g) and methanol (65.0 g), and the mixture was reacted for about 2 days at room temperature under a hydrogen atmosphere. . After completion of the reaction, the platinum resin was removed by filtration and concentrated under reduced pressure. The crude product was dissolved in tetrahydrofuran (70.4 g) by heating at 60 ° C, methanol (130 g) was added to precipitate crystals, and the mixture was stirred under room temperature and filtered. The crystals were cake washed with methanol (130 g × 2 times) and dried to obtain W-A8 (amount: 54.2 g, 96.7 mmol, yield: 92%).

<< synthesis of synthesis example 9 W-A9 >>

[Formula 56]

<Synthesis of Compound [11] and Compound [14]>

4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (20.9 g, 68.7 mmol) and triethylamine (15.3 g, 151 mmol) in tetrahydrofuran (83.6 g) Was injected, and ethanesulfonyl chloride (18.6 g, 145 mmol) was added dropwise under nitrogen atmosphere ice-cooling conditions. After dripping, the reaction temperature was stirred at 40 degreeC for 3 hours, and compound [11] was obtained. Subsequently, 4-[(trans, trans) -4'-pentyl [1,1'-bicyclohexyl] -4-yl] phenol (48.6 g, 149 mmol) dissolved in tetrahydrofuran (188 g); Potassium hydroxide (85.0% product, 20.9 g, 317 mmol) dissolved in pure water (119.2 g) was added to the reaction solution of compound [11], and reacted for 20 hours. After completion of the reaction, the reaction solution was poured into pure water (800 g) to precipitate the crude product, and the mixture was filtered and washed with pure water. Subsequently, slurry washing was performed with a pure water (100 g) and methanol (100 g) mixed solution, followed by filtration, washing with pure water and methanol. The crude product was dissolved in tetrahydrofuran (400 g) by heating at 60 ° C, methanol (100 g) was added to precipitate crystals, followed by stirring under room temperature, followed by filtration and drying to obtain compound [14] (amount: 49.7 g). , 53.9 mmol, yield: 78%).

<Synthesis of W-A9>

In tetrahydrofuran (361 g) and methanol (90.2 g), compound [14] (45.1 g, 48.7 mmol) and 3% platinum carbon (3.60 g) were charged, and about 9 at 0.4 MPa hydrogen pressure atmosphere at 40 ° C. The reaction was time. After completion of the reaction, the solvent was removed by filtration and concentration under reduced pressure, and methanol (135 g) was added to slurry washing. Subsequently, the crude product obtained by filtration was heated and dissolved in tetrahydrofuran (180 g) at 60 ° C., ethyl acetate (120 g) was added, and the crystals were precipitated by stirring under room temperature conditions. Was obtained (amount: 17.8 g, 20.7 mmol, yield: 43%).

<< synthesis of synthesis example 10 W-A10 >>

[Formula 57]

<Synthesis of Compound [15]>

2-fluoro-5-nitrotoluene (91.0 g, 587 mmol), 1,3-propanediol (22.3 g, 291 mmol), potassium hydroxide (85.0% product) in N-methylpyrrolidone (540 g) 71.6 g, 1.08 mol) was injected and stirred at 80 ° C for 20 hours in a nitrogen atmosphere. After completion of the reaction, pure water (1440 g) was added to crystallize charcoal, and after filtration, the crystals were cake-washed with pure water (540 g x 3 times) and methanol (360 g x 2 times), respectively, and dried. Compound [15] was obtained (amount: 57.2 g, 165 mmol, yield: 54%).

<Synthesis of Compound [16]>

In 1,2-dichloroethane (540 g), compound [15] (40.0 g, 116 mmol), N-bromosuccinimide (45.2 g, 254 mmol), 2,2'-azobis (isobutyro) Nitrile) (3.79 g, 23.1 mmol) was injected, and after nitrogen substitution, the mixture was stirred at 100 ° C. for about 7 days. The reaction solution was filtered to remove insoluble succinimide, ethyl acetate (250 g) was added to the filtrate, liquid separation and washing were performed with pure water (250 g × 3 times), and the organic phase was recovered and concentrated. . The obtained concentrate was crystallized and filtered with ethyl acetate (346 g) and hexane (395 g) to recover the crystals. Furthermore, the filtrate was concentrated, crystallized and filtered again with chloroform (223 g) and hexane (434 g), and dried, respectively, to obtain a crude product of Compound [16] (crude yield: 21.3 g, crude ( I) yield: 37%).

<Synthesis of Compound [17]>

P- (trans-4-heptylcyclohexyl) phenol (24.0 g, 87.5 mmol) and potassium carbonate (12.1 g, 87.5 mmol) were injected in N, N-dimethylacetamide (96.0 g) and stirred at 100 ° C. . Compound [16] crude (20.0 g) dissolved in N, N-dimethylacetamide (54.0 g) was added dropwise and reacted for 24 hours. Crystals precipitated from the reaction solution were separated by filtration, and each slurry was washed with methanol (66.0 g) and pure water (67.0 g), and then filtered and dried again to obtain Compound [17] (amount: 4.23 g, 4.75 mmol, yield). : 4.1% (yield based on the injection compound [15]).

<Synthesis of W-A10>

Compound [17] (3.60 g, 4.04 mmol) and 3% platinum carbon (0.290 g) were injected in tetrahydrofuran (28.8 g) and methanol (7.5 g) at 40 ° C. under a hydrogen atmosphere of 0.4 MPa pressurized conditions. Stir for 3 hours. After completion of the reaction, the platinum resin was removed by filtration and concentrated under reduced pressure. The crude product was added with ethyl acetate and methanol to precipitate crystals, and the mixture was stirred under room temperature, filtered and dried to obtain W-A10 (amount: 2.05 g, 2.47 mmol, yield: 54%).

<Synthesis of Polyimide Polymer>

Synthesis Example 1

D2 (2.50 g, 10.0 mmol), W-A1 (3.03 g, 4.00 mmol) and C1 (1.73 g, 16.0 mmol) were mixed in NMP (36.2 g) and reacted at 60 ° C. for 3 hours, followed by D1 (1.78 g, 9.10 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 840 mPa * s when the viscosity of this polyamic-acid solution was measured.

After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass%, acetic anhydride (4.43g) and pyridine (1.37g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (382 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (1). The imidation ratio of this polyimide was 76.4%, the number average molecular weight was 16,165 and the weight average molecular weight was 49,988.

Synthesis Example 2

D2 (2.50 g, 10.0 mmol), W-A2 (3.14 g, 4.00 mmol) and C1 (1.84 g, 16.0 mmol) were mixed in NMP (36.9 g) and reacted at 60 ° C. for 3 hours, followed by D1 (1.84 g, 9.38 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 658 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, acetic anhydride (4.38 g) and pyridine (1.36 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (382 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (2). The imidation ratio of this polyimide was 75.8%, the number average molecular weight was 15,430 and the weight average molecular weight was 45,756.

Synthesis Example 3

D2 (2.50 g, 10.0 mmol), W-A3 (3.25 g, 4.00 mmol) and C1 (1.73 g, 16.0 mmol) were mixed in NMP (37.3 g) and reacted at 60 ° C. for 3 hours, followed by D1 (1.84 g, 9.38 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 656 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, acetic anhydride (4.32 g) and pyridine (1.34 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (382 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (3). The imidation ratio of this polyimide was 74.7%, the number average molecular weight was 13,340 and the weight average molecular weight was 41,948.

[Control Synthesis Example 1]

D2 (1.50 g, 6.0 mmol), C2 (1.83 g, 12.0 mmol), C3 (2.18 g, 9.0 mmol), A1 (3.43 g, 9.0 mmol) were dissolved in NMP (41.1 g) and 3 hours at 60 ° C. After reacting, D3 (1.31 g, 6.0 mmol) was added, and then D1 (3.47 g, 17.7 mmol) and NMP (13.71 g) were added, and it reacted at 25 degreeC for 10 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (50g) and diluting to 6.5 mass%, acetic anhydride (11.1g) and pyridine (3.4g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 3 hours. This reaction solution was poured into methanol (700 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (4). The imidation ratio of this polyimide was 79%, the number average molecular weight was 11000 and the weight average molecular weight was 24000.

Comparative Synthesis Example 1

D2 (2.88 g, 11.5 mmol), A1 (3.50 g, 9.20 mmol) and C1 (1.49 g, 13.8 mmol) were mixed in NMP (40.2 g) and reacted at 60 ° C. for 3 hours, followed by D1 (2.19 g, 11.2 mmol) was added, and it reacted at 40 degreeC for 3 hours, and obtained the polyamic-acid solution of 20 mass% of resin solid content concentration. It was 680 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, acetic anhydride (4.64 g) and pyridine (1.44 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (382 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (R1). The imidation ratio of this polyimide was 75.1%, the number average molecular weight was 15,322 and the weight average molecular weight was 45,800.

Synthesis Example 5

D2 (2.50 g, 10.0 mmol), W-A4 (4.62 g, 6.00 mmol) and C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.5 g) and reacted at 60 ° C. for 3 hours, then D1 (1.92 g, 9.80 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 783 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, acetic anhydride (3.86 g) and pyridine (1.20 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (233 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (5). The imidation ratio of this polyimide was 76.7%, the number average molecular weight was 14,399 and the weight average molecular weight was 38,573.

Synthesis Example 6

D2 (2.50 g, 10.0 mmol), W-A5 (4.70 g, 6.00 mmol) and C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.9 g) and reacted at 60 ° C for 3 hours, followed by D1 (1.92 g, 9.80 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 769 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, acetic anhydride (3.83 g) and pyridine (1.19 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (232 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The imidation ratio of this polyimide was 73.4%, the number average molecular weight was 13,841 and the weight average molecular weight was 37,284.

Synthesis Example 7

D2 (6.26 g, 25.0 mmol), W-A6 (5.05 g, 5.00 mmol) and C1 (4.87 g, 45.0 mmol) were mixed in NMP (62.0 g) and reacted at 60 ° C for 3 hours, then D1 (4.51 g, 23.0 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 658 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (75.0 g) and diluted to 6.5 mass%, acetic anhydride (18.2 g) and pyridine (5.6 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1000 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (7). The imidation ratio of this polyimide was 72.9%, the number average molecular weight was 13,362 and the weight average molecular weight was 38,725.

Synthesis Example 8

D2 (6.26 g, 25.0 mmol), W-A7 (8.06 g, 12.5 mmol) and C1 (4.06 g, 37.5 mmol) were mixed in NMP (69.2 g) and reacted at 60 ° C. for 3 hours, then D1 (4.71 g, 24.0 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 725 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (75.0 g) and diluted to 6.5 mass%, acetic anhydride (16.5 g) and pyridine (5.1 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1000 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (8). The imidation ratio of this polyimide was 73.1%, the number average molecular weight was 13,628 and the weight average molecular weight was 39,937.

Synthesis Example 9

D2 (6.26 g, 25.0 mmol), W-A8 (7.01 g, 12.5 mmol), C1 (4.06 g, 37.5 mmol) were mixed in NMP (66.1 g) and reacted at 60 ° C. for 3 hours, then D1 (4.71 g, 24.0 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 674 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (75.0 g) and diluted to 6.5 mass%, acetic anhydride (17.2 g) and pyridine (5.3 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1000 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (9). The imidation ratio of this polyimide was 73.2%, the number average molecular weight was 10,425 and the weight average molecular weight was 37,759.

Synthesis Example 10

D2 (6.26 g, 25.0 mmol), W-A9 (2.16 g, 2.5 mmol), C1 (5.14 g, 47.5 mmol) were mixed in NMP (54.8 g) and reacted at 60 ° C. for 3 hours, then D1 (4.71 g, 24.0 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 823 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (75.0 g) and diluted to 6.5 mass%, acetic anhydride (20.7 g) and pyridine (6.4 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1000 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (10). The imidation ratio of this polyimide was 71.5%, the number average molecular weight was 13,732 and the weight average molecular weight was 38,921.

Synthesis Example 11

D2 (2.50 g, 10.0 mmol), W-A10 (3.31 g, 4.00 mmol) and C1 (1.73 g, 16.0 mmol) were mixed in NMP (30.2 g) and reacted at 60 ° C. for 3 hours, then D1 (1.84 g, 9.40 mmol) were added and reacted at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 695 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, acetic anhydride (4.35 g) and pyridine (1.35 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (235 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (11). The imidation ratio of this polyimide was 76.1%, the number average molecular weight was 12,913 and the weight average molecular weight was 39,182.

Synthesis Example 12

D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol), C8 (33.0 g, 100 mmol) was mixed in NMP (432 g) and at 60 ° C After reacting for 3 hours, D1 (18.8 g, 96.0 mmol) was added, and it reacted at 40 degreeC for 3 hours, and obtained the polyamic-acid solution of 20 mass% of resin solid content concentration. It was 721 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (100 g) and diluted to 6.5 mass%, acetic anhydride (16.0 g) and pyridine (4.96 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1150 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (12). The imidation ratio of this polyimide was 75.1%, the number average molecular weight was 14,736 and the weight average molecular weight was 39,645.

Synthesis Example 13

D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C6 (20.5 g, 60.0 mmol), C8 (6.61 g, 20.0 mmol), C7 (27.9 g, 70.0 mmol) was converted into NMP (471). After mixing in g) and making it react at 60 degreeC for 3 hours, D1 (18.8g, 96.0 mmol) was added, and it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 771 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (100 g) and diluted to 6.5 mass%, acetic anhydride (14.9 g) and pyridine (4.63 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1150 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (13). The imidation ratio of this polyimide was 76.2%, the number average molecular weight was 15,835 and the weight average molecular weight was 39,145.

Synthesis Example 14

D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C6 (17.0 g, 50.0 mmol), C8 (16.5 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol) was charged with NMP (434 After mixing in g) and making it react at 60 degreeC for 3 hours, D1 (18.8g, 96.0 mmol) was added, and it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 701 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (100 g) and diluted to 6.5 mass%, acetic anhydride (16.0 g) and pyridine (4.97 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1150 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (14). The imidation ratio of this polyimide was 74.8%, the number average molecular weight was 17,635 and the weight average molecular weight was 41,647.

Synthesis Example 15

D4 (43.9 g, 196 mmol), W-A1 (30.3 g, 40.0 mmol), C4 (13.9 g, 70.0 mmol), C8 (16.5 g, 50.0 mmol), C5 (7.59 g, 40.0 mmol) was charged with NMP (455 It mixed in g) and made it react at 60 degreeC for 15 hours, and obtained the polyamic-acid solution of 20 mass% of resin solid content concentration. It was 662 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (100 g) and diluted to 6.5 mass%, acetic anhydride (17.9 g) and pyridine (5.55 g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . This reaction solution was poured into methanol (1160 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (15). The imidation ratio of this polyimide was 71.7%, the number average molecular weight was 13,329 and the weight average molecular weight was 40,527.

Synthesis Example 16

D2 (25.0 g, 100 mmol), C2 (21.3 g, 140 mmol), C10 (24.6 g, 60.0 mmol) was dissolved in NMP (284 g) and reacted at 60 ° C. for 3 hours, then D5 (14.3 g, 40.0 mmol), D1 (11.0 g, 56.0 mmol) and NMP (100 g) were then added, and it reacted at 25 degreeC for 10 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (100g) and diluting to 6.5 mass%, acetic anhydride (21.0g) and pyridine (6.52g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. The reaction solution was poured into methanol (1170 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (16). The imidation ratio of this polyimide was 75.8%, the number average molecular weight was 14679 and the weight average molecular weight was 35747.

Synthesis Example 17

D2 (25.0 g, 100 mmol), C6 (50.0 g, 120 mmol), C9 (15.1 g, 60.0 mmol), W-A1 (15.1 g, 20.0 mmol) was dissolved in NMP (385 g) and at 60 ° C. After reacting for 3 hours, D1 (18.8 g, 96.0 mmol) and NMP (75.3 g) were added, and it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution of 20 mass% of resin solid content concentration was obtained. It was 753 mPa * s when the viscosity of this polyamic-acid solution was measured.

After adding NMP to this polyamic-acid solution (100g) and diluting to 6.5 mass%, acetic anhydride (17.6g) and pyridine (5.47g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (1160 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (17). The imidation ratio of this polyimide was 71.1%, the number average molecular weight was 17635 and the weight average molecular weight was 38427.

Comparative Synthesis Example 2

D2 (6.26 g, 25.0 mmol), A2 (12.23 g, 30.0 mmol) and C1 (2.16 g, 20.0 mmol) were mixed in NMP (76.7 g) and reacted at 80 ° C. for 5 hours, followed by D1 (4.90 g, 25.0 mmol) was added, and it reacted at 40 degreeC for 12 hours, and obtained the polyamic-acid solution of 20 mass% of resin solid content concentration. It was 338 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (75.0 g) and diluted to 6.5 mass%, acetic anhydride (15.0 g) and pyridine (4.6 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1000 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (R2). The imidation ratio of this polyimide was 73.0%, the number average molecular weight was 10,175 and the weight average molecular weight was 23,642.

Comparative Synthesis Example 3

D2 (6.26 g, 25.0 mmol), A3 (7.06 g, 25.0 mmol) and C1 (2.70 g, 25.0 mmol) were mixed in NMP (62.8 g) and reacted at 80 ° C. for 5 hours, then D1 (4.90 g, 25.0 mmol) was added, and it reacted at 40 degreeC for 12 hours, and obtained the polyamic-acid solution of 20 mass% of resin solid content concentration. It was 446 mPa * s when the viscosity of this polyamic-acid solution was measured.

NMP was added to the obtained polyamic acid solution (75.0 g) and diluted to 6.5 mass%, acetic anhydride (18.3 g) and pyridine (5.7 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1000 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (R3). The imidation ratio of this polyimide was 72.2%, the number average molecular weight was 11,636 and the weight average molecular weight was 24,624.

The composition of the polyimide powder obtained by the synthesis example and the comparative synthesis example is put together in Table 1.

<Preparation of liquid-crystal aligning agent>

In an Example and a comparative example, the preparation example of a liquid-crystal aligning agent is described. Preparation of the liquid crystal display element and various evaluation were performed using the liquid-crystal aligning agent obtained by the Example and the comparative example.

<Example 1>

NMP (28.2g) was added to the polyimide powder (1) obtained by the synthesis example 1, and (3.00g), and it stirred for 24 hours and made it melt | dissolve at 70 degreeC. NMP (g) and BCS (18.8g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid-crystal aligning agent (V-1). Abnormalities, such as haze and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that it is a uniform solution.

<Example 2> and <Example 3>

In Example 1, using the polyimide powder (2) and (3) instead of the polyimide powder (1), by the procedure similar to Example 1, a liquid-crystal aligning agent (V-2) and (V-3) ) Abnormalities, such as haze and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that it is a uniform solution.

<Control 1>

In Example 1, the liquid-crystal aligning agent (V-4) was obtained by the procedure similar to Example 1 using the polyimide powder (4) obtained by the control synthesis example 1 instead of the polyimide powder (1). . Abnormalities, such as haze and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that it is a uniform solution.

<Example 4>

7.0 g of liquid-crystal aligning agent (V-4) obtained by 3.0 g and control 1 as liquid crystal aligning agent (V-1) obtained from Example 1 were mixed as a 2nd component, and stirred for 1 hour, and a liquid-crystal aligning agent (V-5) was obtained.

<Example 5>-<Example 6>

Example 4 WHEREIN: Liquid crystal aligning is carried out by the same procedure as Example 4 using a liquid-crystal aligning agent (V-2) or (V-3) instead of a liquid-crystal aligning agent (V-1) as a 1st component, respectively. Treatment agents (V-6) and (V-7) were obtained.

<Comparative Example 1>

NMP (28.2g) and BCS (18.8g) are added to the polyimide powder (R1) obtained by the comparative synthesis example 1, and (3.00g), and it stirred at 70 degreeC for 24 hours, and liquid-crystal aligning agent (R-V1) was added to it. Got it. Abnormalities, such as haze and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (R-V1), preparation of the liquid crystal display element, evaluation of the vertical alignment property, evaluation of the pretilt angle, evaluation of voltage retention, and evaluation of the afterimage characteristic were performed.

<Example 7>

NMP (22.0g) was added to the polyimide powder (5) obtained by the synthesis example 5, and (3.00g), and it stirred for 24 hours and made it melt | dissolve at 70 degreeC. E2 (1 wt% NMP solution) 3.0g and BCS (20.0g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid-crystal aligning agent (V-8). Abnormalities, such as haze and precipitation, were not seen by this liquid-crystal aligning agent, and it confirmed that it was a uniform solution.

<Examples 8-13, 15-17, 19, 20, and Comparative Examples 2-4>

Polyimide powders (6) to (11), (13) to (15) obtained in Synthesis Examples 6 to 11, 13 to 15 and 17, Comparative Synthesis Examples 1 to 3, and Control Synthesis Example 1 by the same operation as in Example 7. , (17), (R1-R3), (4) were used, and the liquid-crystal aligning agent (V-9-V-21) and (R-V2-R-V4) were prepared.

<Example 14>

NEP (22.0g) was added to the polyimide powder (12) obtained by the synthesis example 12, and (3.00g), and it stirred for 24 hours and made it melt | dissolve at 70 degreeC. NEP (3.0g) and BCS (20.0g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid-crystal aligning agent (V-15). Abnormalities, such as haze and precipitation, were not seen by this liquid-crystal aligning agent, and it confirmed that it was a uniform solution.

<Example 18>

The polyimide powder (16) obtained in Synthesis Example 16 was also subjected to the same operation as in Example 14 to obtain a liquid crystal aligning film treatment agent (V-19).

<Example 21>

Resin in a liquid crystal aligning agent 7.0g and crosslinking agent E1 were used as a 2nd component for the liquid-crystal aligning agent (V-15) obtained from Example 14 as a 1st component, 3.0g and the liquid-crystal aligning agent (V-19) obtained in Example 18, respectively. The liquid-crystal aligning agent (W-2) was obtained by mixing so that it may become 5 weight% with respect to the component, and stirring for 1 hour.

<Examples 22 to 24>

About the liquid-crystal aligning agent (V-16)-(V-21) obtained in Examples 15-20, the liquid-crystal aligning agent (W-3)-(W-5) was obtained by operation similar to Example 21.

Using the liquid-crystal aligning agent obtained by the Example and the liquid-crystal aligning agent obtained by the comparative example, preparation of a liquid crystal display element, evaluation of a vertical alignment property, a scratch test, evaluation of a pretilt angle, evaluation of voltage retention, and evaluation of an afterimage characteristic are performed. It was.

<Preparation of liquid crystal display element for voltage retention measurement>

The liquid-crystal aligning agent obtained by the Example and the liquid-crystal aligning agent obtained by the comparative example were filtered under pressure with the membrane filter of 1 micrometer of pore diameters. The obtained solution was spin-coated on the ITO surface of the glass substrate with a 40 mmx30 mm ITO electrode (length: 40 mm, width: 30 mm, thickness: 1.1 mm) wash | cleaned with pure water and IPA (isopropyl alcohol), The heat treatment was performed at 70 degreeC for 90 second at 70 degreeC on the hotplate for 30 minutes at 230 degreeC, and the ITO board | substrate with a liquid crystal aligning film with a film thickness of 100 nm was obtained. Two obtained ITO board | substrates with a liquid crystal aligning film were prepared, and the bead spacer (Niki-Kita Chemical Co., Ltd. make, Jinsa-gu, SW-D1) of diameter 4micrometer was apply | coated to the liquid crystal aligning film surface of the one board | substrate.

Next, the circumference was apply | coated with the sealing compound (Mitsui Chemicals XN-1500T). Subsequently, the surface of the side in which the liquid crystal aligning film of the other board | substrate was formed was made inside, and after bonding together with the previous board | substrate, the sealing material was hardened and the empty cell was manufactured. Liquid crystal MLC-3023 (Merck & Co., Ltd. brand name) was injected into this empty cell by the pressure reduction injection method, and the liquid crystal cell was produced.

Then, 15 J / cm <2> of ultraviolet rays which passed the bandpass filter of wavelength 365nm were irradiated using the ultraviolet irradiation device using the high pressure mercury lamp to the light source in the state which applied the DC voltage of 15V to the obtained liquid crystal cell, And the vertical alignment type liquid crystal display element were obtained. In addition, the UV-35 light receiver was connected to OR-C UV-M03A and used for the measurement of the amount of ultraviolet irradiation.

<Preparation of liquid crystal display element for pretilt angle and residual image evaluation>

The liquid-crystal aligning agent obtained by the Example was filtered under pressure with the membrane filter of 1 micrometer of pore diameters. An ITO electrode substrate (length: 35 mm, width: washed with pure water and IPA (isopropyl alcohol)) and formed with an ITO electrode pattern having a pixel size of 200 mu m x 600 mu m and a line / space of 3 mu m each. 30 mm, thickness: 0.7 mm), and spin-coated on an ITO surface of a glass substrate with an ITO electrode (length: 35 mm, width: 30 mm, thickness: 0.7 mm) each patterned with a photospacer having a height of 3.2 mu m. It heat-processed at 230 degreeC for 30 minutes in the heat circulation type clean oven for 70 second at 70 degreeC on the hotplate, and obtained the ITO board | substrate with a liquid crystal aligning film whose film thickness is 100 nm.

In addition, the ITO electrode substrate in which this ITO electrode pattern is formed is divided into four in the shape of a cross checker (check pattern), and can drive separately for every four areas.

Next, the circumference was apply | coated with the sealing compound (Mitsui Chemicals XN-1500T). Subsequently, the surface of the side in which the liquid crystal aligning film of the other board | substrate was formed was made inside, and after bonding together with the previous board | substrate, the sealing material was hardened and the empty cell was manufactured. Liquid crystal MLC-3023 (Merck & Co., Ltd. brand name) was injected into this empty cell by the pressure reduction injection method, and the liquid crystal cell was produced.

Thereafter, a 15 V DC voltage was applied to the obtained liquid crystal cell, and the ultraviolet rays passed through a band pass filter having a wavelength of 365 nm using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source while all pixel areas were driven. Was irradiated with 10 J / cm <2>, and the vertical alignment type liquid crystal display element was obtained. In order to measure the amount of ultraviolet radiation, a UV-35 light receiver was connected to UV-M03A manufactured by ORC.

In addition, in Examples 1-3 and Comparative Example 1, in addition to the above-mentioned standard conditions, as an excessive condition, the vertical alignment type was carried out under the same conditions as described above except that the liquid crystal alignment film was formed at 120 ° C. for 120 minutes. A liquid crystal display device was manufactured.

<Evaluation>

(Vertical orientation)

The liquid crystal aligning property of the liquid crystal display element was observed with the polarization microscope (ECLIPSE E600WPOL) (made by Nikon Corporation), and confirmed whether the liquid crystal was orientating vertically. Specifically, the defects due to the flow of the liquid crystal and the bright spots due to the orientation defect were not observed. Table 2 shows the results of the evaluation.

(Voltage retention)

After applying the voltage of 1V to the application time of 60 microseconds and the space | interval of 1667 milliseconds to the liquid crystal display element for voltage retention evaluation produced above, the voltage retention (%) after 1667 milliseconds after application | release cancellation was measured. The measurement apparatus used VHR-1 by Toyo Technica. Table 2 shows the results of the evaluation.

(Pretilt angle)

The measurement was performed about the liquid crystal display element which the defect by the flow of a liquid crystal was not seen among the liquid crystal display elements for pretilt angle evaluation produced above using the LCD analyzer (LCA-LUV42A by Meiyo Technica Co., Ltd.). Table 2 shows the results of the evaluation.

(Afterimage characteristic)

Using the liquid crystal display element for residual image evaluation produced above, AC voltage of 60 Hz and 20 Vp-p was applied to two diagonal areas among four pixel areas, and it was driven for 168 hours at the temperature of 23 degreeC. Thereafter, all four pixel areas were driven at an AC voltage of 5 Vp-p, and the luminance difference of the pixels was visually observed. The state which hardly confirmed a luminance difference was made favorable. Table 3 shows the results of the evaluation.

(Scratch test)

About the orientation film surface of the board | substrate with a polyimide coating film obtained in the Example, the scratch test was done using UMT-2 (made by Burka AX Corporation).

FVL was selected for the sensor of UMT-2, and the sapphire ball of 1.6 mm was attached to the front end of a scratch part.

The scratch test was performed by changing a load from 1 mN to 20 mN over 100 second in the range of 0.5 mm width and 2.0 mm length in the state which contacted the scratch part front-end with the surface of a liquid crystal aligning film by 1 mN of loads. At this time, the movement direction of the tip of the scratch portion was reciprocated horizontally, and the movement speed was performed at 5.0 mm / second. The movement of the scratch area in the longitudinal direction was performed by moving the substrate with the liquid crystal alignment film at 20 μm / sec in the vertical direction.

After the scratch test, MLC-3022 (negative liquid crystal manufactured by Merck Corporation) was added dropwise to the liquid crystal alignment film surface on which the scratch test was completed. The thing which spread | dispersed 4 micrometers spacers on the other board | substrate with a liquid crystal aligning film obtained in Example 1 there was overlapped so that liquid crystal aligning film surfaces mutually faced, and the dripped MLC-3022 was interposed.

The point which performed the scratch test was observed in the state which made the polarization axis of the upper and lower polarizing plates of the polarization microscope (ECLIPSE E600WPOL) (made by Nikon) become 90 degrees (cross nicol), and observed whether light transmitted. Table 6 shows a state where no bright spots or light leaks are observed, a state where a few bright spots or light leaks are observed, and a state where the entire scratched spots are light leaks. .

As a result of the above, specifically, the liquid crystal display element using the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention, as it turns out from the comparison of Examples 1-3 and Comparative Example 1 shown in Table 4, is also a premature condition. It was found that there was no change in the tilt angle and the liquid crystal alignment property was good.

Moreover, as shown in Table 5, in Example 4-Example 6 which mixed the liquid-crystal aligning agent (V-4), it turned out that an afterimage characteristic becomes a favorable result.

Moreover, it turned out that the liquid crystal aligning film obtained using the specific side chain type diamine is excellent in stability of a pretilt angle, even when baked on extreme conditions. Moreover, even when there existed physical contact with the liquid crystal aligning film like a scratch test, it was also confirmed that there is little damage to an oriented film, and can maintain favorable vertical alignment property.

Industrial availability

The liquid crystal display element using the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention can be used suitably for a liquid crystal display element. And these elements are also useful in a liquid crystal display for display purposes, and also a light control window, an optical shutter, etc. which control the transmission and interruption of light.

Claims (9)

Liquid crystal aligning agent containing the diamine component containing the diamine represented by following formula [1], and the at least 1 sort (s) of polymer chosen from the polyimide which is a reaction product of the tetracarboxylic-acid component, and its imide.
Formula [1], X is a single _{bond, -O-, -C (CH 3)} 2 -, -NH-, -CO-, - (CH 2) m -, -SO 2 -, and their random Divalent organic group which consists of a combination of these, m shows the integer of 1-8, Y represents the structure of following formula [1-1] each independently;
Formula [1-1] in, Y ¹ and Y ³ are, each independently, a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -CH 2 O-, - At least one selected from the group consisting of CONH-, -NHCO-, -COO-, and -OCO-;
Y ² represents a single bond or - (CH _{2) b} - represents a (b is an integer of 1 to 15.) (where, Y ¹ or Y ³ is only bond, - (CH _{2) a} - if, Y ² is Y ¹ is a single bond and at least one species selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO-, and -OCO-, and / or Y ³ is- In the case of at least one member selected from the group consisting of O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, Y ² is a single bond or-(CH ₂ ) _b- ( Provided that when Y ¹ is -CONH-, Y ² and Y ³ are a single bond));
Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, and the cyclic group Arbitrary hydrogen atoms of a phase may be substituted by a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom;
Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms. The group, the C1-C3 fluorine-containing alkyl group, the C1-C3 fluorine-containing alkoxy group, or the fluorine atom may be substituted;
Y ⁶ is at least selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy group having 1 to 18 carbon atoms 1 type is represented;
n represents the integer of 0-4.

The method of claim 1,
The diamine represented by the said Formula [1] is a liquid crystal aligning agent represented by a following formula [1 '].

The method according to claim 1 or 2,
The diamine represented by said formula [1] is a liquid crystal aligning agent represented by following formula [1] -a1, following formula [1] -a2, or following formula [1] -a3.

The method according to any one of claims 1 to 3,
The diamine represented by said formula [1] is following formula [1] -a1-1, following formula [1] -a2-1-following formula [1] -a2-4, following formula [1] -a3-1 or Liquid crystal aligning agent represented by following formula [1] -a3-2.

The method according to any one of claims 1 to 4,
Y represented by the structure of said Formula [1-1] is a following formula [1-1] -1-[1-1] -22 (In formula, * is said Formula [1] and said Formula [1 ']. And the position which couple | bonds with the phenyl group in said Formula [1] -a1-said Formula [1] -a3; m shows the integer of 1-15, n shows the integer of 0-18) Liquid crystal aligning agent represented by either.

The method according to any one of claims 1 to 5,
The said diamine component further contains the diamine represented by following formula [2].
(In formula [2], A <_1> and A <_2> respectively independently represent a hydrogen atom or a C1-C5 alkyl group, a C2-C5 alkenyl group, or a C2-C5 alkynyl group;
Y ₁ represents a divalent organic group.)
Liquid crystal aligning agent.

The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-6. Process of apply | coating the liquid crystal aligning agent in any one of Claims 1-6 on a board | substrate, and forming a coating film;
Baking the coating film; And
Orientation process of the film | membrane obtained by baking;
The manufacturing method of a liquid crystal aligning film which forms a liquid crystal aligning film by having Liquid crystal aligning film of Claim 7; Or liquid crystal aligning film obtained by the manufacturing method of Claim 8; Liquid crystal display element provided with.