KR20230129509A - Polymer composition, liquid crystal aligning agent, resin film, liquid crystal aligning film, liquid crystal display element manufacturing method and liquid crystal display element - Google Patents

Abstract

(각 기호의 정의는 명세서에 기재된 바와 같다.)

(각 기호의 정의는 명세서에 기재된 바와 같다.)Provided is a polymer composition suitable for a liquid crystal aligning agent that is excellent in resistance to AC afterimages and produces a liquid crystal aligning film with high film strength.
A polymer composition comprising the following components (A) and (B).
(A) Component: At least one type of polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide that is an imidate of the polyimide precursor.
(B) Component: A polyurethane that has a repeating unit represented by the following formula (1) and does not have a repeating unit represented by the following formula (a) and its imidized structure.

(The definition of each symbol is as described in the specification.)

(The definition of each symbol is as described in the specification.)

Description

Polymer composition, liquid crystal aligning agent, resin film, liquid crystal aligning film, manufacturing method of liquid crystal display element, and liquid crystal display element

The present invention relates to a polymer composition, a liquid crystal aligning agent, a resin film, a liquid crystal aligning film, a method for producing a liquid crystal display element, and a liquid crystal display element.

Liquid crystal display elements used in liquid crystal televisions, navigators, smart phones, etc. usually have a liquid crystal alignment film formed within the element to control the alignment state of the liquid crystals. A liquid crystal alignment film has a function of controlling the orientation of liquid crystal molecules in a certain direction in a liquid crystal display element. For example, a liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched between liquid crystal alignment films formed on each surface of a pair of substrates. There, the liquid crystal molecules are oriented in a certain direction by the liquid crystal aligning film, and respond by voltage application to the electrode formed between the substrate and the liquid crystal aligning film. As a result, the liquid crystal display element displays a desired image using the change in orientation due to the response of the liquid crystal molecules. As a liquid crystal alignment film, a polyimide-based liquid crystal alignment film has been mainly used so far, in which a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid or a solution of soluble polyimide is applied to a glass substrate or the like and fired. there is.

Recently, with the improvement of the performance of liquid crystal display elements, liquid crystal display elements have been used for applications such as large-screen, high-resolution liquid crystal televisions, as well as for automotive applications (e.g., car navigation systems and meter panels), surveillance cameras, and monitors for medical cameras. are being used, and due to the demand for viewing angle characteristics, transverse electric field methods such as the IPS (In Plane Switching) method and the FFS (fringe field switching) method are being examined (Patent Document 1).

International Publication No. 2019-082975

The liquid crystal alignment film used in the liquid crystal display element of the IPS drive system or FFS drive system requires an orientation regulation force to suppress afterimages (hereinafter also referred to as AC afterimages) generated by long-term alternating current drive. In the liquid crystal display devices that are rapidly becoming more sophisticated, high display quality is becoming more important, and specifications for display defects called “afterimages” are becoming more and more stringent.

Additionally, as a reliability test for liquid crystal display elements for vehicle use, a vibration test of the panel may be performed. In this vibration test, it is required that defects such as bright spots do not occur.

Additionally, in the rubbing alignment treatment applied in the process of producing a liquid crystal alignment film, there is a problem that dust resulting from the liquid crystal alignment film being scraped is likely to be generated when the alignment characteristic is expressed by the rubbing treatment. When dust is generated, not only does the dust adhere to the surface of the liquid crystal alignment film, causing display defects, but also circuit destruction of the TFT element occurs, resulting in a decrease in yield.

In view of the above, the present invention provides a polymer composition suitable for a liquid crystal aligning agent from which a liquid crystal aligning film having excellent resistance to AC afterimage and high film strength can be obtained, the liquid crystal aligning agent, the liquid crystal aligning film, and the liquid crystal aligning film. It aims at providing the liquid crystal display element which has.

As a result of extensive research in order to achieve the above-described problem, the present inventor has found that forming a resin film using a polymer composition containing a specific component is effective for achieving the above-mentioned object, and has completed the present invention.

This invention is based on this knowledge, and makes the following a summary.

A polymer composition characterized by containing the following components (A) and (B).

(A) Component: At least one type of polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide that is an imidate of the polyimide precursor.

(B) Component: A polyurethane that has a repeating unit represented by the following formula (1) and does not have a repeating unit represented by the following formula (a) and its imidized structure.

[Formula 1]

(X represents a tetravalent organic group. Y represents a divalent organic group derived from diamine. Two R's each independently represent a hydrogen atom or a monovalent organic group. Two Z's each independently represent a hydrogen atom or represents a monovalent organic group.)

[Formula 2]

(A ₁ is a divalent organic group derived from diisocyanate. A ₂ is a divalent organic group obtained by removing the hydrogen atom contained in the two hydroxy groups from the organic diol. At least one of A ₁ and A ₂ has the following formula It has a divalent organic group represented by (EG).)

[Formula 3]

(n is an integer greater than or equal to 5. R represents a hydrogen atom or a methyl group.)

According to the liquid crystal aligning agent of the present invention, a polymer composition suitable for a liquid crystal aligning agent from which a liquid crystal aligning film having excellent resistance to AC afterimage and high film strength is obtained, the liquid crystal aligning agent, the liquid crystal aligning film, and the liquid crystal aligning film. A liquid crystal display element having Moreover, the liquid crystal display element has a high display quality with few display defects.

The mechanism by which the above effect of the present invention is obtained is not necessarily clear, but is roughly estimated as follows. In other words, it is thought that the above effect was obtained because the polymer composition contained a specific polyurethane, thereby improving the membrane strength through hydrogen bonding, and also because the extensibility of the membrane was improved by introducing a specific ethylene glycol chain into the specific polyurethane. do.

Below, each component contained in the liquid crystal aligning agent of this indication, and other components arbitrarily mix|blended as needed are demonstrated.

In addition, in this specification, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom.

＜Polymer (A)＞

The polymer composition of the present invention is from the group consisting of a polyimide precursor (hereinafter also referred to as polyimide precursor (A)) having a repeating unit represented by the above formula (a) and a polyimide that is an imidate of the polyimide precursor. It contains the at least 1 sort(s) of polymer (A) chosen. 1 type or 2 or more types may be sufficient as a polymer (A).

(Repeating unit represented by equation (a))

In the formula (a), Y represents a divalent organic group derived from diamine. In addition, the divalent organic group derived from diamine includes, for example, a divalent organic group obtained by removing two amino groups from diamine. Examples of the diamine include the following diamines. This diamine may be used individually by 1 type, and may be used in combination of 2 or more type.

Diamine represented by the following formula (O); Diamine having a photo-alignment group such as 4,4'-diaminoazobenzene or diaminothran; Diamines having an amide bond or a urea bond, such as diamines represented by the following formulas (h-1) to (h-6); 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4 -aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, diamine represented by the following formula (d _o ); Diamine having at least one nitrogen atom-containing structure (hereinafter also referred to as a specific nitrogen atom-containing structure) selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and the following formula (3b-1) - diamines having a carboxyl group, such as diamines represented by formula (3b-4); 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1- (4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; diamines having a photopolymerizable group at the terminal, such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline; Cholestanyloxy-3,5-diaminobenzene, Cholestanyloxy-3,5-diaminobenzene, Cholestanyloxy-2,4-diaminobenzene, Cholestanyl 3,5-diaminobenzoate, diamines having a steroid skeleton such as 3,5-diaminobenzoic acid cholesthenyl, 3,5-diaminobenzoic acid lanostanyl, and 3,6-bis(4-aminobenzoyloxy)cholestane; Diamine represented by the following formulas (V-1) to (V-6); Groups of the following formulas (5-1) to (5-11), such as "-N(D)-" (D represents a protecting group that is removed by heating and replaced by a hydrogen atom, and is preferably a tert-butoxycarbonyl group. ) diamine with ; Diamines having siloxane bonds, such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and diamine represented by the following formula (Ds-1); Diamines having oxazoline structures such as the following formulas (Ox-1) to (Ox-2); Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'- Methylenebis(cyclohexylamine), a diamine in which two amino groups are bonded to a group represented by any of the formulas (Y-1) to (Y-167) described in International Publication No. 2018/117239, etc.

[Formula 4]

(Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ar may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is a monovalent group. May be substituted. p is an integer of 0 or 1. Q ₂ is -(CH ₂ ) _n - (n is an integer from 2 to 18), or -(CH ₂ ) _n - of -CH ₂ - Indicates a group in which at least part of the group has been replaced with any of -O-, -C(=O)-, or -OC(=O)-.)

[Formula 5]

[Formula 6]

(When there are two or more ms, the two or more ms may be the same or different. One or more hydrogen atoms on the benzene ring may be substituted with a monovalent group.)

[Formula 7]

(In formula (3b-1), A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO- is represented, m1 and m2 are each independently an integer of 0 to 4, and m1+m2 is an integer of 1 to 4. In formula (3b-2), m3 and m4 are each independently an integer of 1 to 5. In formula (3b-3), A ² represents a straight-chain or branched alkyl group of 1 to 5 carbon atoms, and m5 is an integer of 1 to 5. Formula (3b) -4) Among them, A ³ and A ⁴ are each independently a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N-(CH ₃ )CO-, and m6 is an integer of 1 to 4.)

[Formula 8]

(In formulas (V-1) ^to ( _V -6 ⁾ _, X ^{v1 to} ), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-, ^v5 represents -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. X _a is a single bond, -O-, -NH-, or -O-(CH ₂ ) represents _m -O- (m represents an integer of 1 to 6), and R ^v1 to R ^v4 and R ^1a to R ^1b are each independently an alkyl group of 1 to 20 carbon atoms or an alkyl group of 1 to 20 carbon atoms. Represents an alkoxy group or an alkoxyalkyl group having 2 to 20 carbon atoms. The two k may be the same or different.)

[Formula 9]

(In formulas (5-1) to (5-11), Boc represents a tert-butoxycarbonyl group.)

[Formula 10]

[Formula 11]

In the formula (d _o ), the monovalent group includes a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a fluoroalkyl group with 1 to 10 carbon atoms, Examples include a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxyl group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.

As diamine represented by said formula (d _o ), from a viewpoint of improving liquid crystal orientation, diamine represented by the following formula (d _o -1) - (d _o -6), 3,3'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferred.

[Formula 12]

In the diamine represented by the above formula (O), any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring may be substituted with a monovalent group. Examples of the monovalent group include a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a fluoroalkyl group with 1 to 10 carbon atoms, and a group with 2 to 10 carbon atoms. Examples include a fluoroalkenyl group, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.

As diamine represented by said formula (O), diamine represented by following formula (o-1) - (o-16) is preferable from a viewpoint of improving liquid crystal orientation.

[Formula 13]

[Formula 14]

[Formula 15]

(In formula (o-14), two m's may be the same or different.)

Examples of nitrogen atom-containing heterocycles that the diamine having the specific nitrogen atom-containing structure may have include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, and benzoimine. Dazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, and hexamethylene imine. Among these, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine are preferred.

The secondary amino group and tertiary amino group that the diamine having the above-mentioned specific nitrogen atom-containing structure may have are represented by the following formula (n), for example.

[Formula 16]

In the formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "*" represents a bond bonded to a hydrocarbon group, and at least one bond to an aromatic hydrocarbon group.

Examples of the monovalent hydrocarbon group of R in the formula (n) include alkyl groups such as methyl, ethyl, and propyl groups; Cycloalkyl groups such as cyclohexyl groups; Aryl groups such as phenyl group and methylphenyl group can be mentioned. R is preferably a hydrogen atom or a methyl group.

Specific examples of diamines having the above-mentioned specific nitrogen atom-containing structure include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 3,6-diamino. Carbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-dia Minocarbazole, N-phenyl-3,6-diaminocarbazole, diamine represented by the following formulas (Dp-1) to (Dp-8), and represented by the following formulas (z-1) to formula (z-18) Diamine can be mentioned.

[Formula 17]

[Formula 18]

[Formula 19]

Y is a diamine represented by the formula (O), a diamine having an amide bond or a urea bond, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamin Minodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-amino) Benzyl)benzene, diamine represented by the above formula (d _o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and the group “-N(D)-” (D is A divalent organic group derived from a diamine selected from the group consisting of diamines having a protective group that is removed by heating and replaced by a hydrogen atom, and is preferably a tert-butoxycarbonyl group, is preferred. When Y satisfies the configuration, the effect of reducing afterimages generated during long-term alternating current driving is obtained, which is preferable.

In the formula (a), X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. In addition, the tetravalent organic group derived from tetracarboxylic dianhydride or its derivatives includes, for example, a tetravalent organic group obtained by removing four carboxyl groups from the corresponding tetracarboxylic acid. The tetravalent organic group includes a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride or a derivative thereof, or aromatic tetracarboxylic group. Examples include tetravalent organic groups derived from acid dianhydride or its derivatives.

Here, acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it is not necessary to be composed only of a chain-like hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxyl groups are bonded to the aromatic ring. Moreover, it is not necessary to be comprised only of an alicyclic structure, and may have a chain-like hydrocarbon structure or an aromatic ring structure in part. Aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring.

Derivatives of the tetracarboxylic acid dianhydride include tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide.

The tetracarboxylic dianhydride or its derivative may be used individually by 1 type, or may be used in combination of 2 or more types.

The acyclic aliphatic or alicyclic tetracarboxylic dianhydride, or a derivative thereof, is, among others, at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, from the viewpoint of increasing the liquid crystal orientation. It is preferable that they are tetracarboxylic dianhydride or derivatives thereof which have one kind of partial structure.

Said X is preferably a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof represented by the following formula (t).

[Formula 20]

In the formula, X ₁ is a structure selected from the following formulas (X1-1) to (X1-25). * indicates a binding hand.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In formulas (X1-1) to (X1-4), R ₁ to R ₂₁ are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, or a C 2 to 2 alkyl group. It represents an alkynyl group of 6, a monovalent organic group of 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * indicates a binding hand. From the viewpoint of improving the liquid crystal orientation, R ₁ to R ₂₁ are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and are more preferably a hydrogen atom or a methyl group.

In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, - COO-, represents a phenylene group, a sulfonyl group, or an amide group. A plurality of A ₂ may be the same or different.

Specific examples of the formula (X1-1) include the following formulas (1-1) to (1-6). From a viewpoint of improving liquid-crystal orientation, formula (1-1) and (1-2) are especially preferable. * has the same meaning as above.

[Formula 25]

Preferred specific examples of the above formulas (X1-24) and (X1-25) include the following formulas (X1-26) to (X1-41). * has the same meaning as above.

[Formula 26]

[Formula 27]

From the _viewpoint of increasing the liquid crystal orientation, the or (X1-26) to (X1-30) are preferred, and the above formulas (X1-1), (X1-5), (X1-7) to (X1-10), (X1-21), (X1 -23), (X1-24) to (X1-25), or (X1-26) to (X1-30) are more preferable, and the formulas (1-1), (1-2), (X1- 5), (X1-7), (X1-9), or (X1-26) to (X1-30) are more preferable.

The monovalent organic group for R and Z in the above formula (a) is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO-, and -COO -, -COS-, -NR ³ - (However, R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.), -CO-NR ³ - (However, R ³ is a hydrogen atom or a carbon number. It is a monovalent hydrocarbon group with 1 to 10 carbon atoms), -Si(R ³ ) ₂ - (However, R ³ is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms), -SO ₂ -, etc. At least one of the hydrogen atoms bonded to the monovalent group A, the monovalent hydrocarbon group, or the carbon atom of the monovalent group A is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxy group, 1 formed by substitution with an alkoxy group, nitro group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulfino group, phosphino group, carboxyl group, cyano group, sulfo group, acyl group, etc. Examples include a valent group and a monovalent group having a heterocyclic ring. The monovalent organic groups for R and Z in the formula (a) include, among others, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, and tert-butoxy. A carbonyl group or a 9-fluorenylmethoxycarbonyl group is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable.

From the viewpoint of obtaining the effects of the present invention, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the formula (a), X, Y, R, and Z may be one type or two or more types, respectively.

The content ratio of the polymer (A) is preferably 70 to 99 parts by mass, and more preferably 80 to 98 parts by mass, in 100 parts by mass of the polymer composition.

(Repeating unit constituting polymer (A))

The polymer (A) in the present invention is at least one type of polymer selected from the group consisting of a polyimide precursor having a repeating unit represented by the above formula (a) and a polyimide that is an imidate of the polyimide precursor. The polymer (A) may have the repeating unit and terminal group represented by said formula (a).

Here, the terminal group refers to a group bonded to the terminal of the repeating unit constituting the polymer (A). Examples of the terminal group include an amino group, a carboxy group, an acid anhydride group, an isocyanate group, or derivatives thereof. The amino group, carboxyl group, acid anhydride group, and isocyanate group are obtained by a conventional condensation reaction, and the derivative can be obtained by sealing the terminal group using, for example, an end capping agent, as described later.

The total of the repeating unit represented by formula (a) and its imidized structure is preferably 10 mol% or more, and more preferably 20 mol% or more of the total repeating units constituting the polymer (A).

(Repeating unit represented by formula (U))

The polymer (A) in the present invention may further have a repeating unit represented by the following formula (U).

[Formula 28]

(U ₁ is a divalent organic group, U _1' is a divalent organic group derived from diamine, and C ₁ and C _1' are each independently a hydrogen atom or a monovalent organic group.)

In the above formula (U), U ₁ is a divalent organic group. Examples of U ₁ include a divalent organic group derived from diisocyanate. The diisocyanate may be used individually by 1 type, or may be used in combination of 2 or more types.

Here, examples of diisocyanate include aromatic diisocyanate and aliphatic diisocyanate.

Here, "aromatic diisocyanate" means diisocyanate having at least one aromatic group. Additionally, “aliphatic diisocyanate” means diisocyanate that has an aliphatic group and no aromatic group.

Examples of U ₁ include (i) 2 derived from aromatic diisocyanate, wherein in the diisocyanate structure (O=C=NRN=C=O), R is an organic group of 6 to 30 carbon atoms having at least one benzene ring; 2 derived from an aliphatic diisocyanate, which is a valent organic group, or (ii) a diisocyanate structure (O=C=NRN=C=O) where R is an organic group of 4 to 30 carbon atoms having an aliphatic group and no aromatic group. A organic group can be mentioned.

Moreover, an aliphatic group includes both an acyclic aliphatic group and an alicyclic group.

Specific examples of U ₁ include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate (e.g., 2,4-diisocyantolylene, 2,6-diisocyanate) Tolylene isocyanate), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylene, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 4,4 '-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanate phenyl)propane, 4,4'-diisocyanate diphenylmethane (4,4'-diphenylmethane diisocyanate), 4, Aromatic diisocyanates such as 4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, and 2,2'-diisocyanate benzophenone. and divalent organic groups derived from aliphatic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

In the above formula (U), U _1' is a divalent organic group derived from diamine. Examples of the diamine include the diamines exemplified by the repeating unit (a), and preferred embodiments are the same as above.

The monovalent organic groups of C ₁ and C _1' in the formula (U) include the structures exemplified by R and Z of the repeating unit (a). From the viewpoint of obtaining the effects of the present invention, C ₁ and C _1' are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the above formula (U), one type of U ₁ , U _1' , C ₁ , and C _1' may be used, respectively, or two or more types may be used.

When the polymer (A) in the present invention has a repeating unit represented by the formula (U), the content ratio of the repeating unit represented by the formula (U) is determined by the repeating unit ( a), 1 to 30 mol% is preferable, and 2 to 25 mol% is more preferable, relative to a total of 100 mol% of the imidized structure of the repeating unit (a) and the repeating unit represented by the formula (U).

＜Polyurethane＞

The polymer composition of the present invention contains a polyurethane that has a repeating unit represented by the formula (1) and does not have a repeating unit represented by the formula (a) and its imidized structure. At least one of A ₁ and A ₂ in the formula (1) has a divalent organic group represented by the formula (EG).

Polyurethane may be used individually by 1 type, and may be used in combination of 2 or more type.

(Repeating unit represented by equation (1))

In the above formula (1), A ₁ is a divalent organic group derived from diisocyanate. In addition, the divalent organic group derived from diisocyanate includes, for example, a divalent organic group obtained by removing two isocyanate groups (-N=C=O) from diisocyanate. The diisocyanate may be used individually by 1 type, or may be used in combination of 2 or more types.

Here, examples of the diisocyanate include diisocyanate (DI EG ) having a divalent organic group represented by the above formula ( _EG ), aromatic diisocyanate other than diisocyanate (DI _EG ), and aliphatic diisocyanate.

Here, "aromatic diisocyanate" means diisocyanate having at least one aromatic group. Additionally, “aliphatic diisocyanate” means diisocyanate that has an aliphatic group and no aromatic group.

Examples of the diisocyanate (DI _EG ) include diisocyanate shown below.

[Formula 29]

As aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ), for example, (i) in the diisocyanate structure (O=C=NRN=C=O), R is the formula (EG) In the aromatic diisocyanate, or (ii) diisocyanate structure (O=C=NRN=C=O), which is an organic group of 6 to 30 carbon atoms and has at least one benzene ring and does not have a divalent organic group represented by Examples of the aliphatic diisocyanate include an aliphatic diisocyanate that has an aliphatic group and is an organic group having 4 to 30 carbon atoms without a divalent organic group or an aromatic group represented by the above formula (EG).

Additionally, the aliphatic group includes both acyclic aliphatic groups and alicyclic groups.

Specific examples of aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ) include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate (e.g., 2, 4-diisocyanate tolylene, 2,6-diisocyanate tolylene), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylene, 3,3'-dimethyl- 4,4'-diisocyanate biphenyl, 4,4'-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanate phenyl)propane, 4,4'-diisocyanate diphenylmethane (4 Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate), 4,4'-diphenyl sulfone diisocyanate, 3,3'-diphenyl sulfone diisocyanate, and 2,2'-benzophenone diisocyanate. , isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

In the above formula (1), A ₂ is a divalent organic group obtained by removing the hydrogen atoms contained in two hydroxy groups from the organic diol. The organic diol may be used individually by 1 type, or may be used in combination of 2 or more types. As the organic diol, a diol containing a divalent organic group represented by the above formula (EG); Diols not containing a divalent organic group represented by the above formula (EG), specifically, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1, 4-Butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol , alkylenediols such as 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol; Dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), dimethylolbutanoic acid (2,2-bis(hydroxymethyl)butanoic acid), 2,3-dihydroxybenzoic acid, 2,4-dihyde Carboxyl group-containing diols such as hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid; polypropylene glycol; Random copolymer of polypropylene glycol and neopentyl glycol; Polyesterdiol obtained by reacting a polyhydric alcohol with a polybasic acid; Polycarbonate diol having a carbonate skeleton; Polycaprolactone diol obtained by subjecting lactones such as γ-butyllactone, ε-caprolactone, and δ-valerolactone to a ring-opening addition reaction; Bisphenol A; Ethylene oxide adduct of bisphenol A; Ethylene oxide adduct of hydrogenated bisphenol A; Propylene oxide adduct of bisphenol A; Hydrogenated bisphenol A; and propylene oxide adducts of hydrogenated bisphenol A.

The diol containing the divalent organic group represented by the formula (EG) is not particularly limited as long as the molecule contains the formula (EG), but diol containing the divalent organic group represented by the formula (EG) is reacted with a polybasic acid. or a diol in which hydrogen atoms are bonded to both ends of the formula (EG), preferably a diol in which hydrogen atoms are bonded to both ends of the formula (EG). In the diol in which hydrogen atoms are bonded to both ends of the formula (EG), the upper limit of n is preferably set such that the upper limit of the weight average molecular weight of the diol is 5,000 or less, and the upper limit of the weight average molecular weight of the diol is 4,000 or less. More preferably, it is set so that the upper limit of the weight average molecular weight of the diol is set to be 3,000 or less. As for the upper limit of n from a viewpoint of improving liquid-crystal orientation, 40 is preferable, 30 is more preferable, and 20 is especially preferable. From the viewpoint of improving the liquid crystal orientation, the lower limit of n is preferably 5, and more preferably 6. More specifically, the diol containing the divalent organic group represented by the formula (EG) is pentaethylene glycol, hexaethylene glycol, trade names PEG-300, PEG-400, PEG-600, PEG-1000 manufactured by Sanyo Chemical Industry Co., Ltd.; PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000; Product names PEG300, PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, PEG20000, PEG35000 manufactured by Merck; Product numbers P2139, P3265, P3515, 81210, 81240, 81260, 81285, 81310, 181986, 181994, 182001, 182028, 189456, 202304, 202312, manufactured by SIGMA-ALDRICH 202320, 202339, 202398, 202421, 202436, 202444, 202452, 295906, 309028, 372773, 372781, 373001, 412325, 435406, 435422, 435457, 637726 ; Product names SINOPOL PEG600, SINOPOL PEG1500, SINOPOL PEG4000 manufactured by Sino-Japan Synthetic Chemical Company; Product names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M manufactured by Lion Specialty Chemicals, PEG#6000M, product name Polyethylene Glycol 400 manufactured by Tokyo Chemical Industry Co., Ltd. One commercially available product is Polyethylene Glycol 600. Preferable specific examples of diols having hydrogen atoms bonded to both ends of the above formula (EG) include pentaethylene glycol, hexaethylene glycol, trade names PEG-300, PEG-400, PEG-600, PEG-1000, manufactured by Sanyo Chemical Industry Co., Ltd., manufactured by Merck. Product name PEG300, PEG1000 manufactured by Merck, PEG300 manufactured by Merck, PEG1000 manufactured by Chongil Synthetic Chemical Co., Ltd., trade name SINOPOL PEG600, trade name PEG#300, PEG#400, PEG#600, PEG#1000 manufactured by Lion Specialty Chemicals, Polyethylene glycol represented by the product names Polyethylene Glycol 400 and Polyethylene Glycol 600 of Tokyo Chemical Industry Co., Ltd., or pentapropylene glycol, hexapropylene glycol, and polypropylene glycol (a more preferable average molecular weight is polypropylene glycol having an average molecular weight of 400 to 5,000 .), and copolymers made of ethylene oxide and propylene oxide with an average molecular weight of 500 to 5000. As the polyethylene glycol or polypropylene glycol, those obtained by subjecting ethylene oxide or propylene oxide to anionic ring-opening polymerization may be used. The polymerization reaction can be carried out using a polymerization initiator (eg, water, ethylene glycol, propylene glycol, etc.) and a catalytic amount of base (eg, potassium hydroxide).

In addition, the average molecular weight of the glycol illustrated in the diol containing a divalent organic group represented by the above (EG) is a weight average molecular weight obtained on the basis of polystyrene by gel permeation chromatography (GPC).

(Repeating unit that makes up polyurethane)

The polyurethane in this invention is a polyurethane which has the repeating unit represented by said formula (1), and does not have the repeating unit represented by said formula (a) and its imidation structure. The polyurethane in the present invention may have a repeating unit and a terminal group represented by the above formula (1). The terminal group is as described above.

10 mol% or more of the whole repeating unit which comprises polyurethane is preferable, and, as for the content rate of the repeating unit represented by said formula (1), 20 mol% or more is more preferable.

In addition, the content ratio of the repeating unit represented by formula (1), where A ₂ is a divalent organic group derived from a diol with hydrogen atoms bonded to both ends of the formula (EG), is 10 mol% or more of the total repeating units constituting the polyurethane. is preferable, 20 mol% or more is more preferable, and 50 mol% or more is still more preferable.

In the above formula (1), one type of A ₁ and A ₂ may be used, or two or more types may be used.

The polyurethane content in the present invention is preferably from 1 to 30 parts by mass, more preferably from 2 to 20 parts by mass, based on 100 parts by mass of the polymer composition.

<Production of polymer (A)>

Examples of the polyimide precursor of the polymer (A) include polyamic acid and polyamic acid ester.

Polyamic acid (polyimide precursor having a repeating unit represented by formula (a) in which R in the formula (a) is a hydrogen atom) can be manufactured by the following method. Specifically, the tetracarboxylic acid component containing the tetracarboxylic dianhydride or a derivative thereof and the diamine component containing the diamine are stored at -20 to 150°C, preferably 0 to 50°C, in the presence of an organic solvent. It can be synthesized by conducting a (polycondensation) reaction for 30 minutes to 24 hours, preferably for 1 to 12 hours. When the polyamic acid has the repeating unit (U), the polyamic acid represented by O=C=NU ₁ -N=C=O (U ₁ is the same as U ₁ in the formula (U)) It can be synthesized by reacting an isocyanate compound with the tetracarboxylic acid component and the diamine component.

Specific examples of the organic solvent used in the above reaction include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N -Dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone can be mentioned. Moreover, when the solvent solubility of a polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] - formula [D- 3] The solvent represented by can be used. These may be used in mixture of two or more types.

[Formula 30]

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.).

The reaction can be carried out at any concentration, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be initially carried out at a high concentration, and then a solvent may be added. In reaction, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic acid component is 0.8-1.2. As with a typical polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced.

The polyamic acid obtained by the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring it well. Further, a purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heat. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

When the polyimide precursor is a polyamic acid ester, (1) a method of esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine, (2) a method by reaction of tetracarboxylic acid diester dichloride and diamine, (3) It can be produced by known methods such as polycondensation of tetracarboxylic diester and diamine.

[End sealant]

When synthesizing the polymer (A) in the present invention, a tetracarboxylic acid component containing tetracarboxylic dianhydride or a derivative thereof, a diamine component, and optionally a diisocyanate compound together with a suitable terminal blocker It may be used to synthesize an end-blocked polymer.

As the end capping agent, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, the following formula (m -1) The compound represented by - (m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoro Acid anhydrides such as loisobenzofuran-1,3-dione and 4-ethynylphthalic anhydride;

[Formula 31]

Diester dicarbonate compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; Chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; Aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine , monoamine compounds such as n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; monoisocyanate compounds such as isocyanates having unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate; Isothiocyanate compounds, such as ethyl isothiocyanate and allyl isothiocyanate, are mentioned.

The use ratio of the terminal blocker is preferably 20 parts by mole or less, more preferably 10 parts by mole or less, based on 100 parts by mole in total of the diamine component used and the organic diol component used as necessary.

Moreover, polyimide can be obtained by ring-closing (imidizing) the polyimide precursor (A) of the polymer (A). In addition, the imidation rate as used herein refers to the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof). The imidization rate does not necessarily have to be 100% and can be arbitrarily adjusted depending on the use or purpose.

As a method of imidating the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to the solution of the polyimide precursor is exemplified.

The temperature in the case of thermal imidation of the polyimide precursor in the solution is preferably 100 to 400 ° C., more preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction to the outside of the system do.

Catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor, followed by stirring at preferably -20 to 250°C, more preferably 0 to 180°C. The amount of the basic catalyst is preferably 0.5 to 30 mole times, more preferably 2 to 20 mole times the amount of the amic acid group, and the amount of the acid anhydride is preferably 1 to 50 mole times, more preferably 3 to 30 mole times the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like, and among these, pyridine is preferable because it has a basicity suitable for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among these, acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidization rate by catalyst imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate it, when collect|recovering the produced|generated polyimide precursor or polyimide from the polyimide precursor or the reaction solution of a polyimide. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by pouring into the solvent can be recovered by filtration, and then dried by heating or at room temperature under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by repeating, for example, 2 to 10 times the operation of redissolving the polymer recovered by precipitation in an organic solvent and recovering by reprecipitation. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more types of solvents selected from among these, since the efficiency of purification is further increased.

The molecular weight of the polymer (A) used in the present invention is 5,000 to 5,000 as a weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of film formation, and the coating film property are considered. It is preferably 1,000,000, and more preferably 10,000 to 150,000.

＜Manufacture of polyurethane＞

The polyurethane is obtained, for example, by reacting component (o) containing an organic diol having two hydroxy groups in a molecule with component (i) containing a compound containing two isocyanate groups in a molecule. Here, at least one of the compounds constituting the above-mentioned component (o) and component (i) has in its molecule a partial structure represented by the following formula (EG).

[Formula 32]

(n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)

The number of (o) component and (i) component may be one, respectively, and two or more types may be sufficient as them.

(o) Components include, for example, organic diols exemplified by the repeating unit represented by the above formula (1), and "HA ₂ -H" (A ₂ is A ₂ in formula (1) (Same as.) Diol compounds represented by can be mentioned.

(i) Components include, for example, diisocyanate compounds represented by O=C=NA ₁ -N=C=O (A ₁ is the same as A ₁ in formula (1)). there is.

In the case where (o) a diol compound represented by "HA ₂ -H" is contained as a component and a diisocyanate compound represented by O=C=NA ₁ -N=C=O as (i) component, "HA ₂ - At least one of A ₂ in the diol compound represented by “H” and A ₁ in the diisocyanate compound represented by O=C=NA ₁ -N=C=O has a partial structure represented by the above formula (EG). It has within the molecule. Preferred specific examples thereof are as described above.

The reaction of component (o) and component (i) is usually carried out in an organic solvent. The organic solvent used at that time is not particularly limited as long as it dissolves the produced polyurethane. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, hexamethyl phosphate triamide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone. , methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl. Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutylacetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone. , methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate. , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methoxy ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, diglyme, or 4-hydroxy-4-methyl-2-pentanone; and the like. . These may be used individually or mixed. Additionally, even if it is a solvent that does not dissolve polyurethane, it may be used by mixing it with the above solvent. In addition, since moisture in the organic solvent is a cause of inhibiting the polymerization reaction, it is preferable to use a dehydrated organic solvent.

A method for synthesizing a polyurethane obtained by reacting component (o) containing an organic diol used in the present invention with component (i) containing a diisocyanate compound containing two isocyanate groups in a molecule includes (o) component and ( i) The blending amount of the component is organic such that the ratio of the number of hydroxy groups to the number of isocyanate groups is isocyanate group/hydroxy group = 0.8 or more and 1.2 or less, preferably 0.9 or more and 1.2 or less, more preferably 0.9 or more and 1.1 or less. It is obtained by reacting in a solvent.

In addition, when two or more types of organic diols are used, the reaction with the diisocyanate compound may be performed after mixing the two or more types of organic diols, or each organic diol and the diisocyanate compound may be reacted separately. Moreover, after reacting an organic diol and a diisocyanate compound, the obtained terminal isocyanate compound may be reacted with another organic diol compound, and this may be reacted again with a diisocyanate compound. Moreover, the same applies when two or more types of diisocyanate compounds are used. In this way, the desired polyurethane can be produced.

The reaction temperature of component (o) and component (i) is preferably 0 to 160°C, and more preferably 10 to 150°C. The reaction time can be appropriately selected depending on the reaction scale and the reaction conditions employed. Additionally, if necessary, the reaction may be carried out in the presence of a catalyst such as a metal or semimetal compound such as tertiary amines, alkali metal, alkaline earth metal, tin, zinc, titanium, and cobalt. The concentration of the total amount of component (o) and component (i) is preferably 1 to 50 mass%, more preferably 5 to 30 mass% in the reaction liquid. The reaction may be initially carried out at a high concentration, and then an organic solvent may be added.

The molecular weight of the polyurethane used in the present invention is 4,000 to 80,000 as a weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, when considering the strength of the liquid crystal alignment film obtained therefrom, workability at the time of film formation, and coating film properties It is preferable, and more preferably, it is 6,000 to 60,000.

The polymer composition of the present invention may contain other polymers other than polymer (A) and polyurethane. Specific examples of other polymers include polyimide precursors other than polymer (A) or imidates thereof, polyurethanes other than the above polyurethanes, polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, and cellulose derivatives. , polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinylether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) ) derivatives, polymers selected from the group consisting of poly(meth)acrylates, etc. Specific examples of the poly(styrene-maleic anhydride) copolymer include SMA1000, 2000, 3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac), and the like, and poly(isobutylene-maleic anhydride) ) Specific examples of the copolymer include Isobam-600 (manufactured by Kuraray), and specific examples of the poly(vinyl ether-maleic anhydride) copolymer include GANTREZ AN-139 (methyl vinyl ether maleic anhydride) Acid resin, manufactured by ISP Japan Co., Ltd.) can be mentioned.

Other polymers may be used individually by 1 type, or may be used in combination of 2 or more types. The content of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, still more preferably 20 to 80 parts by mass, based on 100 parts by mass in total of the polymers contained in the polymer composition.

The polymer composition according to the present invention is preferably a liquid composition in which the polymer (A) and polyurethane are dissolved or dispersed in an organic solvent. Specifically, the organic solvent contained in the polymer composition is not particularly limited as long as it dissolves the polymer component uniformly, but may include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, , N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyro Lactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy -N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N- (t-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, Examples include N-methoxybutyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone (these are also collectively referred to as “good solvents”). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ -Butyrolactone is preferred. The content of the good solvent is preferably 20 to 99% by mass of the total solvent contained in the polymer composition, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass.

In addition, as for the organic solvent contained in the polymer composition, it is preferable to use a mixed solvent in which a solvent (also referred to as a poor solvent) that improves the coatability at the time of applying the polymer composition or the surface smoothness of the coating film is used in combination with the above solvent. . Specific examples of poor solvents used in combination are given below, but are not limited to these. The content of the poor solvent is preferably from 1 to 80% by mass, more preferably from 10 to 80% by mass, particularly preferably from 20 to 70% by mass, based on the total amount of solvents contained in the polymer composition. The type and content of the poor solvent are appropriately selected depending on the coating device, application conditions, application environment, etc. of the liquid crystal aligning agent.

As a poor solvent, for example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether. Butyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, Ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy) -1-Propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether , Diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, Diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl acetate. Ether, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl propionate, butyl 3-methoxypropionate, Examples include n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, and diisobutyl ketone (2,6-dimethyl-4-heptanone).

Among them, diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2 -Pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred.

Preferred combinations of good solvents and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, and ethylene glycol monobutyl ether. , N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4 -Hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether, N -Ethyl-2-pyrrolidone and 3-ethoxy ethyl propionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 3-ethoxy ethyl propionate and diethylene glycol monopropyl ether, N-ethyl- 2-pyrrolidone, ethyl 3-ethoxypropionate, diethylene glycol monopropyl ether, N-methyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone, and dipropylene glycol. Dimethyl ether, N,N-dimethyllactamide and ethylene glycol monobutyl ether, N,N-dimethyllactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone, diethylene glycol diethyl ether, N-ethyl -2-pyrrolidone, diethylene glycol monoethyl ether, butyl cellosolve acetate, N-methyl-2-pyrrolidone, diethylene glycol monomethyl ether, butyl cellosolve acetate, N,N-dimethyllactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-ethyl-2- Pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentaone Paddy and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy- 4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2- Pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether , γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N -Methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisobutyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diiso Propyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol Monobutyl ether and diisobutylcarbinol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol Dimethyl ether, N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, N- Ethyl-2-pyrrolidone, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, propylene glycol diacetate, N-ethyl-2-p Rolidone and propylene glycol monobutyl ether and diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and diisobutyl ketone, N-ethyl-2-pyrrolidone and N,N-dimethyl Lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone, ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, γ-butyrolactone, ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate, propylene glycol dimethyl ether, N-methyl-2-pyrrolidone, 4-methyl-2-pentyl acetate, ethylene glycol monobutyl ether, N-ethyl -2-pyrrolidone, cyclohexyl acetate and diacetone alcohol, N,N-dimethylpropionamide and 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylpropionamide and propylene glycol diacetate; Tetramethylurea and 4-hydroxy-4-methyl-2-pentanone, tetramethylurea and propylene glycol diacetate, N,N-dimethylpropionamide and propylene glycol monobutyl ether, tetramethylurea and propylene glycol monobutyl ether , tetramethyl urea, cyclohexanone and propylene glycol monomethyl ether, N,N-dimethylpropionamide and propylene glycol monomethyl ether, N,N-dimethylpropionamide and ethylene glycol monobutyl ether acetate, N,N-dimethylpropionamide. and ethylene glycol monobutyl ether, tetramethyl urea and propylene glycol monomethyl ether, N,N-dimethylpropionamide, cyclohexanone and diethylene glycol diethyl ether, N,N-diethylformamide and propylene glycol monomethyl ether, N,N-diethylformamide and 4-hydroxy-4-methyl-2-pentanone, N,N-diethylformamide and propylene glycol monomethyl ether, cyclohexanone and propylene glycol monomethyl ether, cyclopentanone Examples include propylene glycol monomethyl ether, N-methyl-2-pyrrolidone, cyclohexanone, and propylene glycol monomethyl ether.

The polymer composition of the present invention may additionally contain components other than the polymer component and the organic solvent (hereinafter also referred to as additive components). These additive components include, for example, crosslinkable compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, compounds for adjusting the dielectric constant and electrical resistance of the resin film, etc. I can hear it.

Examples of the crosslinkable compound include a crosslinkable compound (c- 1), and a crosslinkable compound (c-2) having a polymerizable unsaturated group.

By containing the crosslinkable compound, the effect of being able to obtain a liquid crystal display element with reduced occurrence of so-called flicker, which occurs when backlight light is irradiated to the liquid crystal display element immediately after driving the liquid crystal, is also obtained.

Preferred specific examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds.

As a compound (c-1) having an epoxy group, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl. Dyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 , 5,6-tetraglycidyl-2,4-hexanediol, bisphenol A-type epoxy resins such as Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), and bisphenol F-type epoxy resins such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation). , hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), biphenyl skeleton-containing epoxy resins such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), and phenol novolaks such as EPPN-201 (manufactured by Nippon Chemical Company). type epoxy resin, (o,m,p-) cresol novolac type epoxy resin such as EOCN-102S (manufactured by Nippon Chemical Co., Ltd.), tetrakis(glycidyloxymethyl)methane, N,N,N',N' -Tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4.4'-diaminobiphenyl, 2,2-bis[ Agents such as 4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom; N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N, N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycy) Dil-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycy) dilaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4- Bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-di Compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom such as glycidylaminomethyl)benzene, isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.), Japanese Patent Publication Review a compound described in paragraph [0037] of No. 10-338880, a compound described in WO2017/170483, and the like;

As a compound having an isocyanate group, the above-mentioned diisocyanate compound, etc.;

As a compound (c-1) having an oxetanyl group, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (aronoxetane OXT-121 (XDO)), di [2-(3-oxetanyl)butyl]ether (alonoxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), Compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of WO2011/132751, etc.;

As a compound (c-1) having a cyclocarbonate group, N,N,N',N'-tetrakis[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-dia Minodiphenylmethane, N,N'-bis[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine, compounds described in WO2011/155577, etc.;

Compounds having a block isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Milionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B. -820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals), two described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978 Compounds having the above protected isocyanate groups, compounds having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of WO2015/141598, etc.;

As a compound (c-1) having a hydroxy group and/or an alkoxy group, N,N,N',N'-tetrakis(2-hydroxyethyl)adipoamide, 2,2-bis(4-hydroxy -3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihyde Roxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, a compound described in paragraph [0058] of International Publication No. 2015/072554 or Japanese Patent Publication No. 2016-118753, Japanese Patent Publication 2016- Compounds described in No. 200798, compounds described in WO2010/074269, etc.;

As a crosslinkable compound (c-2) having a polymerizable unsaturated group, glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-body mixture), glycerin tris(meth)acrylate Latex, glycerol 1,3-diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono. (meth)acrylate, pentaethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, etc.

More preferable examples of the crosslinkable compounds (c-1) and (c-2) include compounds represented by any of the following formulas (CL-1) to (CL-12).

[Formula 33]

[Formula 34]

The above is an example of a crosslinkable compound, and is not limited to these. Moreover, the number of crosslinkable compounds used for the liquid crystal aligning agent of this invention may be one, and two or more types may be combined.

Content of the crosslinkable compound in the liquid crystal aligning agent of this invention is 0.1-150 mass parts, or 0.1-100 mass parts, or 1-50 mass parts with respect to 100 mass parts of all polymer components.

Compounds for adjusting the dielectric constant and electrical resistance of the resin film include monoamines having a nitrogen atom-containing aromatic heterocycle, such as 3-picolylamine. When using a monoamine having a nitrogen-containing aromatic heterocycle, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the polymer composition.

Preferred specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltrimethoxysilane. Propyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxy Silane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris( Examples include 3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanate propyltriethoxysilane. When using a functional silane compound, the amount used is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the polymer composition.

The solid content concentration in the polymer composition (the ratio of the total mass of components other than the solvent in the polymer composition to the total mass of the polymer composition) is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 1 to 10 mass%. It is a range. That is, the polymer composition is applied to the surface of the substrate, as described later, and is preferably heated to form a resin film.

The range of a particularly preferable solid concentration varies depending on the method used when applying the polymer composition to the substrate. For example, when using the spin coating method, it is particularly preferable that the solid content concentration is in the range of 1.5 to 4.5% by mass. In the case of the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa·s. The temperature when preparing the polymer composition is preferably 10 to 50°C, more preferably 20 to 30°C.

＜Uses and resin film＞

The polymer composition described above can be applied, for example, on a substrate, and a resin film can be formed by volatilizing the solvent component, preferably by heat treatment. The polymer composition and resin film according to the present invention can be effectively applied to various technical applications, such as liquid crystal aligning agents, electronic circuit materials, semiconductor materials, electrical insulation materials, wire coating materials, lighting applications, and molding materials. It can be applied to a variety of uses. Specifically, it can be applied to various resin films equipped with display elements, semiconductor elements, actuators such as motors, various sensors such as piezoelectric sensors and pyroelectric sensors, etc., and liquid crystal alignment films (a liquid crystal alignment film for phase difference films, scanning antennas, liquid crystal alignment film for liquid crystal array antenna or liquid crystal alignment film for transmission scattering type liquid crystal light control device), protective film (e.g. protective film for color filter), spacer film, interlayer insulating film, antireflection film, wiring coating film, antistatic film, motor An insulating film (gate insulating film of a flexible display), etc. can be mentioned. Among these, the polymer composition concerning this invention can be preferably applied as a liquid crystal aligning agent.

＜Liquid crystal alignment agent＞

The liquid crystal aligning agent which concerns on this invention consists of the polymer composition which concerns on this invention. That is, the liquid crystal aligning agent concerning this invention contains the said polymer (A) and polyurethane similarly to a polymer composition. Moreover, it is preferable to contain at least any of other polymers, organic solvents, and additive components. The description of the polymer composition can be applied to the details of the polymer (A), polyurethane, other polymers, organic solvents, additive components, blending ratio, solid concentration, and the like.

[Liquid crystal alignment film and liquid crystal display device]

By using the polymer composition or the liquid crystal aligning agent, a liquid crystal alignment film can be produced as a resin film. Moreover, the liquid crystal display element which concerns on this invention is equipped with the liquid crystal aligning film formed using the said polymer composition or the said liquid crystal aligning agent. The operation mode of the liquid crystal display device related to the present invention is not particularly limited, and examples include TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), It can be applied to various operation modes such as in-plane switching type (IPS type), FFS type, and optical compensation bend type (OCB type).

The liquid crystal display device of the present invention is, for example, a method comprising the following steps (1) to (4), a method including steps (1) to (2) and (4), and steps (1) to (3). ), (4-2), and (4-4), or a method including steps (1) to (3), (4-3), and (4-4).

＜Step (1): Step of applying a liquid crystal alignment agent on a substrate＞

Process (1) is a process of apply|coating the liquid crystal aligning agent of this invention on a board|substrate. Specific examples of step (1) are as follows.

The liquid crystal aligning agent of the present invention is applied to one surface of the substrate on which the patterned transparent conductive film is formed by an appropriate coating method such as, for example, a roll coater method, a spin coat method, a printing method, or an inkjet method. Here, the substrate is not particularly limited as long as it is a substrate with high transparency. In addition to a glass substrate and a silicon nitride substrate, a plastic substrate such as an acrylic substrate or polycarbonate substrate can also be used. In addition, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only one side of the substrate, and a light-reflecting material such as aluminum can also be used for the electrode in this case. In addition, when manufacturing an IPS type or FFS type liquid crystal display element, a substrate on which an electrode made of a transparent conductive film or metal film patterned in a patch shape is formed and a counter substrate on which no electrode is formed are used.

Methods for applying a liquid crystal aligning agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, or a spray method. Among them, coating and film forming methods using the inkjet method can be preferably used.

<Step (2): Process of baking the applied liquid crystal aligning agent>

Step (2) is a step of baking the liquid crystal aligning agent applied on the substrate and forming a film. Specific examples of step (2) are as follows.

After applying the liquid crystal aligning agent on the substrate in step (1), the solvent is evaporated by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, or polyamic acid or polyamic acid. Thermal imidization of the ester can be performed. The drying and baking process after apply|coating the liquid crystal aligning agent of this invention can select arbitrary temperature and time, and may be performed multiple times. As a temperature which reduces the solvent of a liquid crystal aligning agent, it can be implemented at 40-180 degreeC, for example. From the viewpoint of shortening the process, it may be carried out at 40 to 150°C. The firing time is not particularly limited, but examples include 1 to 10 minutes or 1 to 5 minutes. When heat imidating a polyamic acid or polyamic acid ester, after the said process, you may add the process of baking in the temperature range of 150-300 degreeC, or 150-250 degreeC, for example. The firing time is not particularly limited, but examples include a firing time of 5 to 40 minutes or 5 to 30 minutes.

Since the reliability of the liquid crystal display element may decrease if the film thickness of the film-like material after baking is too thin, it is preferably 5 to 300 nm and more preferably 10 to 200 nm.

<Step (3): Process of performing orientation treatment on the film obtained in step (2)>

Step (3) is a step of subjecting the film obtained in step (2) to an orientation treatment, as the case may be. That is, in a liquid crystal display element of a horizontal alignment type such as an IPS system or an FFS system, an orientation ability providing process is performed with respect to the coating film. On the other hand, in vertical alignment type liquid crystal display elements, such as VA system or PSA mode, although the formed coating film can be used as a liquid crystal aligning film as it is, you may perform orientation ability provision process with respect to the coating film. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method. In the photo-alignment treatment method, the surface of the membranous material is irradiated with radiation deflected in a certain direction, and in some cases, preferably, a heat treatment is performed at a temperature of 150 to 250 ° C. ) can be given. As radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among these, ultraviolet rays have a wavelength of preferably 100 to 400 nm, and more preferably 200 to 400 nm.

The radiation dose is preferably 1 to 10,000 mJ/cm2. Especially, 100 to 5,000 mJ/cm2 is preferable. Moreover, when irradiating radiation, in order to improve liquid crystal orientation, you may irradiate the board|substrate with the said film-like substance while heating at 50-250 degreeC. The liquid crystal alignment film produced in this way can stably orientate liquid crystal molecules in a certain direction.

Moreover, in the said method, the liquid crystal alignment film irradiated with polarized radiation can be contact-processed using water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-processed.

The solvent used for the contact treatment is not particularly limited as long as it dissolves a decomposition product generated from a membranous substance by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate , diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable, and water, 1-methoxy-2-propanol, or ethyl lactate is more preferable, from the viewpoint of versatility and safety of the solvent. . The number of solvents may be one, or two or more types may be combined.

The temperature of the heat treatment for the coating film irradiated with the radiation is more preferably 50 to 300°C, and still more preferably 120 to 250°C. The heat treatment time is preferably 1 to 30 minutes, respectively.

＜Process (4): Process of manufacturing a liquid crystal cell＞

Two substrates on which the liquid crystal alignment film was formed as described above are prepared, and the liquid crystal is disposed between the two substrates facing each other. Specifically, there are two methods listed below.

The first method first arranges two substrates to face each other across a gap (cell gap) so that each liquid crystal alignment film faces each other. Next, the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealant to bring it into contact with the film surface, and then the injection hole is sealed.

There is no particular limitation on the liquid crystal composition, and various liquid crystal compositions containing at least one type of liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. In addition, hereinafter, a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal, and a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.

The liquid crystal composition may include a fluorine atom, a hydroxyl group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano atom, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, and a cycloalkane. , Cycloalkenes, steroid skeletons, benzene rings, or liquid crystal compounds having a naphthalene ring may be included, and compounds having two or more rigid sites (mesogen skeletons) expressing liquid crystallinity in the molecule (eg, rigid It may also contain a bimesogenic compound in which two biphenyl structures or a terphenyl structure are linked to an alkyl group, etc. The liquid crystal composition may be a liquid crystal composition showing a nematic phase, a liquid crystal composition showing a smectic phase, or a liquid crystal composition showing a cholesteric phase.

Additionally, additives may be further added to the liquid crystal composition from the viewpoint of improving liquid crystal orientation. Such additives include photopolymerizable monomers such as compounds having a polymerizable group described below; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); Antioxidants; UV absorber; pigment; Antifoaming agent; polymerization initiator; Or a polymerization inhibitor, etc. can be mentioned.

Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, or MLC-7081 manufactured by Merck & Co., Ltd.

Negative liquid crystals include, for example, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100 manufactured by Merck & Co., Ltd., or MLC-7029, etc. can be mentioned.

In addition, in PSA mode, MLC-3023 manufactured by Merck & Co., Inc. can be cited as a liquid crystal containing a compound having a polymerizable group.

Additionally, the second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealing agent is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is dropped onto a predetermined number of points on the liquid crystal alignment film surface. Then, the other board|substrate is bonded together so that a liquid crystal aligning film may face, and a liquid crystal composition is pressed and spread|spread on the whole surface of a board|substrate, and it is made to contact a film surface. Next, the sealant is cured by irradiating ultraviolet light to the entire surface of the substrate. In either case, it is preferable to remove the flow alignment during liquid crystal charging by heating to a temperature at which the used liquid crystal composition exhibits an isotropic phase and then slowly cooling to room temperature.

In addition, when rubbing treatment is performed on the coating film, the two substrates are arranged to face each other so that the rubbing direction in each coating film is at a predetermined angle, for example, perpendicular or antiparallel.

As the sealant, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used. Liquid crystals include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable.

The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound that polymerizes with at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device (PSA type liquid crystal display device) manufactured through a step of polymerizing a polymerizable compound by disposing a liquid crystal composition and applying at least one of active energy ray irradiation and heating while applying a voltage between electrodes. do.

Moreover, the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board|substrates provided with electrodes, and the polymeric group which superposes|polymerizes by at least one of an active energy ray and heat between the said pair of board|substrates is formed. It is suitably used also for the liquid crystal display element (SC-PVA mode liquid crystal display element) manufactured through the process of arrange|positioning the containing liquid crystal aligning film and applying a voltage between electrodes.

＜Step (4-2): For PSA type liquid crystal display device＞

The procedure is the same as (4) above except that the liquid crystal composition containing the polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule.

＜Step (4-3): For SC-PVA mode liquid crystal display device＞

After performing the same procedure as in (4) above, a method of manufacturing a liquid crystal display element through a process of irradiating ultraviolet rays described later may be adopted. According to this method, as in the case of manufacturing the PSA type liquid crystal display device above, a liquid crystal display device with excellent response speed can be obtained with a small amount of light irradiation. The compound having a polymerizable group may be a compound having one or more of the polymerizable unsaturated groups in the molecule, and its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all polymer components. It is the mass part. Moreover, the polymer used for a liquid crystal aligning agent may have the said polymerizable group, Examples of such a polymer include the polymer obtained by using the diamine component containing the diamine which has the said photopolymerizable group at the terminal for reaction. there is.

＜Step (4-4): Process of irradiating ultraviolet rays＞

The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above. The voltage applied here can be, for example, direct current or alternating current of 5 to 50 V. Further, as the light to be irradiated, for example, ultraviolet rays and visible rays containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. As the light source for the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The amount of light irradiated is preferably 1,000 to 200,000 J/m2, and more preferably 1,000 to 100,000 J/m2.

And, if necessary, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is stretched and oriented is sandwiched between protective films of cellulose acetate or a polarizing plate made of the H film itself. there is.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, It can be used in various display devices such as various monitors, liquid crystal televisions, and information displays.

Example

Below, the present invention will be described in detail through Examples, etc., but the present invention is not limited to these Examples. In addition, the abbreviations for compounds and solvents are as follows.

(organic solvent)

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: Ethylene glycol monobutyl ether

(diamine)

DA-1 to DA-7: Compounds represented by the following structural formulas (DA-1) to (DA-7), respectively

(tetracarboxylic acid derivative)

CA-1 to CA-3: Compounds represented by the following structural formulas (CA-1) to (CA-3), respectively

(Diisocyanate)

DI-1: 4,4'-diphenylmethane diisocyanate

(Dior)

EG-1: Polyethylene Glycol 400 (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in formula (EG) where R is a hydrogen atom and n is 5 or more)

EG-2: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in formula (EG) where R is a hydrogen atom and n is 5 or more)

EG-3: Ethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in formula (EG) where R is a hydrogen atom and n is 1)

EG-4: Diethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in formula (EG) where R is a hydrogen atom and n is 2)

EG-5: Tetraethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in formula (EG) where R is a hydrogen atom and n is 4)

(End sealant)

Boc ₂ O:2 di-tert-butyl carbonate

(additive)

AD-1 to AD-3: Compounds represented by the following structural formulas (AD-1) to (AD-3), respectively

[Formula 35]

[Formula 36]

[Formula 37]

＜Viscosity＞

In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, a cone rotor TE-1 (1°34', R24), and a temperature of 25°C. did

<Measurement of imidization rate of polyimide>

The imidation rate of the polyimide in the synthesis example was measured as follows. 30 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ϕ5 (manufactured by Kusano Science Co., Ltd.)) and mixed with deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). product) (0.53 mL) was added, and ultrasonic was applied to completely dissolve it. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by Nippon Electronics Datum Co., Ltd.). The imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the integrated peak of the proton derived from the NH group of amidic acid appearing around 9.5 ppm to 10.0 ppm. value was obtained by the following formula.

Imidation rate (%) = (1-α·x/y) × 100

In the above formula, It is the ratio of the number of standard protons to one proton.

[Synthesis of polymer]

(Synthesis Example 1)

DA-1 (8.02 g, 28.0 mmol) and NMP (58.8 g) were weighed and added to a 100 mL eggplant flask equipped with a stirring device and a nitrogen inlet tube, and stirred to dissolve while flowing nitrogen. While stirring this diamine solution under water cooling, CA-1 (5.11 g, 26.0 mmol) and NMP (37.4 g) were added and stirred in a nitrogen atmosphere for 2 hours to obtain a solution of polymer (polymer-1) (viscosity: 182). mPa·s).

(Synthesis Examples 2 to 5)

Solutions of polymers (polymer-2) to (polymer-5) shown in Table 1 below were obtained by carrying out the same procedure as in Synthesis Example 1 except that the diamine and tetracarboxylic acid derivatives shown in Table 1 below were used. In Table 1, the numerical value indicated under the compound name represents the mass of each compound used for synthesis.

(Synthesis Example 6)

DA-2 (6.84 g, 28.0 mmol) and NMP (61.6 g) were weighed and added to a 100 mL eggplant flask equipped with a stirring device and a nitrogen inlet tube, and stirred to dissolve while flowing nitrogen. CA-2 (4.52 g, 20.2 mmol) and NMP (21.7 g) were added while stirring this diamine solution under water cooling, and it stirred at 40 degreeC under nitrogen atmosphere for 2 hours. Additionally, DI-1 (1.40 g, 5.60 mmol) and NMP (10.3 g) were added and stirred at 23°C for 2 hours under a nitrogen atmosphere to obtain a solution of polymer (polymer-6) (viscosity: 242 mPa·s). .

(Synthesis Example 7)

DA-5 (8.04 g, 40.2 mmol), DA-6 (4.36 g, 10.9 mmol), DA-7 (12.2 g, 21.9 mmol) and NMP (98.4 g) was weighed and dissolved by stirring while passing nitrogen. CA-3 (9.40 g, 47.5 mmol) and NMP (37.6 g) were added while stirring this diamine solution under water cooling, and it stirred at 50 degreeC under nitrogen atmosphere for 2 hours. Additionally, CA-1 (4.65 g, 23.7 mmol) and NMP (18.6 g) were added and stirred at 23°C for 2 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PAA-I) (viscosity: 1230 mPa·s) ).

In a 200 mL Erlenmeyer flask containing a stirrer, the solution (100 g) of polyamic acid (PAA-I) obtained above was added, Boc ₂ O (1.24 g, 5.68 mmol) was added, and the mixture was stirred at 40°C for 15 hours. , a solution of end-blocked polyamic acid (PAA-I-1) was obtained.

In a 200 mL Erlenmeyer flask containing a stirrer, aliquot the above solution (PAA-I-1) (100 g), add NMP (66.7 g), acetic anhydride (14.2 g), and pyridine (4.70 g), and stir at room temperature. After stirring for 30 minutes, it was made to react at 60 degreeC for 4 hours. This reaction solution was poured into methanol (650 g), and the obtained precipitate was separated by filtration. After washing this precipitate with methanol, it was dried under reduced pressure at 80°C to obtain polyimide powder (imidation rate: 90%).

Additionally, this polyimide powder (9.60 g) was aliquoted into a 100 mL Erlenmeyer flask containing a stirrer, NMP (70.4 g) was added, and the polyimide (polymer-7) was dissolved by stirring at 70°C for 24 hours. A solution of (viscosity: 76 mPa·s) was obtained.

(Synthesis Example 8)

EG-1 (4.80 g, 12.0 mmol) and NMP (7.20 g) were weighed and added to a 100 mL round-bottomed flask equipped with a stirring device and a nitrogen inlet tube, and stirred to dissolve while flowing nitrogen. While this solution was stirred under water cooling, DI-1 (2.97 g, 11.9 mmol) and NMP (4.50 g) were added, and the solution was stirred for 2 hours under a nitrogen atmosphere. After the reaction, NMP (58.3 g) was added to obtain a polymer (polymer-8) solution (viscosity: 12 mPa·s).

(Synthesis Examples 9 to 12)

Solutions of polymers (polymer-9) to (polymer-12) shown in Table 2 below were obtained by carrying out the same procedure as in Synthesis Example 8, except that the diisocyanate and diol shown in Table 2 below were used. In Table 2, the numerical value indicated under the compound name represents the mass of each compound used for synthesis.

[Preparation of liquid crystal aligning agent]

(Example 1)

Weigh and add the solution (5.83 g) of the polymer (polymer-1) obtained in Synthesis Example 1 and the solution (0.28 g) of the polymer (polymer-7) obtained in Synthesis Example 7 into a 50 mL Erlenmeyer flask containing a stirrer. , NMP (0.59g), GBL (9.30g) and BCS (4.00g) were added, and the liquid crystal aligning agent (1) was obtained by stirring at room temperature for 2 hours.

(Examples 2 to 12, Comparative Examples 1 to 12)

Liquid crystal aligning agents (2) to (24) were obtained by performing the same operation as Example 1 except that the types and amounts of the polymer solution, solvent, and additive to be used were changed as shown in Table 3 below. Among the additives in Table 3, AD-1 to AD-3 were added as NMP solutions each containing 10% by mass. In the case of adding additives (AD-1 to AD-3, EG-1 to EG-2), they were added before adding NMP, GBL and BCS.

[Production of Liquid Crystal Display Element]

A liquid crystal cell having a configuration of a fringe field switching (FFS) mode liquid crystal display element was fabricated.

First, a substrate with electrodes was prepared. As the substrate, a glass substrate having a size of 35 mm x 40 mm and a thickness of 0.7 mm was used. On the substrate, an ITO electrode with a solid pattern constituting the counter electrode is formed as a first layer, and as a second layer, SiN (silicon nitride) formed into a film by CVD (chemical vapor deposition) method is formed on the counter electrode of the first layer. ) film was formed. As the SiN film of the second layer, a film having a thickness of 500 nm that functions as an interlayer insulating film was used. On the SiN film of the second layer, a patch-shaped pixel electrode formed by patterning an ITO film as the third layer is disposed, and two pixels, a first pixel and a second pixel, are formed, and the size of each pixel is 10 vertically. mm and was about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the third layer has a plurality of electrode elements with a width of 3 μm bent at an internal angle of 160° in the center, arranged in parallel at intervals of 6 μm, and one pixel has a plurality of electrodes. It had a first region and a second region with the boundary of the line connecting the bent part of the element.

When comparing the first region and the second region of each pixel, the formation directions of the electrode elements of the pixel electrodes constituting them were different. That is, based on the rubbing direction of the liquid crystal alignment film described later, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise rotation direction) in the first area of the pixel, and the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise rotation direction) in the first area of the pixel. The electrode element was formed to form an angle of -10° (clockwise direction). That is, in the first region and the second region of each pixel, the directions of rotational motion (in-plane switching) of the liquid crystal within the substrate surface caused by application of voltage between the pixel electrode and the opposing electrode are opposite to each other. It was structured so that

Next, the liquid crystal aligning agent obtained above was filtered through a filter with a pore diameter of 1.0 μm, and then an ITO film was formed on the front and back surfaces of the substrate with electrodes (first glass substrate) prepared above, forming a pillar shape with a height of 4 μm. It was applied by spin coating to the surface of a glass substrate with a spacer (second glass substrate). Next, after drying on an 80 degreeC hot plate for 2 minutes, baking was performed for 30 minutes in a 230 degreeC hot air circulation type oven, and the board|substrate with a liquid crystal aligning film with a film thickness of 60 nm was obtained. After rubbing (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm/sec, indentation length: 0.4 mm) the surface of the substrate with the liquid crystal alignment film (YA-20R manufactured by Yoshikawa Chemical Company) with rayon cloth. , cleaning was performed by ultrasonic irradiation in pure water for 1 minute, water droplets were removed by air blowing, and then dried at 80°C for 15 minutes to obtain a substrate with a liquid crystal alignment film. The two obtained substrates with a liquid crystal alignment film were made into one set, and a sealant (XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) was printed in the form of leaving a liquid crystal inlet on the substrate, and the other substrate was placed with the liquid crystal alignment film surfaces facing each other in the rubbing direction. They were matched so that they were antiparallel. After that, heat treatment was performed at 150°C for 60 minutes to cure the sealant, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal MLC-7026 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced-pressure injection method, the injection port was sealed, and an FFS-type liquid crystal display element was obtained. After that, the obtained liquid crystal display element was heated at 120°C for 1 hour, left at 23°C overnight, and then used for evaluation.

[Evaluation of afterimage characteristics by long-term alternating current drive]

With respect to the FFS drive liquid crystal cell produced above, an alternating current voltage of ±5.8 V was applied at a frequency of 60 Hz for 120 hours in a constant temperature environment of 60°C. Then, it was set as the state which shorted between the pixel electrode of a liquid crystal cell and a counter electrode, and it was left to stand at room temperature for one day as it was.

Regarding the liquid crystal cell that performed the above treatment, the deviation between the orientation direction of the liquid crystal in the first region of the pixel and the orientation direction of the liquid crystal in the second region in the state of no voltage application was calculated as an angle Δθ.

Specifically, a liquid crystal cell is installed between two polarizing plates arranged so that the polarization axes are orthogonal, the backlight is turned on, the arrangement angle of the liquid crystal cell is adjusted so that the intensity of transmitted light in the first region of the pixel is minimal, and then The rotation angle (Δθ) required when the liquid crystal cell was rotated so that the intensity of transmitted light in the second region of the pixel was minimized was determined. It can be said that the afterimage characteristic by long-term alternating current drive is better as the value of this rotation angle is smaller. Specifically, when the rotation angle was 0.15 degrees or less, it was evaluated as “○,” when it exceeded 0.15 degrees and was 0.25 degrees or less, it was evaluated as “△,” and when it exceeded 0.25 degrees, it was evaluated as “×.” A result is shown in Table 4.

[Film strength evaluation]

The liquid crystal aligning agent filtered through a filter with a pore diameter of 1.0 µm was applied to the ITO surface of a glass substrate with an ITO electrode on the entire surface by spin coating, and dried on an 80°C hot plate for 2 minutes. Then, baking was performed for 30 minutes in a 230 degreeC hot air circulation type oven, and the board|substrate with a liquid crystal aligning film with a film thickness of 60 nm was obtained. This liquid crystal alignment film was rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm/sec, press length: 0.6 mm). The haze value of this board was measured using an HZ-V3 haze meter manufactured by Suga Test Instruments. It can be said that the smaller the haze value, the less the film is chipped, that is, the higher the film strength is. If the haze value was 0.1 or less, it was evaluated as "○", if it exceeded 0.1 and 0.2 or less, it was evaluated as "△", and if it exceeded 0.2, it was evaluated as "×". The results are shown in Table 4.

[Evaluation of flicker that occurs during operation]

The FFS type liquid crystal display device manufactured above is installed between two polarizers arranged so that the polarization axes are orthogonal, and the backlight (light source: LED, luminous intensity: 20000 cd/㎡) is turned on in a state without voltage being applied, and the transmitted light is transmitted. The arrangement angle of the liquid crystal cell was adjusted so that the luminance was the lowest. Next, the V-T curve (voltage-transmittance curve) was measured while applying an alternating voltage with a frequency of 30 Hz to this liquid crystal cell, and the alternating voltage at which the relative transmittance was 23% was calculated as the driving voltage.

In the measurement of flicker, the backlight that has been turned on is turned off once and left in the dark for 72 hours, then the backlight is turned on again, and at the same time as the backlight starts to turn on, an alternating voltage with a frequency of 30 Hz that causes a relative transmittance of 23% is applied to the liquid crystal cell. was driven for 60 minutes to track the flicker amplitude. The flicker amplitude was read using a data collection/data logger switch unit 34970A (manufactured by Agilent technologies) connected through a photodiode and an I-V conversion amplifier using transmitted light from the backlight that passed through two polarizers and a liquid crystal cell between them. Based on this data, the value calculated using the formula below was taken as the flicker level.

Flicker level (%) = {Flicker amplitude/(2 × z)} × 100

In the above formula, z is the value read by the data acquisition/data logger switch unit 34970A of the luminance when driven with an alternating voltage with a frequency of 30 Hz, which gives a relative transmittance of 23%.

The above-described flicker evaluation was conducted under temperature conditions where the temperature of the liquid crystal cell was 40°C, and the value 30 minutes had elapsed from the start of lighting of the backlight and application of alternating voltage was used as the flicker level (%) ) was made. The results are shown in Table 5.

The smaller the flicker level, the better the flicker characteristics.

By using the liquid crystal aligning agent of the example of the present invention, a liquid crystal display element with good liquid crystal alignment (i.e., excellent AC afterimage characteristics) was obtained.

In addition, since the liquid crystal aligning agent described in the examples of the present invention has good film hardness, it is difficult for the film to be chipped during the rubbing treatment.

Furthermore, the liquid crystal aligning agent to which a crosslinkable compound was added as an additive showed good flicker characteristics.

In addition, the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-004434 filed on January 14, 2021, and the specification of Japanese Patent Application No. 2021-176483 filed on October 28, 2021 , the entire contents of the claims, drawings and abstract are incorporated herein by reference and are hereby incorporated by reference as a disclosure of the specification of the present invention.

Claims (21)

A polymer composition comprising the following components (A) and (B).
(A) Component: At least one type of polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide that is an imidate of the polyimide precursor.
(B) Component: A polyurethane that has a repeating unit represented by the following formula (1) and does not have a repeating unit represented by the following formula (a) and its imidized structure.

(X represents a tetravalent organic group. Y represents a divalent organic group derived from diamine. Two R's each independently represent a hydrogen atom or a monovalent organic group. Two Z's each independently represent a hydrogen atom or represents a monovalent organic group.)

(A ₁ is a divalent organic group derived from diisocyanate. A ₂ is a divalent organic group obtained by removing the hydrogen atom contained in the two hydroxy groups from the organic diol. At least one of A ₁ and A ₂ has the following formula It has a divalent organic group represented by (EG).)

(n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.) According to claim 1,
In the above formula (EG), n is an integer of 5 to 40. The method of claim 1 or 2,
Y in the formula (a) is diamine represented by the following formula (O), diamine having an amide bond or urea bond, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane , 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1, 4-bis(4-aminobenzyl)benzene, diamine represented by the following formula (d _o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and group “-N( A polymer composition which is a divalent organic group derived from a diamine selected from the group consisting of diamines having D)-」(D represents a protecting group that is detached by heating and replaced by a hydrogen atom).

(Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ar may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is a monovalent group. May be substituted. p is an integer of 0 or 1. Q ₂ is -(CH ₂ ) _n - (n is an integer from 2 to 18), or -(CH ₂ ) _n - of -CH ₂ - Indicates a group in which at least part of the group has been replaced with any of -O-, -C(=O)-, or -OC(=O)-.)

(When there are two or more ms, the two or more ms may be the same or different. One or more hydrogen atoms on the benzene ring may be substituted with a monovalent group.) The method according to any one of claims 1 to 3,
A ₁ in the above formula (1) is a diisocyanate (DI EG) having a divalent organic group represented by the above formula ( _EG ), an aromatic diisocyanate other than diisocyanate (DI _EG ), or a diisocyanate other than (DI _EG ). A polymer composition comprising a divalent organic group derived from an aliphatic diisocyanate. According to claim 4,
A polymer composition wherein the diisocyanate (DI EG ) having a divalent organic group represented by the above formula ( _EG ) is a diisocyanate selected from the following.

The method of claim 4 or 5,
Aromatic diisocyanates other than the diisocyanate (DI _EG ) have a diisocyanate structure (O=C=NRN=C=O) in which R does not have a divalent organic group represented by the formula (EG), and It is an aromatic diisocyanate, which is an organic group having 6 to 30 carbon atoms and having at least one benzene ring,
Aliphatic diisocyanates other than the diisocyanate (DI _EG ) have a diisocyanate structure (O=C=NRN=C=O) in which R has an aliphatic group and a divalent organic group represented by the formula (EG), and A polymer composition that is an aliphatic diisocyanate, which is an organic group having 4 to 30 carbon atoms without an aromatic group. The method according to any one of claims 1 to 6,
A polymer composition wherein the organic diol in the formula (1) is a diol containing a divalent organic group represented by the formula (EG). According to claim 7,
A polymer composition in which the diol containing a divalent organic group represented by the formula (EG) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by the formula (EG). The method according to any one of claims 1 to 8,
In (a) above, A polymer composition comprising a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. The method according to any one of claims 1 to 9,
A polymer composition wherein X in the above (a) is a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof represented by formula (t).

(In the formula, X ₁ is a structure selected from the following formulas (X1-1) to (X1-25). * represents a bond.)

(In formulas (X1-1) to (X1-4), R ₁ to R ₂₁ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number 2 Represents an alkynyl group of 1 to 6 carbon atoms, a monovalent organic group of 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * represents a bond.
In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, - COO-, phenylene, sulfonyl group, or amide group. A plurality of A ₂ may be the same or different.) The method according to any one of claims 1 to 10,
A polymer composition in which the polymer (A) further has a repeating unit represented by the following formula (U).

(U ₁ is a divalent organic group, U _1' is a divalent organic group derived from diamine, and C ₁ and C _1' are each independently a hydrogen atom or a monovalent organic group.) The method according to any one of claims 1 to 11,
A polymer composition wherein the polymer (A) is an end-blocked polymer. The method according to any one of claims 1 to 12,
A polymer composition in which the content ratio of the repeating unit represented by the above formula (1) is 10 mol% or more of the total repeating units constituting the polyurethane. The method according to any one of claims 1 to 13,
At least one additive selected from the group consisting of crosslinkable compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant or electrical resistance of the resin film A polymer composition further comprising ingredients. The method according to any one of claims 1 to 14,
A crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an isocyanate group, oxetanyl group, cyclocarbonate group, block isocyanate group, hydroxy group, and alkoxy group, and a crosslinkable compound having a polymerizable unsaturated group A polymer composition further containing at least one crosslinkable compound selected from the group consisting of compound (c-2). According to claim 15,
A polymer composition wherein the crosslinkable compound is a compound represented by any of the following formulas (CL-1) to (CL-12).

A liquid crystal aligning agent comprising the polymer composition according to any one of claims 1 to 16. A resin film obtained by using the polymer composition according to any one of claims 1 to 16. A liquid crystal aligning film formed using the liquid crystal aligning agent according to claim 17. A liquid crystal display element comprising the liquid crystal alignment film according to claim 19. A method for manufacturing a liquid crystal display element, comprising the following steps (1) to (3).
Process (1): A process of applying the liquid crystal aligning agent according to item 17 onto a substrate.
Step (2): A step of baking the applied liquid crystal aligning agent to obtain a film.
Step (3): A step of subjecting the film obtained in step (2) to an orientation treatment.